Richard E. Gillilan and Gregory S. Ezra - Transport and Turnstiles in Multidimensional Hamiltonian Mappings For Unimolecular Fragmentation: Application To Van Der Waals Predissociation

Transport a d turnstiles in multidi ensional Hamiltonian mappings for unimolecular fragmentation: Application to van der Waals predissociation
Richard E. Gillilat?) and Gregory S. Ezrab)

Baker Laboratory, Department of Chemistry, Cornell University, Ithaca, New York 14853
(Received 30 August; accepted 15 November) A four-dimensional symplectic (Hamiltonian) mapping of the type studied by Gaspard and Rice is used to model the predissociationof the van der Waals complex He-I,. Phasespace structure and unimolecular decay in this mapping are analyzed in terms of a generalapproach recently developedby Wiggins. The two-dimensional area preserving map obtained by restricting the 4D map to the T-shapedsubspace studied first. Both the Davis-Gray theory is and the analog of the alternative RRKM theory of Gray, Rice, and Davis for discrete maps are applied to estimate short-time decay rates. A four-state Markov model involving three intramolecular bottlenecks (cantori) is found to give a very accurate description of decay in the 2D map at short to medium times. The simplest version of the statistical Davis-Gray theory, in which only a single intermolecular dividing surface is considered,is then generalized to calculate the fragmentation rate in the full 4D map as the ratio of the volume of a fourdimensional turnstile lobe and a four-dimensional complex region enclosedby a multidimensional separatrix. Good agreementwith exact numerical results is found at short times. The alternative RRKM theory is also applied, and is found to give a level of agreement with the Davis-Gray theory comparableto the 2D case.When the height of the barrier to internal rotation in the van der Waals potential is increased,however, it is found that volumeenclosingturnstile no longer exist in the 4D phasespace,due to the occurrenceof homoclinic tangency.The implications of this finding for transport theories in multimode systemsare briefly discussed.
1. INTRODUCTION
There is continued interest in the possibility of nonstatistical behavior in elementary chemical processes. Much theoretical work has focused on understanding the conditions for applicability of conventional statistical approaches such as transition state theory, RRKM theory,3 and phase spacetheory,4which are widely usedto predict and correlate the rates of chemical reactions. Many researchers have applied the concepts and methods of nonlinear dynamic? to develop a deeperunderstanding of the dynamical origin of nonstatistical behavior of molecules.6 The fundamental picture of phasespacetransport in terms of flux across partial barriers developedby MacKay, Meiss, and Percival,Bensimon and Kadanoff, and Channon and Lebowitz has been particularly useful; such a picture makesrigorous the ofteninvoked concept of bottlenecks in molecular phasespace. It is well establishedthat conventional RRKM theory overestimates classicalvibrational predissociationrate of the weakly bound van der Waals complexessuch as He-I, by at least an order of magnitude. Davis and Gray have however shown that accurate values for the unimolecular decay rate of a two-dimensional classical model of He-I, can be obtained from a statistical theory incorporating transport betweena small number of phasespaceregions bounded by dynamically determined bottlenecks. Multiexponential behavior in rate curves on short to medium time scalescan be successfully modeled, although power law decay typically
Present address: Department of Chemistry, University of California, San Diego, La Jolla, CA 92093. b, Alfred P. Sloan Fellow; Camille and Henry Dreyfus Teacher-Scholar.
found at long times requiresan infinite hierarchy of bottlenecks describing trapping around sticky islands.r3*i4Statistical approachesin which it is assumedthat randomization is rapid within phasespaceregions bounded by partial barriers thereforeretain their utility even when the systemis nonstatistical according to conventional criteria. Other applications of theseideashave beenmade in two-dimensional models for IVR in OCS,Is unimolecular decay of van der Waals complexes,16 isomerization,* and bimolecular reactions.i9,*0 A major outstanding problem is the extension of the methodology outlined aboveto systemswith more than two degreesof freedom. Such an extensionis of course essential for application to realistic models of polyatomic molecules, but there have been few attempts to date. In the so-called alternative RRKM theory of Gray, Rice, and Davis, the i unimolecular decayrate is determinedby Monte Carlo evaluation of the outgoing flux across an approximate phase spacedividing surface.Although reasonablyaccuratevalues for the dissociation rate are obtained in this way for a twomode model of He-I,, results for a three-dimensionalmodel incorporating the van der Waals bending mode were disappointing. Wozny and Gray definedan approximate separatrix for three-dimensional Ne-Cl2 by decomposing the problem into a family of effective two-mode Hamiltonians, and havepresentedevidencethat trajectories are confined by this multidimensional separatrix. Tersigni and Rice have examined the robustnessof cantori in a two-mode system under perturbation due to a third mode, and conclude that the golden mean cantorus remainsa significant bottleneck in the full system.23The possible importance of pairwise frequency incommensurabilities in multidimensional systems
@I 1991 American Institute of Physics 2648 J. Chem. Phys. 94 (4), 15 February 1991 0021-9606/91/042648-21$03.00 Downloaded 03 Jan 2001 to 128.253.229.100. Redistribution subject to AIP copyright, see http://ojps.aip.org/jcpo/jcpcpyrts.html.
FL E. Gillilan and G. S. Ezra: Mappings for unimolecuiar fragmentation
2649
was also emphasizedby Martens, Davis, and Ezraz4 (cf. also Ref. 25). The recent development of a formal theory of phase spacetransport in multidimensional systemsby Wiggins26,27 [reviewed below; for related recent work see also Refs. 28 and 29) provides a firm foundation for extension of the Davis-Gray theory to polyatomic systems.In the present paper we apply Wigginsapproach to a four-dimensional Hamiltonian (that is, symplectic mapping representing the vibra) tional predissociation of the complex He-I, with both the van der Waals stretch and bending modes included (overall rotation is however excluded). Iteration of such mappings is computationally much more efficient than integration of continuous-time trajectories for investigation of phase-space structure. The four-dimensional Hamiltonian map provides a computationally tractable yet reasonablyrealistic example with which to investigate the generalization of the DavisGray approach to unimolecular decay in a multimode system. This paper is organized as follows: In Sec. II we discuss general properties of Hamiltonian maps, and introduce the particular system treated here. Section III contains a discussion of phasespacebasedtheories of unimolecular decay.We first review the approach for two-mode systems developed by Davis and Gray. We then discuss the generalapproach to transport in multidimensional systems due to Wiggins,26 which generalizes the turnstile-based theory of MacKay, Meiss, and Percival to higher dimensional systems. In Sec. IV, after preliminary study of a two-dimensional restriction of the four-dimensional map to the T-shape subspace,we examine the dissociative dynamics of the 4D van der Waals map from the standpoint of Wiggins theory. We compare exact fragmentation rates with those obtained using a simple statistical approach which is the generalization of the DavisGray theory to multidimensional systems, in which only a single, intermolecular bottleneck is taken into account. The alternative RRKM theory is also applied to the 4D map. Interesting topological problems that arise in attempting to define turnstiles in higher dimensions are discussed.Section V concludes with a discussion of some points arising from the calculations of Sec.IV. The Appendix contains details of the algorithms for finding invariant manifolds in the multidimensional case.
II. HAMILTONIAN MAPPINGS FOR MOLECULAR FRAGMENTATION
nian mappings that mimic the behavior of classical models for unimolecular dissociation of van der Waals molecules., They explored the phase space structure of both two- and four-dimensional maps and found behavior in reasonableaccord with previous classical trajectories studies of van der Waals predissociation. Most notably, both 2D and 4D maps were found to exhibit multiply exponential decay on short to medium time scales,indicating the presenceof both inter and intramolecular bottlenecks.3gIn 2D maps, shorttime decay is known to be governed by an intermolecular bottleneck that divides directly scattered trajectories (those with only a single inner radial turning point) from those associatedwith complex formation. Decay on longer time scales in 2D mappings can be modeled quite accurately by kinetic schemesinvoking intramolecular bottlenecks associated with cantori,7 which are the remnants of invariant curves having particularly irrational winding numbers (cf. Sec. IV).4o On very long times scales, there is typically an invariant set of nonzero measure consisting of points in the quasiperiodic region that are bound for all time (in addition to the fractal repellor composed of all bound unstable periodic and aperiodic orbits ) .39Trapping near the sticky boundaries of the quasiperiodic region leads to power law decay of population at very long times. l2 The effects of resonances on the measureof the invariant set in the 2D map were also studied by Gaspart and Rice.3g One major difference betweenthe 2D and 4D casesnoted by Gaspart and Rice was the existence of a quasi-invariant set for the latter; that is, although the invariant set is apparently of zero measurefor the 4D case, there exists a quasi-invariant set of nonzero measure that persists for very long times. Due to the existence of the quasi-invariant set, the decay at long times (presumably governed by Arnold diffusions727~41 not well ) is characterized.3g In the present paper the computational convenienceof Hamiltonian mappings is exploited to investigate in detail the dissociation kinetics and phase spacestructure in a 4D symplectic map modeling the well-studied van der Waals complex He-I,.
A. General properties of Hamiltonian mappings
The use of symplectic (Hamiltonian) mappings in the study of nonlinear classical dynamics has a long history.30-38 Symplectic mappings provide a computationally efficient means of exploring the long-time behavior and the fine details of phase-spacestructure for dynamical systems. The simplest such maps are area-preservingmaps of the plane, which may be thought of as generatedby the PoincarC surface of section for a two degree of freedom autonomous Hamiltonian system or a periodically forced one degreeof freedom system.5 Many of the recent advances in understanding transport in Hamiltonian systems have come from the study of the area-preservingstandard map.7,30v40
There is a close relation betweencontinuous-time trajectory evolution and discrete Hamiltonian (symplectic) mappings. For a continuous-time, autonomous system with N degreesof freedom, the Poincarh surface of section of the (2N - 1)-dimensional constant energy hypersurface in phase space defines a mapping of a (2N - 2)-dimensional slice of the spaceonto itself.s*27A three degreeof freedom continuous-time system can therefore in principle be reduced to a four-dimensional surface of section mapping. Becausethe mapping is the result of Hamiltonian time evolution, it is a member of the special class of symplectic transformations.5.42 Symplectic transformations preserve phasespacevolume (Liouville theorem) as well as a set of s lower-dimensional invariants.5*42 Although the symplectic mapping associatedwith a given continuous-time evolution cannot in generalbe obtained explicitly, a periodically kicked integrable system is an ex-
Recently, Gaspard and Rice3have studied Hamilto-
ceptionalcase.Considera freeparticle moving in onedimen-
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R. E. Gillilan and G. S. Ezra: Mappings for unimolecular fragmentation
sion, periodically kicked by a delta-function potential with Hamiltonian

H=HO f&J?-, + TV(q) nd&*,...Sit-nny (2.1)
(2.7)
where T is the period of the kick and V(q) the potential. The particle momentum is constant betweenkicks. If the coordinatesjust before a kick are (p,q), integrating Hamilton s equations over one interval between kicks determines the coordinates (p ) just before the next kick by the map ,q
p+p =p-TE, aq
qfqrL-q+~.
(2.2)
It is readily verified that this map is area preserving, and symplectic in the multidimensional case.When T = 1 and V= sin 0, Eq. (2.2) is just the familiar standard map.30Tersigni, Gaspard,and Rice havealsostudied the casewhereHo is the Hamiltonian for a Morse oscillator. The relation between Hamiltonian mappings and continuous-time trajectory integration can be further illuminated as follows: Consider the N degreeof freedomcontinuoustime Hamiltonian system (mass m = 1)
Here, ,u is the reduced mass of I,, m is the &-He reduced mass,1is the rotational constant of the I, molecule,s is the I, bond length, Ythe distancefrom the He atom to the I2 center of mass,y the anglebetweenthe diatom axis and the He to I, vector, andp,, p,, andp, the respectiveconjugatemomenta. I is the orbital angular momentum (J - p,, ), withJ the total angular momentum for rotation in the plane. V(s,r,y) is the potential energy. Before converting the continuous-time Hamiltonian Eq. (2.7) into a map, we invoke the classical centrifugal sudden (CCS) approximation;45that is, we take I to be constant. Mulloney and Schatz have found the CCS approximation to be quite accurate for calculation of rotationally inelastic cross sections for He/I, collisions. The CCS approximation is convenient for our purposesas it leadsto an explicit symplectic map. When running trajectories the value of 1is usually taken to be fixed by the initial conditions.45 For simplicitly, we take I = 0 (zero impact parameter), so that the Hamiltonian is
H=&+Pf+&+
2p
2m
21
V((sry)
) *
(2.8)
4
dt =
dp -= dt
--, dV ap
(2.39
2. Sympectic
mapping for He-/2
Newton equations of motion expressedin finite difference s form yield the Verlet algorithm3 for the positions at time t + At in terms of those at times t and t - At: q(t+At)=2q(t)--(t-At) Setting
P(t + I&) N qit +
Now consider the model nonautonomousHamiltonian corresponding to a free particle (He) plus free rotor (I,) described within the zero impact parameter CCS approximation periodically kicked by a potential V( r, y) :
H=&+$+TV(r,y) 2 S(t--nT). n =o, * I.... (2.9)
-At ?.
acl
(2.49
At9 - nit) At
(2.59
Integrating over one period T, we obtain a symplectic map acting in the four-dimensional space (pr,p,,,r,y) :
pr-P:=P,--$:,
and rearranging yields the Hamiltonian form of the Verlet algorithm (the leapfrog algorithm),
p(t+&At) qit+A.t) =p(t-$At) =s(t) -At% [ait (2.69
pr-+p; +Atpit+@t), r4r
=pu - Tz, ay
f zp;, m
rp; I
which is equivalent to the multidimensional version of Eq. (2.2) with Ts At. For small T, the Hamiltonian mapping is thereforea (third-order) symplectic trajectory integrator.44 There are then two interpretations one can give to a particular 2Ndimensional symplectic mapping: first, as the Poincare return map for a periodically driven N degreeof freedom (such a systemis often referred to as an N + 1 degreeof freedom system); second, as an N degreeof freedom symplectic trajectory integrator.44 The first interpretation is usedhere.
B. Hamiltonian map for He+
Y-Y+
mod(2a).
The potential V(r,y) is the full three-dimensionalpotential evaluated with the IZ bond length s fixed at its value at the kick (for example,at equilibrium). A mapping of this type was studied by Gaspard and Rice.39 In addition to the obvious periodicity in the angle y, the phasespace (p,,pY,r,y) is also periodic in the rotor angular momentum p,,, so that the (y,p, 9 subspaceis a 2 torus (cf. the usual standard map3 The period Ap, is given by 9.
TA&, _ 5-, ~ r
1. The Hamiltonian
The classical Hamiltonian for planar He-I, is
where the absenceof a factor of 2 on the right-hand side of Eq. (2.11) is due to the potential V being periodic in y with
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2651 (Sec. II). All quantities
period r, rather than 27r. For T = 8000, the p,, period is 1485.27a.u. By symmetry, the map (2.10) has two-dimensional invariant subspaces corresponding to y = + z-/2 or y = 0, v with P,, = 0. In these invariant subspaces,the four-dimensional map acts as an area-preservingmap in the two-dimensional subspace(r,p, 1:
TABLE I. Parameters for the He-I, Hamiltonian are given in atomic units. W (van der Waals well depth)
B (height of barrier to internal rotation)

r,,,,, (He-1 distance at potential minimum) P (Morse parameter) T (I, vibrational period for u = 0) T (I, vibrational period for u = 10) T (I, vibrational period for u = 20) T (I, vibrational period for u = 30) T (I, vibrational period for u = 40) s (equilibrium I, bond length) m (reduced mass of He-I? system) I (moment of inertia of 12)
p,-tp: =pr - T$,

r-tr+ fPi.
(2.12)
1.62x10-4 8.72X 10-S 7.0 0.6033 10 986 12 485 14717 17 859 31502 5.716 7 069.4 3 782 220.8,
The kicking period Tshould in principle equal the vibrational period of the I, molecule in its initial vibrational state. In practice, we find it necessaryto use T values smaller than the I2 vibrational period in order to obtain dynamics qualitatively similar to the continuous-time case.The reasonis that the free motion between kicks allows the helium atom to penetrate more closely into regions of high potential during one period than it is able to do in the continuous-time system at physically relevant energies.Those He atoms that have penetrated near the repulsive core of the potential subsequently receivevery hard kicks, with the result that the overall dynamics is more chaotic than the corresponding continuous-time system. To the extent that the dissociation dynamics of the driven system Eq. (2.9) are similar to those of the full Hamiltonian (2.7), the resulting 4D symplectic map is a useful tool for the study of van der Waals predissociation. Irrespective of its ability to quantitatively reproduce the results of trajectory calculations, the driven system (2.9 9 provides a computationally tractable way to study the phase spacestructure of three degreeof freedom systems undergoing dissociation.
3. The po ten tia/
are in reasonableagreementwith the sum of pairwise potentials used in continuous-time studies.46*4g potential paThe rameters are related to the well depth ( W) of the potential at the T-shaped minimum, the value of r at the minimum (rmin ), and the internal barrier height B as follows (B,Ww>O):
a= D= B/W 2-(B/WI W(1 -a),
(2.14)
r, = rmin - [ln( 1 - Cr)I//?.
A realistic set of parameter values is given in Table I. For reasonsexplained below, we shall mainly report results for a value of the barrier height B = 4.0 X 10 e--s(au.), which is about half of the physical value. Figure 1 is a contour plot of the model potential V(r,y). The potential profile along y = q/2 is Morse-like in appearance.
HI. TRANSPORT AND UNIMOLECULAR A. Two degrees of freedom DISSOCIATION
We use a simple form of the type proposedby Gaspard and Rice,39 consisting of a Morse-type potential in the r coordinate with a y-dependent repulsive portion:
V(r,y)
Davis and Gray studied a two degreeof freedom model for the vibrational predissociation of He-I,,
==D{[l +a:cos(2y)]e-2- C
-2e-P r-rc)].
(2.13) This potential has the very useful property that the asymptotic (r,p,.) motion (r--t M)) is independentof y. The important parameter Q (O<a: < 1) couples the van der Waals bending ( y) and stretching (r) motions, and determines the barrier height for integral rotation. Potential parametersare chosen so that Eq. (2.13) approximates the more accurate potential function V(s,r,y) given by a sum of Morse pair potentials with s = s, .46 Experimentally, the He-I, complex is preparedwith the Iz subunit in a vibrationally excited state on the B 3110: excited electronic surface.47The vibrational period of the I, is approximately 10 986 atomic units for u = 0 (harmonic frequency; for other u values seeTable I),48 and we study the mapping with T values ranging from 8000 to 12 000. A value T = 8000 results in a phasespaceresembling that of continuous-time studies for u = 20. The potential parameters (D,@, r, ) are chosen so that the equilibrium, position and
y=j
0.0
0.3
0.5 7/n
0.8
1.0
well depth and the height of the barrier to internal rotation
FIG. 1. Contour plot of V(r,y), the model potential energy function for the He+ map.
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0 cd
He-I,(v)+I,(v ) + He, U CU. (3.1) In the conventional RRKM approach, the critical surface dividing reactant from product is defined in configuration space.2,3 The rate for the dissociation reaction (3.1) thus obtained is overestimated by orders of magnitude. The location of the transition state r = 6 is somewhat arbitrary for a processsuch as Eq. (3.1) , in which there is no centrifugal barrier with zero orbital angular momentum 1. The approach of Davis and Gray is based upon the properties of the reactive separatrix, which is a surface in phase space dividing the bound complex region from unbound trajectories. Technically, the separatrix is formed by taking the union ofsegments of the stableand unstable manifolds of a fixed point of the Poincare return map.5 (For HeI,, the relevant fixed point is associated with the periodic orbit at infinity, corresponding to oscillation of I, in the presence of stationary He at infinity,) The separatrix partitions phase spaceinto disjoint regions. To illustrate, consider the motion of an unperturbed one-dimensional oscillator with the potential [cf. Eq. (2.13) J V(P) = V(~,Y)[~=~,~. A phase point undergoing oscillatory motion near the bottom of the potential well traces out a closed invariant curve in the (r,pr) plane. The separatrix, defined here by the zero energy condition
9 m
LO ati
9 :
1
3;o
6.0
9.0 12.0 r (Bohr)
15.0
18.0
FIG. 3. Phase portrait for the 2D van der Waals map in the invariant subspace (pu = 0, y = n/2). Orbits near the center are regular (concentric invariant curves) while those closer to the edge are chaotic. Construction of the separatrix yields a pair of homoclinically oscillating branches [the stable and unstable manifolds W&(&) ] that do not join smoothly.
, H, y=t =g+ ( >
V(r) ==o,
(3.2)
is a smooth curve enclosing all bound trajectories (Fig. 2). The phase portrait for the 2D mapping (2.12), -with y=n-/2,p,=O, T==8000,andB=4~10- stronglyresemblessurface of section plots for T-shaped He-I, (Fig. 3). The separatrix is no longer a smooth curve. Instead, the stable and unstable manifolds of the fixed point at infinity (r = 00,pr = 0), which are the oscillatory curves plotted in Fig. 3, intersect transversely at so-called homoclinic points. The resulting homoclinic oscillations are a manifestation of energy transfer between the I, vibrational mode
and the relative translation of the helium atom. As T-+0, the phase portrait of Fig. 3 becomesidentical to the integrable phase spaceof Fig. 2.39 The separatrix, which is formed by taking the union of segmentsof the stable and unstable manifolds, is a surface of no return. That is, it defines an exact transition state for fragmentation; once a trajectory crossesthe separatrix from the inside to the outside, it cannot return. Phase points cross the separatdx through the turnstile, which is the region of phase space mediating transport across the separatrix. Figure 4 shows the path of a typical phase point crossing the
a@..
/
WsP4
//
' 4.0
7.0
10.0 r (Bohr)
13.0
16.0
10.0
r (Bohr)
15.0
FIG. 2. Phase plane for the van der Waals bond stretch at y = 7r/2. The dashed line marks the separatrix dividing bound orbits from scattering orbits.
FIG. 4. Several homoclinic oscillations of the manifolds W(M) (Fig. 3) are shown together with the turnstile lobes A and B. The complex region is enclosed by solid lines, excluding lobe A, which contains points that enter the complex region upon the next iteration of the map. Lobe B contains points leaving the complex region on the next iteration. Dots mark the primary intersection points (pip of the separatrix branches and dashed lines s) show thecontinuation ofthe branches. Successive iterates ofsingle point are plotted (stars) illustrating energy loss from the van der Waals stretch mode leading to capture.
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separatrix. The turnstile consists of two (in general, an even number) of lobes, eachcontaining points that cross in/out of the complex region on the next iteration of the mapping. Exact region-to-region dynamics .on the surface of section may be formulated in terms of the intersections of pre/post images of lobes (see Refs. 50 and 5 1) . In practice, simple statistical approximations for the unimolecular decay rate are found to be quite accurate. Letp be the probability of escapeper iteration of the map, A (L) the areaof the outgoing lobe on the surface of section, and let ii(S) denote the area of the complex region enclosedby the separatrix, excluding those phasepoints in the invariant set (e.g., trapped forever on invariant tori). The simplest statistical approximation top is then A(L) (3.3) p=r4(s)* This approximation assumesrapid randomization of phase points in the stochastic region 5in a single iteration of the map. The unimolecular decay constant is kuni = -+ln (1 -p)+.
(3.4)
separatricesto systems with more than two degreesof freedom.

B. Generalization to many degrees of freedom
(For a continuous-time system, T is the mean return time for the PoincarCmap.52) It is important to point out that, for a 13 degree of freedom system, A(L) is actually the flux (phase-space volumeper unit time) betweenthe two homoclinic trajectories at the intersection of the boundary segments of the lobe. The constant T converts A (S) into a phasespacevolume. A detailed d.iscussionof this relationship may be found in the Appendix of Ref. 29. The randomization assumption implies the loss of a constant fraction of complexes per iteration of the map, i.e., exponential decay. Such exponential decay is found numerically on short to intermediate time scales,even in the presence of significant regular (quasiperiodic) regions of phase space.l1 Davis and Gray obtained improved results by solving kinetic schemestaking into account intramolecular bottlenecks, associatedwith cantori (seenext section). The intramolecular bottlenecks introduce additional time scalesinto the description of the dissociation kinetics, and phasepoints trapped inside such bottlenecks are responsiblefor slow decay at longer times. Multi.state models incorporating one or two important intramolecular bottlenecks were found to give accurate results for unimolecular decay of He-I,. *I The statistical theory basedon dynamically calculated turnstiles has also been applied to Ar-I,. l6 In the so-called alternative RRKM approach,2flux is calculated across an approximate phasespacedividing surface based on a zeroth-order separatrix. The surface corresponds to the condition that the zeroth-order Hamiltonian for the dissociative mode be zero [see Eq. ( 3.2) ] . The alternative RRKM theory was applied both to T-shaped He-I, and to a three-mode model including the van der Waals bend. Although results are much better than the conventional RRKM approach, significant discrepanciesbetween the theoretical and numerical simulation results still remain, especiaily for the 3D case.It-is therefore important to generalize the Davis-Gray approach using dynamically defined
It is well known that, for systems with N>3 degreesof freedom, N-dimensional invariant tori cannot divide the (2N - 1)-dimensional energy shell into disjoint regions.S,41 This fact, which leads to the possibility of Arnold diffusion in multimode systems,41 appearsto be a seriousimpediment to the developmentof a generaltheory of transport in multidimensional phase spacebased on partial barriers. For example, patching up the holes in the multidimensional analog of a cantoruss in an N degree of freedom system would define an N-dimensional object, which has too small a dimensionality to be a barrier to transport. Several numerical investigations, however, have indicated the presenceof bottlenecks to energy transfer in three-mode systems. Pfeifer and Brickmann, for example, observed long-term confine: ment of trajectories in the chaotic regime of a polynomial potential. s4 Carter and Brumer and Wagner and Davis56 observedslow relaxation in a model for OCS. Martens, Davis, and Ezra subsequentlystudied the dynamics of OCS in the frequency domain, and found evidence for trapping inside resonancechannels and in the vicinity of periodic orbits.24 In addition, certain irrational pairwise frequency ratios, important in the vibrational dynamics of collinear OCS,. appear to be associatedwith trapping in 3D OCS.24 Tersigni, Gaspard, and Rice have also noted the importance of pairwise frequency ratios in the multidimensional dynamics 25 a To facilitate generalization of the Davis-Gray approach, we extract the formal essentialsof the two degreeof freedom continuous-time problem. Our treatment here owes much to the paper of Wiggins26 (cf. also the work of Easton and McGehee ) . The abstract concepts introduced in this subsectionare illustrated for the 4D van der Waals Hamiltonian mapping in the next section. For two degreesof freedom, the phase space is fourdimensional, and the energy shell is three-dimensional. A microcanonical transition-state dividing surface must divide the energy shell into disjoint regions, and so must be twodimensional. Such a surface is said to be codimension one, being of dimension one less than the space in which it is embedded (the energy shell in this case). How may such a surface be obtained in general? Consider an unstable periodic orbit, denoted.&. A periodic orbit is one-dimensional,or codimension two in the energy shell. An unstable (hyperbolic) periodic orbit has twodimensional (codimension one) stable and unstable manifolds W(d), consisting of all points that tend asymptotically to JZ in forward (stable) or reverse (unstable) time. In a nonintegrablesystem, such as a typical molecular Hamiltonian, the two-dimensional stable and unstable manifolds of the periodic orbit intersect transversely (that is, the stable and unstable manifolds do not join smoothly) . The intersection set WS(&>f7 W(J) consists of all points that are asymptotic to 4 in both forward and reverse time, and is therefore composedof homoclinic trajectories.7 Each homoclinic trajectory is 2 + 2 - 3 = 1 dimensional.
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[The stable and unstable manifolds of two distinct periodic orbits J and J? intersect in so-called heteroclinic orbits.) If the continuous-time two degreeof freedom system is reducedto an area preserving map R by examining intersections of trajectories on a particular energy shell with a Poincare surface of section Z;, a period-one (ass,umedwithout loss of generality) periodic orbit & becomesa jixed point JZ, = JnZ of R (provided the periodic orbit intersects X). The manifolds VU(,@) intersect B in one-dimensional sets WF(J) nB. If the stable and unstable manifolds intersect transversely, they must intersect on the surface of section at an infinite number of homoclinic points corresponding to the, successiveintersections of homoclinic trajectories with Z (cf. Fig. 4). It is essentialto note that, in the area preserving case,if the stable and unstable manifolds intersect transversely, then Fig. 4 shows the only possible way (apart from the exceptionalcaseof homoclinic tangency) in which they may do so. As we shall seebelow, the topological possibilities in the multidimensional caseare much richer and far from being fully understood. Segmentsof the stable and unstable manifolds emanating from a fixed point at infinity A; and meeting.at a given (primary ) homoclinic point define the boundary or separatrix enclosing the complex region in phase space. On the full energy shell the corresponding pieces of W and W from the two-dimensional (codimension one) boundary of the three-dimensionalcomplex region. In the caseof van der Waals predissociation, the periodic orbit dm is not hyperbolic but is a marginally stable orbit at infinity (that is, both eigenvalues the linearization of the map about the periodic of orbit at infinity are unity). There is however no essential differenceas far as our present application of the theory is concerned. Consider the separatrix consisting of segmentsof Wg (J) and WS, (&) that intersect at a homoclinic point (which is a so-calledprimary intersection point or pip > as shown in Fig. 4. Iteration under the area-preservingmap R then generatestwo (in general, an even number of). lobes, also shown in Fig. 4. In the two lobe case, there are two distinct homoclinic points at the intersection of the piecesof W and W defining the boundaries of the lobes, corresponding to two distinct homoclinic trajectories in the continuous time system. To generalizethis picture, consider first the continuous time case. In A$3 degree of freedom systems, the natural generalizationof an unstableperiodic orbit is a codimensiontwo normally hyperbolic invariant manifold (NHIM), denoted J.26*27958 N = 3, the manifolds J are 5 - 2 = 3For dimensional invariant manifolds. The property of normal hyperbolicity means that expansion and contraction rates normal to the manifold ,& under the flow linearized about J dominate those tangent to ...&.27An important question in dynamics concerns the persistenceof invariant sets under perturbations. The fundamental theorem on NHIMs ensures that normally hyperbolic invariant manifolds, if they exist in a system, survive arbitrary perturbation (that is, they are srructurally stable) .58 We shall assumethat such objects exist (although finding them may be difficultl). To our
knowledge, there are in fact no algorithms available for the computation of arbitrary NHIMs. In many systems, however, such invariant manifolds may be found by symmetry. An important example is a three-mode system with a saddle, i.e., potential barrier. At the saddle, let there be two stable and one unstable directions, let the potential by symmetric in the unstablecoordinate, q,, and let the kinetic energy be a diagonal quadratic form with constant coefficients. The system then has an NHIM &, which is the symmetry determined invariant subspace:
P = {q, = 0, p, = OIH = El.
(3.5)
,& therefore has the topology of the phase space of a two a degreeof freedom system with energy E. If the Hamiltonian for the (ql = O,p, = 0) subspacecorrespondsto bound motion of two coupled oscillators, ,K is an invariant 3-sphere Y3.28.2vSuch a surfacewill survive arbitrary, nonsymmetric perturbation of theHamiltonian.27s58 According to Wiggins, codimension two NHIMs in N degreeof freedom systems are in general 2N - 3 spheres.16 If the Hamiltonian restricted to .JO is integrable, then Jo consists of a one-parameterfamily of 2 tori. Such an object was recognizedas the appropriate analog of an unstable periodic orbit in higher dimensionsby Pollak and Pechukas5 (cf. also Refs. 60-62). Families of so-called reduceddimensionality tori have recently been postulated as dynamically important componentsof the phasespacein the interpretation of the SEP spectrum of Na3.h3 In the continuous three-modevan der Waals case,there exists an invariant 3D manifold A consisting of all points with r = ~13, z 0. At constant total energy E, this manip, fold is parametrized by the rotor angular momentump,, the rotor orientation y, and the vibrational phase angle 19,.The manifold ..& is not normally hyperbolic, but is marginally stable (just as the periodic orbit at infinity in the two-mode case is not hyperbolic). Nevertheless, the theory carries through in any case. It is natural to conjecture that in multidimensional systems there exist codimension-two NHIMs associatedwith all single resonanceconditions of the form m-o =0, (3.6) where m is an &dimensional vector of integers, not all zero. [This conjecture has recently been proved by S. Wiggins (private communication).] Moreover, it is plausible that thesesurfacesmay be determined by a variational principle, by analogy with periodic orbits in two degree of freedom systems. A further consequence normal hyperbolicity is that of NHIMs ,# have stable and unstable manifolds that are themselvesstructurally stable. Let the stable (unstable) * manifolds of&? be denoted W(A ); Ws( (.A consist ) of all points that tend asymptotically to ..&in forward (stable) or reverse (unstable) time. These manifolds are codimension one, that is, they are of dimension one less than the energyshe11.26 example, in the caseof a three-modesysFor tem with a potential barrier, the stable and unstable manifolds ofJo are 4D manifolds with topology y3 X R I. These
2655
manifolds have beencalled cylinder man$olds by Ozorio de Almeida et a1.64 The three-dimensional invariant manifold at infinity .J in the three-mode van der Waals system, although not normally hyperbolic, neverthelesshas four-dimensional stable and unstable manifolds consisting of all points for which pI -+O as Y-, 00 in forward or reverse time. Computation of points on the stable and unstable manifolds is discussedin the next section, In multimode systems, the stable and unstable manifolds of a particular NHIM & may enclosea region of phase spacein a way analogousto that for two degreesof freedom. That is, segments of WS(A) and W (A) may form a boundary such that any point entering or leaving the enclosed region must do so by entering the multidimensional analog of a turnstile. For two degreesof freedom, if the stable and unstable manifolds intersect transversely, then they must enclosea region of phasespacein the above-mentioned sense.This is not necessarily the casefor multidimensional systems, however, as seenbelow. Successive intersections of trajectories on the energy shell in N degree of freedom autonomous systems with a surface of section Z generatea (2N - 2) -dimensional symplectic mapping. For N= 3 the surface of section is four dimensional, and the four-dimensional symplectic map introduced in the previous section is a very convenient substitute for the computationally intensive calculation of the surfaces of section for a three-mode system. The intersection of codimension-two NHIMs & with S is, in general, a (2N - 4) -dimensional invariant manifold &ZZ. The stable and unstable manifolds WS(A) intersect I: in (2N-- 3)dimensional sets WY(l) = W(l) nx. These have dimension one less than the (2iV- 2)-dimension surface of section, and so may serve as components of the boundary betweenregions of phasespacedefined in the surface of section. For N = 3, then, JZ is 2D with 3D stable and unstable manifolds WY(A). WS, and Wg will in general intersect transversely. In the multidimensional case, the analog of the homoclinic point in the surface of section is a (2N - 3) + (XV-- 3) - (2N- 2) * (2N-- 4)-dimensional transverse homoclinic manifold. 26 The analog of a primary intersection manifold is 2D, and consists of a two-parameter family of points biasymptotic to & By straightforward . generalization of the two degreeof freedom case,one might anticipate the existenceof two distinct two-dimensional primary intersection manifolds, corresponding to the pair of distinct primary homoclinic points. The primary intersection manifolds, each consisting of points that map asymptotically in both forward and reverse time onto AX, are moreover expectedto be continuously deformable into (hoThis expectation is confirmed for certain motopic to) -4, .26 parameter regimesin the 4.D van der Waals map as discussed in the next section. For other parameter regimes, however, the intersection manifold doesnot have such a simple structure. In the casethat there are two distinct primary intersection manifolds homotopic to JZ, the definitions of lobes and turnstiles can be carried over directly to describetrans-
port in the multidimensional case. That is, segments of W (AT)~ and W(A). meeting at a primary intersection manifold enclose the complex region of phase space. Iteration of the map leadsto the formation of two or more lobes comprising the turnstile. Each lobe is bounded by segments of W(V&)z and W(k)= meeting at transverse homoclinic manifolds. Phase points enter or leave the complex region only by mapping into the appropriate lobe. If the volumes of the escapinglobe, the complex region and the invariant set can be calculated, a simple statistical estimate of the escaperate can be made following Davis and Gray (seenext section). Ifthesegmentsof WS(.M)x and W (A), do not enclose a region of phase space, however, it is not obvious how to develop a turnstile-based theory of transport.
IV. PHASE SPACE STRUCTURE AND DYNAMICS OF THE VAN DER WAALS MAP
In this section we study the phase spacestructure and unimolecular fragmentation dynamics of the 4D symplectic map for the van der Waals molecule He-I, describedin Sec. II. We first consider the dissociation of points confined to the 2D invariant subspacepy = 0, y = r/2. We apply the statistical theory of Davis and Gray* to this case,and show that, for physically relevant parameter values, a multistate model basedon one intermolecular bottleneck (the separatrix) and a small number of intramolecular bottlenecks (defined by periodic orbit approximants to cantori ) gives an accurate description of the decaykinetics at short to medium times. The analog of the alternative RRKM theory for !. discrete maps is also applied, and found to give reasonably accurate predictions for short-time decay rates. We then turn to the 4D map. The general concepts introduced in the previous section are illustrated by application to the particular caseof the 4D van der Waals map for He-I,. A method for computation of points on invariant manifolds in the 4D phase space is discussed (cf. also the Appendix), and sections through the multidimensional manifolds examined to confirm the existence of higher dimensional analogs of turnstiles. The generalized DavisGray statistical theory for unimolecular decay is then applied. A kinetic schemeincorporating a single intermolecular bottleneck (reactive separatrix) is used to predict the short-time decay rate, and compared with both numerical simulation results and the alternative RRKM theory for maps. The existence of multidimensional turnstiles is central to the extension of the MacKay, Meiss, and Percival theory of phase space transport to systems with many degreesof freedom proposed by Wiggins26 and applied in the present paper to the 4D van der Waals map. An important observation made here is that turnstiles may fail to form in the 4D van der Waals map, even in physically relevant parameter regimes. The reasonsfor this failure (which was predicted by Wiggins and also noted by us in a study for coupled standard maps) and its implications for generalization of the Gray-Davis theory to multimode molecules are briefly discussed.
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2656
A. Two-dimensional
mapping
Consider the invariant subspace of the 4D van der Waals mapping defined by the condition p,, = 0, y = n-/2. The 2D map obtained by the action of the full 4D map in this invariant subspacedescribes a periodically kicked van der Waals stretch mode [cf. Eq. (2.12) ] in the T-shapedconfiguration (bending angle fixed at y = r/2).
I. Fragmentation dynamics
A phaseportrait for the 2D map with T = 8000 is shown in Fig. 3. To study dissociation rates, ensemblesof initial conditions (r,p, ) were chosenin three different ways. First, a quasiclassicaldistribution6 corresponding to the ground vibrational state of the I,-He van der Waals bond was used, where the harmonic approximation was made for the bond potential V(r,y = r/2). The resulting ensemble of points lies completely within the reactive separatrix dividing surface. Second,a Wigner distribution66 corresponding to the ground vibrational wave function for the van der Waals bond was used,again making a harmonic approximation for the potential. The Wigner function for the harmonic oscillator ground state is a Gaussian distribution in both P and pr, and there is therefore a small probability that points in the initial ensemblelie outside the reactive separatrix. Third, a uniform distribution of (r,p, ) points was chosen,subject to the constraint that H,(r,p,) be less than - e, where e/W= 0.37. The constraint ensures that no points in the ensembleare initially outside the separatrix. Each ensemble contains at least 1000 points, up to a maximum of 20 000 points for those values of T for which decay is most rapid. A trajectory is defined to have dissociated if r > 20 a.u. and the van der Waals bond energyH, ( y = r/2) is greater than zero. The lifetime is then the time (number of iterations times T) up to the last inner turning point before dissociation, i.e., the point at which the final change of sign of p, occurs. Let N(0) be the number ofpoints in the ensemble,let N(n) be the number of points remaining undissociatedafter 12 iterations, and let N( nJ) be the number of points remaining after a large number of iterations nf (corresponding to the fixed time T, = lo7 a.u.). The ratio N(n/)/N(O) is approximately the fraction of the initial ensemblein the invariant set; N( n/> is nonzero when the phasespaceconsists of a typical mix of chaotic and quasiperiodic regions, in which case the invariant set is of nonzero measure. Decay curves plotting are obtained by IdiN -N(q) J/ [N(O) - N( nf) ] >, and are linear for simple exponential decay. Figure 5 shows decay curves for two of the three different ensemblesof initial conditions (results for the Wigner ensembleare similar to those for the constrained uniform ensemble,and are not shown) for four T values. At short times (up to about 150 iterations, ignoring initial transients), the decay curves are linear and can be fit to yield short time decay rate constants. Our results show a pronouncedensembledependence the short-time decay rate. of The quasiclassicalensembledecay is markedly slower than either the uniform or Wigner ensembles all T values,and for is on a time scale characteristic of the longer time decay of
' 0.0
1.5 t (x IO'
3.0 am.)
4.5
6.0
0.0
123 t (x 10'
3.0 au.)
4.5
6.0
FIG. 5.Population decay curves for the uniform ensemble (solid line), the quasiclassical ensemble (dotted line), and the Davis-Gray predictioh for short-time decay rate (dashed line) in the 2D submap. The function fit) =In{[N(n) --N(n,-)]/[N(O) -N(q)]). (a) T=9000. (b) T= 10000. (c) T= 11000. (d) TS 12000.
the other two ensembles.The short-time decay rate for the Wigner ensembleis consistently lower than that for the uniform ensemble.The GaussianWigner distribution is peaked at the origin Y = r,,,, pr = 0, so that the majority of phase points are concentrated close to the central quasiperiodic region and associatedsticky boundary. 14r3 longer times, At decay in the uniform and Wigner ensemblesappearsbi- or multiexponential, as noted by Gaspard and Rice. (At very long times systemswith mixed phasespacestructure typically exhibit power law decay. )
2. Phase space structure and unimoiecular decay
As discussedin Sec.II, the simplest version of the statistical theory of Davis and Gray for the unimolecular decay rate gives N(n) - N(n,) = (1 -p)[N(O) - N(nf)], (4.1) wherep is the probability of escapeper iteration of the map, and is the ratio of the area of the turnstile lobe [A(L) ] to the areaof the complex region minus the area of the invariant set [A (S) 1. The separatrix and associatedlobe for T = 8000 are shown in Fig. 3. Points (r,p,> on the stable and unstable manifolds of the fixed point at infinity (Am) are obtained by noting that, for r--t CO, they satisfy i*39 pr = f 2(m&-~-~) /2 (4.2) Points seeded this fashion are iterated backwards (p, > 0) in or forwards (p, ~0) in time to form the stable or unstable manifolds, respectively.3gThe areasof the lobe and the complex region are found by numerical quadrature. The short-time decay curves corresponding to the Davis-Gray prediction are plotted in Fig. 5. The plots show that the short-time decay rates for the constrained uniform ensembleare predicted quite accurately by a statistical theory with a single intermolecular bottleneck. Numerically determined short-time decay rates are compared with those of the statistical theory in Table II. The overall level of agreement betweenthe simplest Davis-Gray theory for the short-
R.E. Gillilan and G. S. Ezra: Mappingsforunimolecularfragmentation
2657
TABLE II. Predissociation in two-dimensional van der Waals map, Eq.

(2.12).
T 8oQo
9ooo
P
0.0946 0.0621
Pob
0.0286 0.0435 0.0748 0.0657 0.1059
PwC
0.0255 0.0380 0.0653 0.0529 0.0912
Pa/
0.0032 0.0168 0.0416 0.0485 0.0695
Pm
0.0384 0.0572 0.0681 0.0815 0.0989
P;
0.1439 0.1619 0.1807 0.1943 0.2173
10000
11cQO 12000
0.0445
0.0022 0.0183
Fraction of complex region occupied by invariant set, estimated from the fraction of trajectories in the uniform ensemble undissociated after T, - 10 atomic units. bShort-time escape probability per iteration for constrained uniform ensemble with H,< - 6.0X 10w5. Short-time escape probability per iteration for ground state harmonic Wigner ensemble. dShort-time escape probability per iteration for ground state quasiclassical ensemble. Probability of escape per iteration calculated using Davis-Gray statistical theory with a single (intermolecular) bottleneck. Probability of escape per iteration calculated using alternative RRKM theory for discrete maps.
' 4.0
7.0
10.0 r (Bohr)
13.0
16.0
FIG. 6. Zero-order separatrix for the 2D van der Waals map (solid line), together with its iterate under the map (dashed line).
time decay rate and the numerical results for the uniform and Wigner ensembles good. As noted above,decay rates is for the quasiclassical ensemble are markedly lower than those for either the uniform or Wigner ensembles.For all values of T, a significant fraction of points in the quasiclassical ensemblecorresponding to the van der Waals stretch ground state is located either in the central invariant region or close to the boundary of the quasiperiodic region. Decay of the quasiclassicalensembleis therefore governed by the flux through intra- rather than intermolecular bottlenecks (seebelow). There is a noticeablediscrepancybetweenthe numerical and statistical values of the short-time decay rate for the uniform ensembleat T = :l 1000. The reasonfor this apparent anomaly is discussedin more detail below. Whereas good agreementbetweenthe Davis-Gray statistical theory and numerical simulation is obtained using a dynamically determined separatrix and turnstile, it is also of interest to apply the analog of the alternative RRKM approach of Gray, Rice, and Davis to dissociation in the 2D map, where transport through an approximate separatrix is used to define the rate. The zero-order separatrix is defined by the condition H, (r,p,) = Cl(cf. Ref. 2 1), and the resulting phase curve is shown in Fig. 6. To determine the transport through the approximate separatrix per iteration of the map, the zero-energycurve is iterated once (Fig. 6). Since the zero-order separatrix is not an invariant curve, its iterate intersects the original curve at isolated points, producing a set of five lobes containing points that cross in or out of the approximate separatrix. The outward flux of phasepoints is then given by the total area of the two lobes that lie outside the zero-energy curve (as the map is area preserving, the outgoing area is equal to the in-going area, leading to zero net flux). Note that the outward flux through the approximate separatrix is not localized in a single lobe as it is for the dynamically determined separatrix. In the alternative
RRKM theory it is assumedthat all points passingout of the approximate separatrix proceed to dissociate without recrossing the intermolecular dividing surface, so that the probability of escapeper iteration is
PO=-, A IO\
AOW)
A,(L)
where A,(L) and A,(S) are analogous to the quantities A (L) and A (S), but are defined for the zero-order separatrix. We have calculatedA,(L) and A,(S) for a number of T values, and the resulting values of p. are shown in Table II. Agreement with the numerical results and the Davis-Gray statistical theory is reasonable,within a factor of 2-5. The ratios of the alternative RRKM and Davis-Gray statistical escapeprobabilities as a function of Tare plotted in Fig. 7. We now return to the discrepancy betweenthe statistical short-time rate and the numerical dissociation rate noted
10 4 0 4
8000
9000
10000 T (a.u.)
11000
12000
FIG. 7. Ratio of alternative RRKM rate to the Davis-Gray rate for both the 2D map (circles) and the full 4D map (triangles) as.a function of T. The dependence of the ratio on Tis similar in both cases, although the alterna-
tive RRKM result is consistently higher for the 4D mapping.
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2658
above for the case T = 11 000. Consider the stability of the central fixed point of Eq. (2.12), Y = rmi,,, p, = 0. Diagonalization of the Jacobian of the mapping Eq. (2.12) at the central fixed point yields a pair of eigenvaluesthat determine the linear stability character of the tied point. For T< 15 000, the eigenvalueslie on the unit circle in the complex plane, indicating that the fixed point is stable. Very close to T = 11 000, the eigenvaluespass through f i, which is just the condition for a 4:1 resonance.39As noted by Gaspard and Rice,39the area of the invariant (quasiperiodic) region decreases markedly at resonance.At T = 12 000, the system is no longer resonant, the area of the invariant region increases and the short-time rate decay rate increases. Although there is a significant decreasein the area of the quasiperiodic region at resonance, leading to a larger denominator in the rate expression of Eq. (3.3), the statistical rates do not show a dip at T = 11 000. The slow decay rate at T = 11 000 is most likely due to the influence of intramolecular bottlenecks responsible for trapping of phase points in the vicinity of the 4:1 resonance; further study of the effect of resonanceson the decay rate is in progress.6s To describe the decay at longer times, it is necessaryto develop a kinetic model including intramolecular bottlenecks. Following Davis and Gray, we associatethe intramolecular bottlenecks with cantori 7*40corresponding to particular irrational winding numbers (essentially the ratio of the van der Waals bond vibration frequency to that of the I2 bond). Recall that invariant curves of area-preserving maps are smooth and continuous only up to a certain value of the strength of the nonintegrable perturbation (which is is general different for each invariant curve), after which they break up, becoming invariant cantor sets (cantori) with an infinite number of holes.40 Nevertheless, as found by MacKay, Meiss, and Percival,7 the cantori, although no longer able to act as absolute barriers to transport, may continue to restrict the flow of phase points and so act as partial barriers. It is found empirically that cantori corresponding to certain special frequency ratios are the most effective partial barriers (that is, correspond to local minima of the flux) .7 These so-called nobZefrequency ratios are irrational numbers that are the most poorly approximated by rationals,7having continued fraction expansions 1 = [ al,a,,a3,...,a,,l,1,1,...,j, (4.4) 1 aI + 1 a2 + ~ a3 + -.* terminating in an infinite sequenceof 1 The cantorus cors. responding to a given irrational winding number may be approximated by a sequence of periodic orbits with rational winding numbers (p/q) obtained by truncation of the continued fraction expansion at successively higher levels.7 There are in general two periodic orbits associated with a given rational winding number; one is hyperbolic (unstable), while the other is either elliptic (stable) or hyperbolic with reflection (unstable). 4o In practice it is useful to define the partial barrier by taking the union of segments of the stable and unstable manifolds of the hyperbolic points; the flux across this barrier is given by the area of the associated
LO ati
9 7
9 C-J
4.0
7.0
10.0
r (Bohr)
13.0
16.0
FIG. 8. Inter- and intramolecular partial barriers actually used in the rate calculation discussed in Sec. IV. The innermost ring is (approximately) the Iast KAM torus bounding the quasiperiodic region. Only the two most important catori are plotted: [6,2,1,1,1,.,. 1 and [7,1,1,1,... 1. Trapping in the tiny region between the last KAM torus and the cantorns [6,2,1,1,1,...] mainly determines the decay rate at long times.
turnstile lobe (alternatively, the flux is given by the differencein actions of the two orbits homoclinic to the associated unstable periodic orbit with the given rational winding number.7Z52Partial barriers defined in this way enclose regions ) of phase space,as shown in Fig. 8, and the statistical probability of passing from region i to regionj in one iteration of the map is then
A ( L,J > PCi=A(S,)y
(4.5)
where A (L, ) is the area of the lobe L, mediating transport from region i to regionj,50 and A (Si ) is the phase volume (excluding the invariant set) of region i. As shown by Davis and Davis and Gray, such ifitramolecular bottlenecks may be used to make accurate statistical models of IVR and unimolecular decay. A model consisting of a reactive separatrix together with several concentric partial barriers associatedwith periodic orbit approximants to cantori is used to model dissociation in the 2D van der Waals map for T = 8000. The phase space structures are shown in Fig. 8. We assume that the measure of quasiperiodic phase spacelying outside the central region is negligible. Let N, (n) be the number of phase points in regionjafter n iterations ofthe map, wherej = l,...,M labels the region. In the statistical (Markov) model for transport the populations evolve under the difference equations: Nib2 + 1)
=N ,Cn) +Pi-l,iNi-l(n) I,i -(pg+1 +Pj.~-1)fVf(fZ)
+ Pi+
N,
1 (n>,
2>i>M-p,,2N[(n), ,,,N,-
1,
* (n)
N,(n + 1) =N,(n)
N w(n + 1) =N&f(n)
+p,lN,(n)
+p,-
(4.6)
R. E. Gillilan and G. S. Ezra: Mappings for unImolecular fragmentation
2659
where pdisf is the statistical probability of dissociation per iteration from the outermost region M. Numerical solution of this set of discrete evolution equations yields the population of bound complexes: Ne(n) = 2 iVi(n>,
i- 1 (4.7)
6. Four-dimensional 1. Fragmentation
mapping dynamics
as a function of iteration number n. [We have verified that integration of the set of coupled differential equationscorresponding to the continuous time version of Eq. (4.6) gives an essentially identical decay curve.] In the 2D He-II mapping with T = 8000we have identified three cantori that are important in the decay kinetics. A cantorus with frequency ratio [ 7,1,1,1... ] z 3/23 governsdecay at intermediate times, while those with frequencies [6,2,1,1,1,...]~55/32 and [6,1,1,1,...]=:8/53 influence behavior on longer time scales. Two of these bottlenecks are superimposed in Fig. 8. The decay curves shown in Fig. 9 shows the excellent quality of the fit obtained for the resulting four-region model for the constrained uniform ensemble with T = 8000. In general the phase space of a nonintegrable system contains an infinite number of cantorLm As more and more cantori are included in a kinetic model of the type described above, the underlying assumption of randomization within regions betweenuncorrelated barrier crossings becomesless and less useful. The model moreover ignores the influence of partial barriers leading to trapping around the infinite hierarchy of island chains.I3 Our results and those of others1 5, show, however, that simple models involving a * 7 small number of cantori can give a reasonably accurate description of the decay kinetics for short to intermediate times. We note that in the context of unimolecular decay very long time scales are of limited physical interest due to quantum effects and the influence of external perturbations.
To study the fragmentation dynamics of the 4D van der Waals map, we select initial conditions at random from a quasiclassical ensemble@j corresponding to the ground vibrational state of both the van der Waals stretching and bending modes.A harmonic approximation is made for each mode. Within the harmonic approximation, and using the physical value of the barrier height B = 8.72X lo- the , ground state energy is calculated to be - 20.65 cm- with respect to infinitely separated He and I,, as compared to - 20.63 cm - for the theoretical ground state calculated for the full pairwise potential.46With B = 4 X 10- the cal, culated ground state energy in the harmonic approximation is - 21.16 cm - . We also use an ensembleof initial conditions uniformly distributed in (r,p,.,y,p,,), subject to the constraint H, (r,p,;y) < - E. We consider the potential with barrier height B = 4x 10- 5 a.u. As for the 2D case,trajectories are definedto have dissociated whenever r > 20 a.u. and H, (r;p, ) > 0 [recall that the potential V( r,y) becomesindependentas yas Y--P 1. Decay ry-) curves for the quasiclassical and uniform ensemble are shown in Fig. 10 for four values of T. The curves display the characteristic biexponential behavior found abovein the 2D map (also noted by Gaspard and Rice3). Short-time decay rates extracted from decay curves for a number of T values are given in Table III.
2. Multidimensional phase space structure
In order to apply the Davis-Gray theory to the shorttime decay in the 4D map, it is first necessaryto compute the stable and unstable manifolds W(d) of the invariant manifold at infinity, .JYm. The manifolds Ws~U(ut ) are of dm codimension one hi the 4D phase space, so that points on them may in principle be found by a one-dimensionalsearch. To visualize the manifolds W(dm ), which are 3D
0.0
Time
2.0
(atomic
4.0
units) (x
6.0
109
FIG. 10. Population decay curves for the uniform ensemble (solid line), the quasiclassical ensemble (dotted line), and the Davis-Gray prediction for short-time decay rate (dashed line) in the full 4D map. (a) T= 9COO.(b) T= 10 000. (c) T= 11000. (d) T= 12 000.
FIG. 9. Decay curve for the uniform ensemble (solid line) in the 2D van der Waals map at T= 8000 compared with the four-state Markov model
(dashed line).
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2660
TABLE III. Predissociation in four-dimensional van der Waals map, Eq. (2.10).
T
8 000 9Mx) 10 000 11000 12 000
f
0.0758 0.0465 0.0253 0.0069 0.0054
P(W
29 452 26 691 24 283 22 262 20 252
,u(LY
970.2 1207.8 1419.8 1599.6 1749.3
fd%*
34 460 30 626 27 567 25061 22 973
P(L)"=
4330.8 4381.6 4481.6 4534.4 4579.1
PoC
0.0245 0.037 6 0.0538 0.0715 0.0984
PQCS
0.0045 0.0179 0.0418 0.0483 0.0694
POG
Poi
0.128 0.145 0.164 0.181 0.200 .-
0.0310 0.0436 0.0574 0.0715 0.0860
Fraction of complex region occupied by quasi-invariant set, estimated from the fraction of trajectories in the uniform ensemble undissociated after T, = 10atomic units. h Volume of complex region enclosed by dynamical defined separatrix minus volume of quasi-invariant set. Volume of lobe. Volume of complex region enclosed by zeroth-order separatrix. Phase volume passing out of zeroth-order separatrix per iteration of map. Short-time probability of escape per iteration for constrained uniform ensemble. *Short-time escape probability per iteration for ground state quasiclassical ensemble. h Probability of escape per iteration = A(L)/A(S), Davis-Gray theory. Probability of escape per iteration = A(L),/A(S),, alternative RRKM theory.
objects embeddedin a 4D space,we examine a seriesof 2D sections through the phasespace,defined by fixing the values of the variables ( y,pu ). The problem is then to find points (#,pf) at fixed (/itpk) that lie on V(J>, i.e., that satisfy
(4.8) Hi- [R (dpt,Yi,p:)] -,O as 12 CO(stable) or II -) - OD(unstable), where R n repre--+ sentsn-fold iteration of the initial point under the symplectic map. Details of the algorithm used to find such points are given in the Appendix. Points on the homoclinic intersection manifold must satisfy the condition Eq. (4.8) for n -, CO and n-t - ~0,~~ and so must be found by a 2D search at fixed ( y,pr 1 (cf. Appendix 1. A series of 2D (r,~, ) sections through the 4D phase spacefor T = 8000 is shown in Fig. Il. Recall that the phase
FIG. 11. Series of 2D (r,p,) sections of the 3D manifolds W~(.,N~) embedded in 4D phase space for T = 8000 and B = 4~ 10 - 5. The numbers in parentheses give the (y,py) values of the particular sections in units of (7r/2,771/7 It can be seen that the manifolds Wc(,H*) ). enclose a 4D complex region.
space is doubly periodic, of period v in y and period Apv = n-I/T in p,,. The intersection of the manifolds W(.M ) with eachsection is in general one-dimensional. In the uncoupled case (LX= 0, no barrier to internal rotation), Fig. 11 would consist of a set of 2D sections, each identical with Fig. 4. The 4D complex region and turnstile would then be direct products of the corresponding objects for the 2D map with the two-dimensional ( y,p,,) space.The 2D sections of Fig. 11 show the influence of coupling betweenthe van der Waals stretch and bending modes (nonzero CL, = 4 X 10- ) on this zero-order picture. It is apparB ent that for these parameter values the structure of the 4D complex region and associated turnstile formed by W(J m) is topologically identical with the uncoupled case.The 30 stable and unstable manifolds W(J) intersect so as to enclosethe complex region precisely as in the uncoupled case, and each of the 2D sections in Fig. 11 is deformable onto the 2D picture of Fig. 4. As discussedin Sec. III, a straightforward generalization of the pair of distinct primary homoclinic points of Fig. 4 to a multidimensional system is a pair of disjoint two-dimensional homoclinic intersection manifolds. The segments of the manifolds wS(dLQ) and W(,k) shown in Fig. 11 intersect at two points in each of the 2D sections; each of these points is asymptotic in forward and reversetime to drn, and one point of every pair lies on eachof the distinct intersection manifolds. Projections of these homoclinic intersection manifolds onto the (pr,pr ) plane are shown in Fig. 12. Each intersection manifold is continuously deformable onto the invariant manifold LB (a 2 torus).26 It is important to note that the 2D slices shown in Fig. 11 are not invariant planes, as both y and pv will generally changeunder the mapping. Although a point starting inside the separatrix on a particular ( ) plane must eventually y,pI enter an outgoing lobe in order to dissociate,it will in general do so for values of ( y,pu ) different from the initial values. It also follows that the incoming and outgoing lobes on a particular ( y,p, ) plane need not have the same area; it is only necessarythat the areasintegrated over ( y,py ) be the same.
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2661
03 d a o! 0 -+ d I
gLd
0
300 600
p7 FIG. 12. projection of the two disjoint homoclinic intersection manifolds onto the (p,,~?,) plane at T= 8000 and B = 4 x 10 - 5. Points of closest approach of two projections correspond to (y,p,,) values where the turnstile lobes are smallest [cf. Fig. 11 at (i/5,3/5) 1.
900
1200
1500
3. Statistical
theory for short-time
decay rate
In Sec. IV A, the Davis-Gray statistical theory for the short-time decayrate in the 2D map was calculated as a ratio of phasespaceareas (divided by the kicking period T) . Having establishedthat the multidimensional turnstile exists in the4DvanderWaalsmapforB=4x10-5, T=800012 000 a.u., the natural generalization of the statistical expressionto the 4D caseis simply a ratio of the four-dimensional phase space volumes of the outgoing lobe and the complex region minus the invariant set
(4.9)
may be used to find the areas inside the separatrix and the turnstile lobe. A 25 x 21 grid on the (y,pr) plane covering the ranges [0,7r/2] x [O,lrr/T] is then used in a double Simpson integration to obtain the 4D volumes.68The res sulting volumes and rates are given in Table III, and the decay curves predicted by the Davis-Gray theory are included in Fig. 10. Table III shows that the statistical rates basedon a single intermolecular bottleneck are overall in very good agreement with short-time decay rates extracted from decay curves for the constrained uniform ensemble.As in the 2D map, the decay rates for the quasiclassicalensembleare considerably smaller than either the uniform ensembleor statistical theory values. There is however no anomalous dip in the rate at T = 11 000, and all rates increasemonotonically with T. The logarithm of the four-dimensional turnstile volumes for B = 4x 10e5 a.u. are plotted vs l/T in Fig. 13. The nearly linear plot shows that the turnstile volumes approximately obey the same scaling relation as that found by Tersigni, Gaspard, and Rice in the caseof a 2D map p(L) ccc -? (4.11) We have also applied the discrete mapping version of the alternative RRKM theory to estimate the short-time decay rate in the 4D map, with the zero-order separatrix taken to be the three-dimensional surface defined by the condition H,(r,p,;y) = 0. Figure 14 gives a series of 2D (r,p,) sections through the 4D phase space showing the zero-order separatrix. To calculate the alternative RRKM decay rate, it is necessary to compute the four-dimensional outgoing phase space volume enclosedbetween the approximate separatrix and its iterate under the van der Waals map, and to take the ratio of this volume to that of the complex region minus the invariant set [cf. Eq. (4.3) 1. Sectionsthrough the iterated approximate separatrix are also shown in Fig.. 14.As the 2D sections are defined at fixed ( y,pr), points on the iterated separatrix in a 2D section corresponding to a given
The required volumes are evaluated by multidimensional numerical quadrature. In principle, it should be possible to compute lobe volumes by evaluating an action-like flux two form on the homoclinic manifolds (cf. Ref. 7). To date, however, we have not been able to derive such a flux form. The numerical difficulties involved in implementing the multidimensional flux form formalismz8@ for continuous-time systems are discussedin Ref. 29. The problem naturally breaks down into a two-dimensional integration over ( y,pr ) of two-dimensional areas in the (r,p,) planes. For each pair ( y,pr ), the points on W*U(J oo) obtained in the separatrix calculation are sufficiently close together that the simple trapezoid formula
A--C ,1 (PC,+ 1 + Pr,, ) 2 -(Yn+) -rn)
03 cd Ln CD
8.0
9.0
10.0 11.0 l/T (x IO+)
12.0
13.0
(4.10)
FIG. 13. Four-dimensional turnstile volumes (squares) compared with fit to scaling law of Fq. (4.11) (dashed line).
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2662
13.E. Gillilan and G. S. Ezra: Mappings for unimolecular fragmentation

0 hi
9
i
FIG. 14. Series of 2D (p,p,) slices through the zero-order separatrix and its iterate at T= So00 and b = 4x IO- 5. The numbers in parentheses give the (y,~~) values of the particular sections in units of (?r/2,~-1/7 ).
9 N
(y,p,,) have preimages on the zero-order separatrix (in general) d@rent ( y,p,) coordinates.The details of the procedure used to find points on the iterated separatrix with specified (y,p,, ) coordiri&tes are discussedin the Appendix. The 4D volumes neededfor the calculation of the alternative RRKM rate are computed using the same numerical quadrature method discussedabove in connection with the Davis-Gray statistical rate. Alternative RRKM escapeprobabilities for the 4D van der Waals map are shown in Table III. The level of agreement with the numerical results for the uniform ensembleis comparableto that for the 2D map; that is, within a factor of 2-5. Ratios of the alternative RRKM escapeprobabilities to the Davis-Gray statistical values for the 4D map are shown in Fig. 7, and are seento be very similar to those for the 2D case. To obtain a more accurate description of the decay at longer times, multistate statistical models incorporating intramolecular bottlenecks in the 4D phasespacemust be developed. Trajectory studies suggest that bottlenecks associated with pairwise irrational frequency ratios are important in three-mode systems,23-25 that it would be so useful to be able to define intramolecular bottlenecks associated with particular pairwise frequency ratios to provide a rigorous test of this idea. A natural generalization to the 4D map of the (unstable) periodic orbit approximant to a cantors in the 2D map would be a 2D NHIM A,,, associated with a pairwise resonancecondition Eq. (3.6). The stable and unstablemanifolds of J,,, would be three-dimensional, and segmentsthereof could be used to define a 3D dividing surfacein 4D phasespacerepresentingthe multidimensional generalizationof the partial barrier associatedwith a periodic orbit approximant to a cantorus. The major technical obstaclecurrently preventing implementation of this schemeis the lack of an algorithm for computation of arbitrary NHIMs.
pair with
LO Q6
9
i
5.0
7.0
9.0 r
11.0
13.0
15.0
5.0
7.0
9.0
r
11.0
13.0
15.0
FIG. 15. Passage through homoclinic tangency. At T= 8000, B= 2.5x lo-* (a) andB= 4.0~ 10W5 (b), themanifolds Ws(&K) intersect in such a way that 2D (r,pr) sections at (y = 1.309,~~ = 556.0) can be deformed onto the 2D phase portrait of Fig: 4. At B = 5.5X 10m5 (c), however, the stable and unstable manifolds no longer intersect at the lower left-hand corner of the (r,p,) section. This phenomenon precludes the construction of space-enclosing turnstiles.
J. Chem. Phys., Vol. 94, No. 4.15 February 1991
2663
4. Nonexistence of turnstiles All results up to this point have been presentedfor the 4D van der Waals map corresponding to a potential with barrier height B = 4.0X 10 - approximately one half the , physical value.46 To show what happens when the barrier height (and hence the strength of the stretch-bend coupling) increases, we display in Fig. 15 a sequenceof 2D (r,p,> sections at the same (y,p,) point for increasing B values: 2.5X10m5 [Fig. 15(a)]; 4.0X lo- [Fig. 15(b)]; 5.5~10~~ [Fig. 15(c)].ForB= 5.5X10-,thestableand unstable manifolds of -& no longer intersect in the same , manner as the manifolds for smaller B values. On the other hand, sections at different (y,pr) points (not shown here) for B = 5.5 X lo- are of the sameform as those for smaller B values. The fact that the 2D section of Fig. 15(c) is qualitatively different from that of Fig. 15(a), whereas 2D sections taken at different values of (y,pr ) for the same B value (5.5 X lo- ) are similar to Fig. 15(a), means that for this value of B 40 volume enclosing turnstiles no longer exist. We refer to the transition shown in Figs. 15(a)-1 5 (c) as a passage through homoclinic tangency, by analogy with the corresponding phenomenonin area-preservingmaps. Prior to the appearanceof a homoclinic tangency in the 4D phasespace,there exist two disjoint 2D primary homoclinic intersection manifolds, eachsmoothly deformable onto 4 m (as discussed above, cf. Fig. 12). At the B value at which homoclinic tangency first occurs, the two intersection manifolds have a single common point. That is, there is a single ( y,pr ) point at which the area of one of the turnstile lobes in the (r,pr) section shrinks to zero. For larger B values, the two previously disjoint intersection manifolds merge. This fundamental changein topology was predicted by Wiggins2b and observedby us in a study of transport in coupled standard maps.65After the appearanceof homoclinic tangency, the homoclinic manifold is no longer homotopic to the NHIM V&.26Although a full mathematical analysis of such changesin topology of the homoclinic manifold has yet to be given, it is apparent that the onset of homoclinic tangency precludes the complete enclosureof a 4D complex region by W (&) and WU(y&), and prevents a straightforward generalization of turnstile-based transport theories. Figure 16 illustrates the essentialdifficulty preventing enclosure of a 4D complex region when homoclinic tangency occurs. It is possible to find continuous paths in 4D phase space (note: not orbits under the map) connecting points nominally outside (lower left of Fig. 16) the complex region to points inside (top left of Fig. 16), which cross neither the stable nor the unstable manifold of ,ti m. The fact that all lobes are generatedby forward or backward iteration of the primary lobes implies that any lobe may be reached from any other without crossing the separatrix branches. As shown by Davis in his study of the collinear H + H, reaction, several unstable fixed points may be involved in the definition of a complex region, dependingon energy.Our results on the 4D vau der Waals map do not rule out the existenceof turnstiles associatedwith some other nontrivial NHIM, or the possibility that such turnstiles might be important in unimolecular dissociation. Investigation of this possibility will, however, have to await the development of
5.0
6.0
7.0 r
8.0
9.0
5.0
6.0
7.0 r
8.0
9.0
FIG. 16. For the barrier height B = 5.5X lo- there exist continuous , paths in 4D phase space connecting lobes nominally inside and outside the complex region, which cross neither the stable nor the unstable manifold of&? *. Such a path is represented schematically by the arrows. The arrows connecting (a) and (b) correspond to varying y at fixed pr = 557. (a) (r,p,) section at (y= 0.72,~~ = 557). (b) (r,p,) sectionat (y= 1.18,pr = 557).
more general algorithms for computing NHIMs. Figure 17 shows the location of the boundaries in parameter spacebetweenthe region in which 4D turnstiles are well defined and that in which they are not. The trends in parameter values at which tangency first occurs may be readily understood. Qualitatively, factors which tend to decreasethe size of turnstile lobes in the (r,p,) plane sections also make it easier for homoclinic tangency to occur. For example, as the mass m of the adatom is increasedfrom that of helium, the van der Waals stretch and bend frequencies decrease, resulting in weaker coupling (better adiabatic separation) to the I, kick (smaller lobes), so that homoclinic tangency occurs at smaller B values [Fig. 17(a) 1. Decreas-
$
2 $lo 04 dY m+
::
3.0 3.5 4.0 m 4.5 5.0 0.0 1.0 2.0 I 3.0 4.0
J
5.0
z 2 ;; 8 -s? 0
m oi N 4
6000 7000 T 6000 9000
3 0 d z -! 25*
m+ 4 2
-0.53 0.80 0.67 B 0.74 0.61
FIG. 17. Boundaries of regions in parameter space corresponding to the onset of homoclinic tangency. Below the lines, space-enclosing turnstiles can be constructed. Qualitatively, factors which tend to increase turnstile amplitude also favor space enclosure at higher B values.
J. Chem. Phys., Vol. subject to February 1991 Downloaded 03 Jan 2001 to 128.253.229.100. Redistribution94, No. 4,15 AIP copyright, see http://ojps.aip.org/jcpo/jcpcpyrts.html.
2664
ing the kicking period T also decreasesthe size of turnstile lobes [Fig. 17(c) 1, as does decreasingthe Morse parameter ,L? (smaller van der Waals stretch frequency, Fig. 17(d), and the rotor moment of inertia I [smaller rotational frequency, Fig. 17(b)]. Although the onset of homoclinic tangency prevents implementation of the Davis-Gray statistical theory based on dynamically determined separatrices and turnstiles, the alternative RRKM theory may still be applied. Table IV compares alternative RRKM short-time decay rates with numerical rates calculated for T = 8000 and a seriesof B values spanning a range in which passagethrough homoclinic tangency occurs. It can be seen that there is no significant change in the level of agreement between the numerical results and the alternative RRKM results over the full range of
B.
Interestingly, examination of (r,p, ) sections (not shown) through the zero-order separatrix and its iterate for a B value at which homoclinic tangency occurs shows that the number of ingoing and outgoing lobes changes as the (y,py ) coordinates vary, so that the change in topology of the intersection set discussedabove is reflected in the behavior of the zero-order separatrix under iteration of the map.
V. DISCUSSION AND CONCLUSIONS
Hamiltonian or symplectic mappingsprovide a computationally efficient means of studying the phase spacestructure of multidimensional systems. For example, a four-dimensional symplectic map is a very convenient substitute for the PoincarCreturn map in the four-dimensional surface of section obtained by integrating trajectories in a three-mode continuous time molecular Hamiltonian. In the present paper, we have studied a four-dimensional Hamiltonian map modeling vibrational predissociation of the van der Waals molecule He& Our primary aim has been to generalize the Davis-Gray statistical theory of unimolecular dissociation to systemswith more than two degreesof freedom We began by pointing out the close relation between symplectic maps and symplectic trajectory integrators.* As the kick period T tends to zero, a symplectic map generates approximate trajectories for a continuous time system with a number of degreeof freedom equal to half the dimension of the map phasespace (the relation between the discrete map dynamics and that of the corresponding continuous time
TABLE IV. Alternative RRKM and numerical short-time decay rates for the uniform ensemble in the 4D van der Waals map Eq. (2.10). Z 8000. = B 4.0x10-5 5,0x10-* 6.0x10- 7.0x 10-s 8.72x10-
PO
0.1279 0.1229 0.1223 0.1232 0.1297
P
0.0245 0.0266 0.0289 0.0309 0.0332
Height of barrier to internal rotation. Short-time escape probability per iteration. Alternative RRKM Short-time escape probability per iteration. Numerical.
theory.
system will be discussedin more detail elsewhere). A 4D van der Waals map was then derived starting from the full Hamiltonian for planar He-I,. The classical centrifugal sudden approximation was invoked, and the continuous oscil5 lation of the I, bond replaced by a S-function kick acting upon the van der Waals stretch and bend degreesof freedom. After a review of the phasespacetheory of unimolecular decay in two degree of freedom systems due to Davis and Gray, the theory of transport in multidimensional systems recently developedby WigginsZbwas outlined. Wigginstheory provides a rigorous extension of turnstile-based approaches to phasespacetransport7*50 to multimode prob51 lems, and enables the Davis-Gray statistical theory to be generalized to multidimensional systems. An essential element of Wigginsapproach is the observation that the multidimensional analog of an unstable periodic orbit in a two degree of freedom system is a so-called codimension-two normally hyperbolic invariant manifold,27~58 denoted J?. These manifolds have appeared previously in various guises in the chemical physics literature: families of quasiperiodic orbits embedded in the continuum;59 center mani60 folds (cf. also Refs. 28, 29, 62, and 64); reduced dimensionality torib The stable and unstable manifolds of an invariant manifold J are of dimension one less than the energy shell, and so have the correct dimensionality to act as components of the boundary of a phase spaceregion. In preparation for our study of the full 4D map, we first examined the dissociation dynamics in a 2D area-preserving mapping acting upon the invariant subspacecorresponding to the T-shape van der Waals complex. Significant ensemble dependenceof unimolecular decay curves was noted, with the quasiclassical ensemblefor the ground state of the van der Waals stretch mode decaying much more slowly than an ensemble of initial conditions uniformly distributed throughout the complex region. Following the methods of Refs. 11 and 15, kinetic schemeswere developed for vibrational predissociation on short to intermediate time scales, which incorporated both intermolecular (reactive separatrix) and intramolecular (periodic orbit approximants to cantor-i) bottlenecks. The Davis-Gray statistical prediction for the short-time decay rate using a single intermolecular bottleneck gave on the whole good agreement with exact numerical results for the uniform ensemble. An anomaly was however apparent at T = 11 000, and was ascribed to a 4: 1 resonanceat the central fixed point. A four-state kinetic schemeincorporating three intramolecular bottlenecks gave excellent agreement with the exact numerical decay curve for short to intermediate times. In addition to applying the Davis-Gray theory basedon dynamically determined separatrices and turnstiles, the discrete map analog of the alternative RRKM approach of Gray, Rice, and Davis was also used to predict short-time decay rates for the 2D map. The resulting estimatesfor the decay constant were a factor of 25 larger than the Davis-Gray results, with better agreement obtained at larger T values. We next studied the 4D van der Waals map. As for the 2D case, numerical simulation results showed marked differencesbetween the decay behavior of the uniform and the quasiclassical ensembles.For a 4D map with a dissociative
J. Chem. Phys., Vol. 94, No. 4, 15 February 1991
FL E. Gillilan and G. S. Ezra: Mappings for unimolecular
fragmentation
2665
coordinate, such as that investigated here, the relevant codimension-two invariant manifold at infinity, ,drn, may be identified by inspection. Moreover, points on the three-dimensional stable and unstable manifolds W (-4 m) may be + found relatively easily, as shown in Sec. IV. For physically reasonable parameter values, the manifolds W (JY~) were found to intersect in the 4D phase spacein such a way as to enclose a well-defined four-dimensional complex region. In this casethe multidimensional analogs of turnstiles exist and mediate transport in and out of the complex region, Le., complex formation and unimolecular decay. The Davis-Gray estimate of the escapeprobability per iteration of the 4D van der Waals map was obtained by taking the ratio of the 4D volume of the outgoing turnstile lobe to that of the complex region (after subtracting the volume of the invariant set from the latter). This simple statistical theory was found to give very good agreement with numerically determined short-time decay rates for uniform ensembles, The discrete map version of the alternative RRKM theory was also applied to estimate short-time decay rates, and was found to give a level of agreement with the Davis-Gray theory comparable to that obtained for the 2D map (that is, within a factor of 2-5) .,. Although we have therefore shown that it is possible to generalize the Davis-Gray theory to obtain accurate estimates of short-time decay rates in a 4D map modeling van der Waals predissociation, some fundamental and as yet unsolved problems have become apparent from our study. First of all, it would be very useful to be able to improve the description of transport and escape in the 4D map by including the effects of intramolecular bottlenecks, whose existence is inferred from the characteristic biexpoential decay seenon intermediate time scales.Trajectory studies suggest that in some systems i.mportant intramolecular bottlenecks may be associated with pairwise frequency incommensurabilities,23-25in which casethe associatedpartial barrier should be defined in a manner analogous to the procedure used in two degree of freedom systems.771s.40 In that case, codimension-two normally hyperbolic invariant manifolds J,,, must be found corresponding to the single resonance condition m associated with a rational approximation to the particular irrational pairwise frequency ratio defining the bottleneck. A 4D region may then be enclosed by segments of the stable and unstable manifolds W(.&,), and the flux determined by evaluating the volume of the associatedturnstile. Although straightforward in principle, we have been unable to implement this procedure due to the lack of an algorithm for finding invariant manifolds -4,. A second, more fundamental problem arises from the fact that, even for physically reasonable parameter values, 40 turnstiles may simply not exist. Thus, for the 4D He-I, map we found that there exists a critical barrier height for hindered internal rotation above which turnstiles mediating transport across the reactive separatrix are no longer well defined. As discussedin detail in Sec. IV, there is an abrupt change in the topology of the intersection set of the manifolds ?Y%(Y/im) at the parameter value at which the turnstiles cease to be well defined, brought about by passage
through homoclinic tangency. The failure of the manifolds W4u(ygm ) to enclose a four-dimensional phase space volume means that the turnstile-based Davis-Gray theory for the rate of transport acrossthe reactive separatrix is no longer applicable. Although the full ramifications of the passage through homoclinic tangency remain to be explored, our results do indicate the need for development of new methods. As noted above, general algorithms for computation of normally hyperbolic invariant manifolds are required, in order to investigate the possibility that turnstiles associated with invariant manifolds other than Ode exist and are important in transport. In addition, it remains to be seenwhether periodic orbit based theories of asymptotic escaperates69p70 can be extended to multidimensional systems. Even for parameter values where turnstiles do not exist, the alternative RRKM theory may still be applied. Our calculations show that there is no drastic change in the level of agreement between the alternative RRKM rate and the numerically determined escape rate when turnstiles cease to exist. The methods developed here require less human effort than those of Ref. 29, and may be applied to study the phase space structure of continuous-time systems in which there are invariant three-sphere$ determined by symmetry. Direct numerical integration of the volume of a four-dimensional phase space region for the 4D van der Waals map requires on the order of lo7 mapping iterations (several hours of CPU time on a Sun 4 workstation), so that application of these techniques to continuous-time systems, although computationally intensive, should be within the capability of current computing technology. In the three-dimensional surface diffusion problem, Gillilan2 has used a more economical but less accurate method based upon Monte Carlo integration to calculate the 4D volume in the surface of section of a region mediating barrier recrossing. In symmetric planar reactive scattering problems such as H + H, or I + HI, several codimension-two invariant manifolds may readily be identified by inspection. Thus, for H + H, at energieslessthan the triple dissociation threshold there are three different invariant manifolds at infinity, ,& (i), i = 1,2,3, corresponding to the three distinct atom/ diatom subsystems. There are moreover three invariant manifolds & (i) associatedwith C,, symmetric configuc2, rations, which intersect in a one-dimensional subspacecorresponding to symmetric stretch motion. The way in which the stable and unstable manifolds of these objects intersect and determine transport remains to be understood. Investigation of systems with significant reaction path curvature will undoubtedly lead to more complicated phase space structure than that found here (cf. Ref. 19). Understanding such structure remains one of the challenges of modern chemical dynamics. Finally, we note that all our considerations have been limited to classical mechanics. Application of techniques for quantization of maps7should provide insight into the classical-quantum correspondence for multimode systems. For example, it has been established for two-mode systems that quantum effects can suppress transport across a bottleneck
2666
Ft. E. Gillilan and G. S. Ezra: Mappings for unimolecular fragmentation
with classicalflux <h, and it is of interest to know whether * analogous quantum effects occur in higher dimensions.
= jj, a(p-:$f:;~;:w
ACKNOWLEDGMENTS
1) *
(A61
This work was supported by NSF Grant No. CHE8704632. Computations reported here were performed in part on the Cornell National Supercomputer Facility, which is supported in part by NSF and the IBM Corporation. We thank S. Wiggins for a preprint of Ref. 26 and for invaluable discussions on the structure of multidimensional phase space. Helpful discussions with M. J. Davis, R. Easton, R. MacKay, and R. Skodje are also acknowledged.
APPENDIX
A natural choice for the coordinate system is to use time ton the zero-order separatrix:73
r[t,r(O)]
=+-ln
(1 - a) + wmEa2 I
2
1 ,
+ r(())
(A71
a coordinate s, which is distance in the direction normal to the zero-order separatrix given by the gradient of the Hamiltonian on the separatrix trajectory:
dH, dp,=m PI
In this Appendix we discuss some of the technical details of the algorithm used to find points on the invariant manifolds WS*.(U&m)and on the homoclinic intersection manifolds and the zero-order separatrix (cf. Sec. IV).
Separatrix branches
dH 2~ dr
e-2/3)
[(l
_a)e-2/3-r,J
mm,-P(r-r,,,], (A81
Let R a represent IZapplications of the mapping (2.10) to a phasepoint (Pq:, f,pF >, and let
(r&,y,p, > = R V ,P%? ,&). (Al)
and coordinates (y,p,). Although the mapping Q: (t,s, y,pr ) -+ (r,p,,y,p, ) is one-to-one only on and outside the separatrix, the multivaluedness presents no special computational problems since transformations are only made in one direction.
Homoclinic manifolds
In the case that n is negative, R denotes n applications of the inverse mapping R - . If there exists a coordinate system, (~1,~2,~3,~4),in which separatrix branches may be described (at least locally) as singled-valued functions ~4(~,,~2,~3), then a point is on the stable (intermolecular) separatrix branch Ws(dm ) if
To specify points on the primary (homoclinic) intersection manifolds, two coordinates are necessary. Given ( v,,v2) one must find coordinates ( v3,v4) such that
lim XQ(r13,7~4;~1,v2)= 0, 1) n-m H,-%

n-m
lim n-02H,{R ~Q(v~;v,,~,T~) 1) = 0,
(A21
lim H,{R -[Q(q3,~.,;sI,~,>1) = 0.
(A91
where Q: (~,,~,,~,,~7,) -+ (r,pr,y,pu) transforms the special coordinates into the standard set. The samecondition as Eq. (A2) with n-t - COdefines points on the unstable branch WU(d * ). Numerically, points on the stable/unstable manifolds are approximated by points satisfying
This is easily accomplished with a simple two-dimensional Newton search. Solution of the linear system
f-f,@ * [Q(TwwI~~v~ 1) = 0
(A31
for a fixed value of n (typically 10-12). An initial guessfor v., at some fixed ( ~l,~2,~s) is made based on the known separatrix of one of the invariant subspacesof the map Eq. (2. lo), ( y = 7~/2,pr = 0), for example. A one-dimensional Newton search yields a sequence {?I,,) that converges to the desired point:
Hr ;)r14,k+ 1 = v4.k V,P:,~,P; >
JHr[R - YQ,l/h JHrER +(Q>l/a?7, JH,[R + YQ,l/%, - H,[R - YQ,l = (A101 -H,[R +YQ,l yields a correction vector (h~,~~,hr],) which, when added to
JH,CR -(Q>l/h
the initial guess, yields an improved estimate. For a sufficiently close initial guess,a convergent series results:
[::::::I 21. =[;:::

Alternative RRKM surfaces
(All)
dH, ( r,p:, y,p; ) /dr/d .
(A41
The derivative is computed as

--=
Computation of homoclinic manifolds in this way does not require any special coordinate system (as long as the intersection manifold is homotopic to A ), so that r andp, may be varied at fixed ( y,pr ).
dH,
dr/4
(VH r
) t* mz7P:JTP; W ,p;) ,pY
1 *a drl,,
(A51
where the Jacobian matrix is computed cumulatively by a procedure analogous to the continuous-time method of first variation:
Let H,. (r,p,;y) = 0 define a surface in the phase space through which we wish to calculate flux. Again, let Q be a transformation from local coordinates (~1,~2,~3,~~) to
J. Chem. Phys., Vol. 94, No. 4,15 February 1991
2667
(r,pr,y,py ) . A point lies on the forward-mapped surfaceifits preimage satisfies L412) f&CR - EQ(wmg,Q I>= 0. For a specified (~1, )2,~3), the Q satisfying this equation is efficiently obtained with a one-dimensionalNewton search:
?4,k+ 1 = 74.k -
H[R - (Q)l dJf[R - (Q)l/d&
(A13)
This algorithm is essentially the sameas that for computing separatrix branches,but the calculations are naturally much faster. Becausethe zero-order separatrix is not the variationally optimal dividing surface for this problem, the forward image is geometrically more complex and has larger oscillations than the correspondingdynamically determined separatrix. The coordinate system describedpreviously leadsto a multivalued representationi.n this case.To fix this problem, we have implemented a coordinate-independentmethod of computing the curves. Let [r(i),p,(i),y(i),p,.(i)] be a phase space point which satisfies Eq. (A12). At fixed [y(i) ,pr (i) 1, a circle defined by
r=pcosO+r(i),
(A14) withp small, will intersect the iterate of the zero-order separatrix at two points, denoted 8, and 8 _ , which may be found by one-dimensionalroot searches. One of thesepoints, [ r( i + 1) ,p, (i + 1) 1, obtained with a particular choice of angle, may then be taken as the new center of the circle. In this way, it is possibIeto follow the image curve regardlessof its complexity.
pr =p sin 19+p,(j>,
D. Levine and R. B. Bernstein, Molecular Reaction Dynamics (Oxford R. University, Oxford, 1987). 2D. G. Truhlar, W. L. Hase, and J. T. Hynes, J. Phys. Chem. 87, 2664 (1983). P. J. Robinson and K. A. Holbrook, Unimolecular Reactions (Wiley, New York, 1972); W. Forst, Theory of Unimolecular Reactions (Academic, New York, 1973); W. L. Hase, in Dynamicsof Molecular Collisions, edited by W. H. Miller, Part B (Plenum, New York. 1973): D. A. Wardlaw and R. A. hlarcus, Adv. Chem. Phys: 70,231 (1988). . 4P. Pechukas, in Dynamics of Molecular Collisions, edited by W. H. Miller, Part B (Plenum, New York, 1973). J. Lichtenberg and M. A. Lieberman, Regular and Stochastic Motion A. (Springer, Berlin, 1983); M. Tabor, Chaos and Integrability in Nonlinear Dynamics (Wiley, New York, 1989): R. S. MacKav and J. D. Meiss. Hamiltonian Dy~amicaZSystems (Hilger, Bristol, 1986); A. M. Ozorio de Almeida, Hamiltonian Systems: Chaos and Quantization (Cambridge University, Cambridge, 1988). A. Rice, Adv. Chem. Phys. 47,117 (1981); D. W. Noid, M. L. KoszyS. kowski, and R. A. Marcus, Annu. Rev. Phys. Chem. 32,267 ( 1981); E. B. Stechel and E. J. Heller, ibid. 35, 563 (1984); W. P. Reinhardt, J. Phys. Chem. 86,2158 (1982); P. Brumer, Adv. Chem. Phys. 47,201 (1981); M. Tabor, ibid. 46, 73 (1980); P. Brumer and M. Shapiro, ibid. 60, 371 (1985); 70,365 (1988); P. Brumer, Phys. Ser. 40,394 (1989). MacKay, J. D. Meiss, and I. C. Percival, PhysicaD 13,55 ( 1984); 27,1 R. (1987). Bensimon and L. P. Kadanoff, Physica D 13,82 (1984). D. R. Channon and J. L. Lebowitz, Ann. N.Y. Acad. Sci. 357,108 ( 1980). S. I Bunker and W. L. Hase, J. &hem. Phys. 59,462l ( 1973); R. A. MarD. cus, W. L. Hase, and K. N. Swamy, J. Phys. Chem. 88,6717 (1988). M. J. Davis and S. K. Gray, J. Chem. Phys. 84, 5389 (1986).
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J. Chem. Phys., Vol. 94, No. 4,15 February 1991

Richard E. Gillilan and Gregory S. Ezra - Transport and Turnstiles in Multidimensional Hamiltonian Mappings For Unimolecular Fragmentation: Application To Van Der Waals Predissociation

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Richard E. Gillilan and Gregory S. Ezra - Transport and Turnstiles in Multidimensional Hamiltonian Mappings For Unimolecular Fragmentation: Application To Van Der Waals Predissociation

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Transport a d turnstiles in multidi ensional Hamiltonian mappings for unimolecular fragmentation: Application to van der Waals predissociation

Richard E. Gillilat?) and Gregory S. Ezrab)

FL E. Gillilan and G. S. Ezra: Mappings for unimolecuiar fragmentation

Recently, Gaspard and Rice3have studied Hamilto-

ceptionalcase.Considera freeparticle moving in onedimen-

R. E. Gillilan and G. S. Ezra: Mappings for unimolecular fragmentation

sion, periodically kicked by a delta-function potential with Hamiltonian

mapping for He-/2

pr-+p; +Atpit+@t), r4r

The classical Hamiltonian for planar He-I, is

R. E. Gillilan and G. S. Ezra: Mappings for unimolecular fragmentation

2651 (Sec. II). All quantities

B (height of barrier to internal rotation)

p,-tp: =pr - T$,

r, = rmin - [ln( 1 - Cr)I//?.

well depth and the height of the barrier to internal rotation

R. E. Gillilan and G. S. Ezra: Mappings for unimolecular fragmentation

9.0 12.0 r (Bohr)

, H, y=t =g+ ( >

R. E. Gillilan and G. S. Ezra: Mappings for unimolecular fragmentation

separatricesto systems with more than two degreesof freedom.

R. E. Gillilan and G. S. Ezra: Mappings for unimolecular fragmentation

R. E. Gillilan and G. S. Ezra: Mappings for unimolecular fragmentation

R. E. Gillilan and G. S. Ezra: Mappings for unimolecular fragmentation

R.E. Gillilan and G. S. Ezra: Mappingsforunimolecularfragmentation

TABLE II. Predissociation in two-dimensional van der Waals map, Eq.

tive RRKM result is consistently higher for the 4D mapping.

R. E. Gillilan and G. S. Ezra: Mappings for unimolecular fragmentation

R. E. Gillilan and G. S. Ezra: Mappings for unImolecular fragmentation

R. E. Gillilan and G. S. Ezra: Mappings for unimolecular fragmentation

0.0310 0.0436 0.0574 0.0715 0.0860

J. Chem. Phys., Vol. 94, No. 4, 15 February 1991

R. E. Gillilan and G. S. Ezra: Mappings for unimolecular fragmentation

theory for short-time

10.0 11.0 l/T (x IO+)

13.E. Gillilan and G. S. Ezra: Mappings for unimolecular fragmentation

J. Chem. Phys., Vol. 94, No. 4.15 February 1991

R. E. Gillilan and G. S. Ezra: Mappings for unimolecular fragmentation

R. E. Gillilan and G. S. Ezra: Mappings for unimolecular fragmentation

J. Chem. Phys., Vol. 94, No. 4, 15 February 1991

FL E. Gillilan and G. S. Ezra: Mappings for unimolecular

Ft. E. Gillilan and G. S. Ezra: Mappings for unimolecular fragmentation

lim XQ(r13,7~4;~1,v2)= 0, 1) n-m H,-%

lim n-02H,{R ~Q(v~;v,,~,T~) 1) = 0,

lim H,{R -[Q(q3,~.,;sI,~,>1) = 0.

[::::::I 21. =[;:::

dH, ( r,p:, y,p; ) /dr/d .

The derivative is computed as

) t* mz7P:JTP; W ,p;) ,pY

J. Chem. Phys., Vol. 94, No. 4,15 February 1991

R. E. Gillilan and G. S. Ezra: Mappings for unimolecular fragmentation

H[R - (Q)l dJf[R - (Q)l/d&

S&c. 120,303 (1985).

J. Chem. Phys., Vol. 94, No. 4,15 February 1991

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