THE JOURNAL OF CHEMICAL PHYSICS 125, 084505 2006

Molecular dynamics simulations of melting of perfect crystalline hexahydro-1,3,5-trinitro-1,3,5-s-triazine

Lianqing Zheng and Donald L. Thompsona
Department of Chemistry, University of Missouri, Columbia, Missouri 65211

Received 22 March 2006; accepted 30 June 2006; published online 24 August 2006 The melting mechanism of superheated perfect crystalline hexahydro-1,3,5-trinitro-1,3,5-s-triazine -RDX has been investigated using molecular dynamics simulations with the fully exible force eld developed by Smith and Bharadwaj J. Phys. Chem. B 103, 3570 1999 . Sequential 50 ps equilibration simulations of the constant stressconstant temperature ensemble were performed at 10 K intervals over the range of 300 650 K, corresponding to a heating rate of 2.0 1011 K / s. A solid-solid phase transition is observed between 480 and 490 K, followed by melting, which occurs between 500 and 510 K. The solid-solid phase transition, both displacive and rotational, is characterized by an abrupt decrease in the lengths of the unit cell edges a and b and an increase of the length of edge c. The molecular conformation in the new phase is AAE, although the axial nitro groups have different changes: one shift is more axial and the other is more equatorial. Phases other than -RDX have been observed experimentally, however, there are insufcient data for comparisons to ascertain that the new phase observed here corresponds to a real phase. At the high heating rate 2.0 1011 K / s used in the simulations, the melted RDX reaches full orientational disorder at about 540 K and translational freedom at around 580 K. If the simulation at the melting temperature 510 K is run sufciently long complete rotational freedom is achieved in a few hundreds of picoseconds, while complete translational freedom requires much longer. These results show that given a sufciently high heating rate, the system can exist for signicant periods of time in a near-liquid state in which the molecules are not as free to rotate and diffuse as in the true liquid state. The bond lengths and bond angles undergo little change upon melting, while there are signicant changes in the dihedral angles. The molecular conformation of RDX changes from AAE to EEE upon melting. The ramication of this for formulating force elds that accurately describe melting is that it is important that the torsional motions are accurately described. 2006 American Institute of Physics. DOI: 10.1063/1.2238860
I. INTRODUCTION

Direct measurements of molecular-level details of melting are difcult. Molecular dynamics MD simulations provide a practical means of gaining insights that are not accessible experimentally into the microscopic mechanisms by which a solid is transformed to a liquid. Many MD studies of melting of atomic solids have been reported, but only a few of molecular solids. We have reported a series of studies using MD simulations to investigate the melting of complex molecular and ionic solids.16 We have used nitromethane as a prototypical molecular solid. We have developed a force eld that accurately describes the solid, liquid, and melting properties of nitromethane. Agrawal et al.7 compared the results of MD simulations of melting of rigid and exible models of nitromethane, concluding that the melting point is predicted equally well with either model. The molecular structure does not undergo signicant change upon melting.8 In a study of a somewhat larger, more exible molecule, dimethylnitramine, we found that molecular torsional motions are important for accurately modeling the melting transition.9 These results prompt us to investigate melting of
a

crystals of larger, oppier molecules. Here we report the results of MD simulations of perfect crystalline hexahydro1,3,5-trinitro-1,3,5-s-triazine C3N6O6H6 RDX , a widely used energetic material, and an excellent prototypical large, exible molecule. Figure 1 shows the molecular conguration of -RDX; the labeling of the atoms will be used in subsequent discus-

Electronic mail: thompsondon@missouri.edu

FIG. 1. The molecular structure of -RDX with the labeling of the atoms that is used in the discussions. The coordinates were based on the x-ray data Ref. 11 . 125, 084505-1 2006 American Institute of Physics

0021-9606/2006/125 8 /084505/9/$23.00

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084505-2

L. Zheng and D. L. Thompson

J. Chem. Phys. 125, 084505 2006

sions. RDX has close to Cs symmetry. The molecule consists of three CH2NNO2 units arranged in a six-member ring, with two nitro groups N2N5O3O4 and N3N6O5O6 in Fig. 1 of the molecule in the -RDX crystal arranged in the pseudoaxial A position about the ring and a third in the pseudoequatorial E position, i.e., the AAE conformation. Experiments indicate that there are considerable differences in the molecular structure in the two crystalline phases for which there are data, in solution, and in the gas phase.10 The major change is in the relative orientations of the nitro groups. It seems reasonable that if there are intramolecular changes in transitions from the solid to the solution or gas phase, there would be similar changes upon melting. Crystalline RDX exists in several polymorphic forms. The most stable phase at ambient conditions is -RDX, which is orthorhombic and belongs to the space group Pbca with eight molecules in the unit cell.11 The second crystalline phase, -RDX, was rst observed by McCrone12 by recrystallizing RDX on a microscope slide from high boiling-point solvents. It is highly unstable and therefore crystallographic data for it are not available.13 Olinger et al.14 rst observed the third crystalline phase, RDX III, at 293 K when they applied a pressure of over 4 GPa on -RDX. RDX III is orthorhombic and belongs to the Pbca space group. The melting point 462 K of -RDX has been measured.15 Baer et al.16 used Raman spectroscopy to study the phase diagram of RDX at pressures up to 16 GPa and over the temperature range of 150 450 K. They determined the pressure for the -RDX RDX III transition to be 3.8 0.2 GPa and independent of temperature from 150 to 375 K. They found the -RDX RDX III transition to be reversible. They also observed a metastable phase of RDX at high pressure and high temperature, which they concluded was -RDX based on comparisons of their Raman spectra with the IR spectra of -RDX.17 However, there have been no further results to conrm this. When a crystal is subjected to ultrafast heating induced by intense radiation or shock waves, it can undergo superheating before melting.1820 An explosive when shocked or rapidly heated is very likely to undergo some superheating before it melts and detonates.21,22 Our main interest in the present study is the melting mechanism of superheated perfect crystalline RDX, thus the present study is for perfect crystals. We have not attempted to calculate the thermodynamic melting point of RDX.
II. COMPUTATIONAL METHODS A. Force eld

structures of HMX and RDX, we assume that the force eld realistically describes RDX without any modications except for the atomic partial charges. The total potential energy Utotal of this force eld is the summation of the electrostatic UES , van der Waals UvdW , bond stretching Ubond , bondangle bending Uangle , and dihedral Udih, which includes proper dihedrals and out-of-plane bends energies,
N N

Utotal =
i=1 j=i+1

kc +

q iq j Cij + Aij exp BijRij 6 Rij Rij

0 2

Ks KB r r0 2 + bonds 2 angles 2 KT 1 cos n dihedrals 2 KO bends 2

2

+
proper

+
outofplane

where Aij, Bij, and Cij are parameters for the intermolecular van der Waals interactions; qi, Rij, r, , , and are the partial charges, nonbonded interatomic distances, bond lengths, bond angles, proper dihedral angles, and out-ofplane bending improper dihedral angles, respectively; KS, KB, and KO are the harmonic force constants for bond stretching, bond-angle bending, and out-of-plane bending, respectively; KT and n are the barrier and periodicity for the torsional motions, respectively; N and kc are the number of atoms in the simulation supercell and Coulomb constant, respectively. The electrostatic and van der Waals interactions are applied to all intermolecular atoms and atoms separated by three or more bonds in a molecule. The values of the parameters Aij, Bij, Cij, KS, KB, KO, KT, and n are given in Ref. 23 and the partial charges are taken from Ref. 29.
B. Molecular dynamics simulations

The fully exible force eld developed by Smith and Bharadwaj23 SB was used for the simulations. This force eld was at rst developed for dimethylnitramine24 by using quantum-chemistry calculations and later extended to octahydro-1,3,5,7-tetranitro-1,3,5,7-tetra-azacyclooctane HMX . Smith and co-workers have applied this force eld to study the physical properties of crystalline and liquid HMXs, such as density, lattice parameters,25 elastic properties,26 shear viscosity coefcient,27 and thermal conductivity.28 Based on the similarities of the molecular

The MD supercell consisted of 2 3 3 unit cells 144 molecules, 3024 atoms of -RDX. The initial atomic coordinates were calculated according to experimental crystallographic data and the initial supercell was of size 26.364 34.722 32.127 3. Three-dimensional periodic boundary conditions were applied. All simulations were performed using the DLPOLY program30 for the constant-temperature and -stress NST ensemble.3133 The same relaxation time, 1.0 ps, was used for the thermostat and barostat. The time step for trajectory integration was 1.0 fs. The cutoff distance of 11.0 was used for the van der Waals interactions and the electrostatic interactions were calculated using the smooth particle mesh Ewald algorithm.34 The average value of the pressure in all simulations was constrained at 1 atm. Simulations of 50 ps duration were performed at 10 K increments, equivalent to a heating rate of 2.0 1011 K / s. The starting conguration of each simulation was the last conguration of the previous simulation at a lower temperature. The duration of each simulation was 50 ps. The initial temperature was 300 K and then increased to 350 and 400 K, after which the temperature increment was set to be 10 K.

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084505-3

Melting of RDX

J. Chem. Phys. 125, 084505 2006

To monitor the changes in the system with increasing temperature, we dene translational T and orientational O order parameters,
T

rref ri 1 m i = cos 2 Nm i=1 rref 2 i

N

and
O

1 m ref = nCCC,i . nCCC,i 2 . Nm i=1

Here, Nm is the number of molecules in the supercell, and the vectors ri and nCCC,i are, respectively, the coordinates of the center of mass and normal vector of the CCC plane of the ith molecule. The superscript ref denotes the values expected when the MD supercell undergoes only linear thermal expansion. Similar order parameters have been used to study the melting of nitromethane.8 To determine the changes in the molecular orientations in the solid-solid phase transition see below , we have calculated the distribution of an angle-order parameter dened as cos
i ref = nCCC,i nCCC,i .

FIG. 2. Comparison of the calculated circles and experimental squares isotherms of RDX crystal at 300 K. a Relative volume as a function of pressure; b unit cell edge lengths as functions of pressure. The experimental data were taken from Olinger et al., Ref. 14.

III. RESULTS AND DISCUSSION

The values of the density and lattice parameters of crystalline RDX predicted by the SB potential at ambient conditions are in good agreement with experiment.11 The computed density at 300 K and 1 atm is 1.83 g / cm3, about 1.2% larger than the measured value of 1.81 g / cm3. The calculated crystal unit cell lengths a, b, and c are 13.330, 11.497, and 10.532 , respectively, compared to the experimental values of 13.182, 11.574, and 10.709 .11 The calculated unit cell angles , , and are 90.02, 89.98, and 90.00, in excellent agreement with the measured value of 90.0 for the three angles. The calculated 300 K isotherm see Fig. 2 is also in excellent agreement with the experimental data14 up to 4 GPa, where the III phase transition is expected. The SB potential does not predict the III transition, possibly because the repulsive part of the potential is not accurate at high pressure. The bulk modulus B and its pressure derivative B were calculated by tting the isotherm up to 4 GPa to the third-order Birch-Murnaghan equation35 3 PV = B 2 V V0 V V0
7/3

The density and diffusion coefcient D of the carbon atoms over the temperature range of 300 650 K are shown by the solid circles in Fig. 3. These results were obtained using a heating rate of 2.0 1011 K / s. There are abrupt changes in and D between 500 and 510 K due to melting. About 10 K below the melting transition, there is a small 0.9% abrupt decrease in the density, which we discuss below. The density of RDX abruptly decreases by 6.2% at 510 K and there is a sharp increase in the diffusion coefcient from near zero to 1010 m2 / s. This melting temperature of the perfect RDX crystal is comparable to the value of 504 K calculated using a force eld that is a combination of the generalized AMBER Ref. 38 intramolecular interactions and the Sorescu-Rice-Thompson SRT force eld.29 The AMBER-SRT force eld predicts 439 K for the thermodynamic melting point, in reasonable agreement with the mea-

2/3

V V0 ,

5/3

3 4B 4 5

where V0 is the volume at 1 atm. The calculated values of B and B are, respectively, 12.3 GPa and 9.95 compared to 12.1 GPa and 8.65, which were obtained by tting the experimental data14 to Eq. 5 . The reported experimental values of B range from 11.1 to 11.9 GPa,36,37 thus our calculated value of B is in good agreement with all the available results.

FIG. 3. Calculated a density and b diffusion coefcient of RDX as functions of temperature. The rate of heating was 10 K / 50 ps 2.0 1011 K / s .

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084505-4

L. Zheng and D. L. Thompson

J. Chem. Phys. 125, 084505 2006

FIG. 5. Distributions of the order angles i see Eq. 4 of the RDX molecules at 480 K dashed curve and 490 K solid curve .

FIG. 4. Calculated a unit cell volume V and b d edge lengths a, b, and c as functions of temperature. The circle symbols are the results of a heating simulation and the squares are the results for cooling simulation. The points are connected by straight lines for clarity. The rate of heating/ cooling was 10 K / 50 ps 2.0 1011 K / s .

sured value of 462 K.39 We did not compute the thermodynamic melting point for the SB force eld, but given the agreement with the AMBER-SRT for the perfect solid, we would expect good agreement for the thermodynamic melting point, and thus good agreement with experiment. The small drop in the density values shown in Fig. 3 that occurs below the melting point is the result of a solid-solid phase transition. Note that there is not a corresponding increase in the diffusion coefcient. The changes in the volume and shape of the unit cell for this phase change are shown by the circles in Fig. 4. Figure 4 shows the volume and the lengths of the edges of the unit cell for both heating circles and cooling squares over the range of 300 500 K. Heating results in a small but signicant change in the volume between 480 and 490 K, however, upon cooling at the same rate as the heating there is no abrupt change in volume, indicating that the transition is not reversible. The lengths of the unit cell edges a, b, and c are shown, respectively, in panels b , c , and d of Fig. 4. There are abrupt changes in a, b, and c in the interval of 480 490 K from 13.46, 11.64, and 10.71 to 13.35, 11.23, and 11.29 0.8%, 3.5%, and 5.4% , respectively. The average values of the unit cell angles remain 90. This phase is likely an artifact of the SB force eld, and we will refer to it as RDX-SB. There are insufcient data for the crystal phases of RDX to determine whether the RDX-SB phase approximates a real phase. It is reasonable to assume that a solid passes through such transitory phases as the temperature approaches the melting point, although it is expected that it would be less ordered than the one predicted by the SB force eld. Though the difference of the densities of the two solid phases is quite small, the unit cell edge lengths differ signicantly, especially b and c, indicating that RDX-SB and -RDX are dif-

ferent crystalline phases. The fractional coordinates of RDX-SB show that it also belongs to the space group Pbca. Figure 5 shows the distributions of at 480 and 490 K computed using Eq. 4 . Apparently, the distribution for 480 K peaks 7.2 and that for 490 K at 12.5. The distribution for 490 K is broader; the full width at half maximum is 13.6 at 480 K and 17.6 at 490 K. These differences indicate that relatively signicant orientational changes occur in the solid-solid phase transition. The orientational uctuations are limited to the peak region, showing that the RDX-SB phase is crystalline, with no dynamic orientational disorder. The mean-squared displacements msd of the C, N, O, and H atoms at 490 K are shown in Fig. 6 as functions of time. Comparing the msd of the C atoms at 480 K dashed curve , we see that signicant increases in the msd occur during the solid-solid phase transition e.g., the msd of the C atoms increases from 0.45 to 1.1 2 and the uctuations also signicantly increase from about 0.05 to about 0.125 2. These results show that there is signicant thermal uctuation in the RDX-SB phase. The van der Waals, electrostatic, bond stretching, bondangle bending, and dihedral energies and enthalpy H = total energy+ PV of the RDX supercell as functions of temperature up to 650 K are shown in Fig. 7. The UvdW, Ubond, and H undergo no abrupt change at the solid-solid phase transition, while abrupt changes are found in all ener-

FIG. 6. Mean-squared displacements msd of the C, N, O, and H atoms as functions of time at 490 K. The dashed curves denote the msd of the C atoms at 480 K and serve as a reference for those at 490 K.

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084505-5

Melting of RDX

J. Chem. Phys. 125, 084505 2006

FIG. 7. a van der Waals, b electrostatic, c bonding, d bending, and e dihedral energies and f enthalpy per molecule as functions of temperature. The arrows point to where the solid-solid phase transition 490 K and melting 510 K occur, respectively.

FIG. 9. Plots of the logarithm of the orientational and translational order parameters vs the simulation time at 510 K.

gies except the bond stretching energy and enthalpy upon melting. The electrostatic energy is increased by 2.5% from 480 to 490 K and by 6.9% from 500 to 510 K. The bending energy is decreased by 0.9% at the solid-solid phase transition and by 1.8% at the melting. After the RDX supercell becomes the liquid phase, the bending energy begins to increase again with increasing temperature. The dihedral energy including the proper dihedral and out-of-plane bending energies rst is increased by 2.6% when the temperature is increased from 480 to 490 K, drops by 8.6% at the melting, and then begins to increase again with increasing temperature. Figure 8 shows the temporal evolution of the supercell edge lengths, volume, and translational and orientational order parameters at the solid-solid phase transition temperature 490 K and superheating melting temperature 510 K . At 490 K, the supercell edge lengths a and b abruptly drop at about 15 ps of the simulation time, while the edge length c suddenly increases see Fig. 8 a . At the same time, both the

FIG. 8. a The MD supercell edge lengths and b translational and orientational order parameters as functions of time at the solid-solid phase transition temperature 490 K; c supercell volume and d translational and orientational order parameters as functions of time at the melting temperature of 510 K.

translational and orientational order parameters undergo abrupt drops from 0.99 and 0.96 to 0.94 and 0.92, respectively, indicating that this solid-solid phase transition is both displacive and rotational see Fig. 8 b . When the temperature is increased to the melting temperature, the supercell volume begins to expand abruptly see Fig. 8 c , and the order parameters are found to drop quickly see Fig. 8 d . The values of the translational and orientational order parameters for a fully disordered system are, respectively, 0.5 and 0.35.8 Apparently, the given simulation duration of 50 ps is not long enough for both order parameters to reach the equilibrium values. Hence, we extended the simulation time at 510 K to 300 ps see Fig. 9 to investigate the further evolution of the order parameters. It is found that it takes almost 300 ps for the orientational order parameter to reach the nal value of 0.35 while the translational order parameter seems to reach an equilibrium value of 0.77, well above the nal value of 0.5 for complete disorder, at around 150 ps and does not decrease further. These results suggest that the melted RDX retains some translational order, but complete rotational freedom at 510 K. Further insight is gained from the temperature dependences of the order parameters, which are shown in Fig. 10. The translational and orientational order parameters are represented by the circles and squares, respectively, in Fig. 10; each point in Fig. 10 is an average of the property of all the molecules in the simulation cell over the time interval of 50 55 ps; straight lines have been sketched in the gure to illustrate the different stages including the transitions of the system as the temperature increases. Both order parameters remain close to 1.0 up to 480 K, then abruptly drop at 490 K due to the solid-solid phase transition. Larger decreases in the order parameters occur when the RDX crystal melts at 510 K. The orientational order parameter reaches its nal value of 0.35 at 540 K, while the translational order parameter reaches 0.5 at 580 K. At the given heating rate, the melted RDX retains partial translational order, but there is orientational disorder between 540 and 580 K. We have analyzed the molecular structural changes of RDX at the solid-solid phase transition and melting. We will focus on the dihedral angles because the bond lengths do not

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084505-6

L. Zheng and D. L. Thompson

J. Chem. Phys. 125, 084505 2006

FIG. 10. Orientational squares Eq. 2 and translational circles Eq. 3 order parameters as functions of temperature. The rate of heating was 10 K / 50 ps 2.0 1011 K / s . Straight lines have been drawn to illustrate the various stages the system passes through as the temperature is increased.

undergo signicant changes as indicated by the bonding energy ; changes in the bond angles are less than 5. Figure 11 shows three examples of changes in the dihedral angle distributions upon the solid-solid and solid-liquid transitions: C3N3C2N2, H5C3N3C2, and H1C1N2N5 the atom labels are given in Fig. 1 . The peak positions of the C3N3C2N2 dihedral angle shift to smaller angles when temperature is increased from 480 to 490 K, i.e., from 51 to 46. The two pronounced peaks in each of these distributions merge to one broad at peak ranging between 50 after the RDX crystal is melted see Fig. 11 a . This indicates that the ring structure of RDX in the liquid phase changes signicantly with time. The peaks in the H5C3N3C2 dihedral angle distribution shift to larger angles from 69 to 84 in

the solid-solid phase transition see Fig. 11 b . When RDX melts the peak widths in the distributions become much larger at least twice those for crystalline RDX and the peak heights decrease signicantly. There is a shoulder at 135 on the distribution for the liquid phase. Figure 11 c shows that the peaks of the H1C1N2N5 dihedral move toward larger angles from 130 to 157 and their magnitudes increase when the temperature is increased from 480 to 490 K. Unlike the broadening in the distributions of the CNCN and HCNC dihedral angles at 510 K, this dihedral angle undergoes a pronounced shift when the crystal melts: from 157 at 490 K to 65 at 510 K. A small peak at 165 is present in the distribution for the melted RDX. Table I lists the peak positions of all the dihedral angles of the RDX molecules in the simulation supercell at 480, 490, and 510 K. The NCNN dihedral angles are of particular interest because they dene the nitro group positions in the molecules. Figure 12 shows the distributions of three representative NCNN dihedrals at 480, 490, and 510 K. After the solid-solid phase transition the peaks of the N2C1N1N4 see Fig. 12 a shift slightly, from 180 to 160, while the N1C3N3N6 and N1C1N2N5 dihedral angles undergo more pronounced changes see Figs. 12 b and 12 c . The N1C3N3N6 dihedral angle shifts from 93 to 137, however, the N1C1N2N5 dihedral angle shifts from 116 to 85. These results show that though the molecular conformation in the RDX-SB phase remains AAE, the two axialpositioning nitro groups have different changes, that is, one becomes more axial while the other becomes more equatorial see Fig. 13 . At 510 K, all NCNN dihedral angles peak at 180, indicating an AAE to EEE conformational change upon melting.
IV. CONCLUSIONS

FIG. 11. Examples of distributions of the a CNCN, b HCNC, and c HCNN dihedral angles of the RDX molecules at 480, 490, and 510 K.

We have studied the melting of perfect crystalline RDX using molecular dynamics simulations with the fully exible Smith and Bharadwaj force eld.23 The purpose of the study was to investigate molecular and structural changes that occur during the melting of a large, exible molecule. The molecular structure of RDX see Fig. 1 is a exible sixmember ring with three nitro groups attached at alternating ring atomsthus, it should be fairly representative of large, complex, oppy molecules. The simulations were carried out over the temperature range of 300 650 K for the NST constant stress, constant temperature ensemble. The temperature was increased incrementally followed by equilibrations corresponding to a rate of 2.0 1011 K / s. The changes in the solid upon heating were investigated by computing translational and orientational order parameters. The molecular structural changes were monitored by computing bond lengths, bond angles, and dihedral angles. The major molecular structural changes upon melting are due to changes in the torsional angles. A solid-solid phase transition was observed between 480 and 490 K, and melting temperature between 500 and 510 K. The solid-solid phase transition is characterized by abrupt changes in the crystal unit cell lengths a and b de-

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084505-7

Melting of RDX

J. Chem. Phys. 125, 084505 2006

TABLE I. Peak positions in the dihedral angle distributions of the RDX molecules at 480, 490, and 510 K the atom labels are given in Fig. 1 . Peak position deg Dihedral angle C3N1C1N2 C1N2C3N3 C2N3C3N1 C3N3C2N2 C1N2C2N3 C2N2C1N1 N2C1N1N4 N1C3N3N6 N2C2N3N6 N1C1N2N5 N3C2N2N5 N3C3N1N4 H1C1N1C3 H2C1N1C3 H1C1N2C2 H2C1N2C2 H3C2N2C1 H4C2N2C1 H3C2N3C3 H4C2N3C3 H5C3N3C2 H6C3N3C2 H5C3N1C1 H6C3N1C1
a

Peak position deg Dihedral angle H1C1N1N4 H2C1N1N4 H1C1N2N5 H2C1N2N5 H3C2N2N5 H4C2N2N5 H3C2N3N6 H4C2N3N6 H5C3N3N6 H6C3N3N6 H5C3N1N4 H6C3N1N4 C1N1N4O1 C1N1N4O2 C3N1N4O1 C3N1N4O2 C1N2N5O3 C1N2N5O4 C2N2N5O3 C2N2N5O4 C2N3N6O5 C2N3N6O5 C3N3N6O5 C3N3N6O6 480 K 82 40 130 0 0 140 39 157 154 33 80 35 180 0 0 180 180 0 10 170 15 165 165 16 490 K 87 33 157 43 47 161 0 126 102 0 78 42 180 0 0 180 162 20 20 160 0 180 180 0 510 K 65 55 65 53 52 66 53 66 62 58 62 55 180 0 0 180 180 0 0 180 0 180 180 0

480 K 37 40 47 51 47 40 180 93 90 116 107 161 75 165 75 165 180 65 180 65 69 180 75 167

490 K 37 30 35 46 53 50 160 134 120 85 83 180 75 165 66 180 180 62 180 70 84 159 87 154

510 K
a a a a a a

180 180 180 180 180 180 80 150 75 180 180 75 180 90 84 180 87 150

Broad at peak ranging between 50 see Fig. 11 a .

crease and c increases , density, and electrostatic, bond-angle bending, and dihedral energies. This predicted crystalline phase RDX-SB is orthorhombic and belongs to the Pbca space group. The -RDX RDX-SB transition involves both molecular translation and reorientation. It is irreversible upon cooling from 500 to 300 K. The molecular conforma-

FIG. 12. Distributions of the a N2C1N1N4, b N1C3N3N6, and c N1C1N2N5 dihedral angles of the RDX molecules at 480, 490, and 510 K.

tion in the RDX-SB phase remains AAE, however, the two axial-positioning nitro groups have shifted slightly, that is, one becomes more axial and the other becomes more equatorial. While the RDX-SB phase may be an artifact of the potential we have no evidence that it corresponds to a real phase , it may be representative of the kinds of premelting solid-solid phase transitions that likely characterize the behavior of a molecular crystal when heated to melting point. Melting occurs when the temperature is increased from 500 to 510 K. The melting transition is characterized by abrupt changes in the order parameters, density, diffusion coefcient, potential energy, and dihedral angles. At the high heating rate 2.0 1011 K / s used in the simulations, the melted RDX reaches full orientational disorder at about 540 K and translational freedom at around 580 K. If the simulation at the melting temperature 510 K is run sufciently long complete rotational freedom is achieved in a few hundreds of picoseconds, while complete translational freedom requires much longer see Fig. 9 . These results show that given a sufciently high heating rate as might be generated by a shock , the system can exist for long times in a near-liquid state in which the molecules are not as free to rotate and diffuse as in the true liquid state. The bond lengths and bond angles undergo little change upon melting, while there are signicant changes in the dihedral angles. The distributions of the dihedral angles generally become much broader and atter and the peak positions shift upon melting. The molecular conformation of RDX changes from AAE to EEE upon melting. The ramication of

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084505-8

L. Zheng and D. L. Thompson

J. Chem. Phys. 125, 084505 2006

FIG. 13. Color Molecular congurations of RDX molecules: a 480 K and b 490 K. The C, N, O, and H atoms are denoted by gray, blue, red, and green, respectively.

this for formulating force elds that accurately describe melting is that it is important that the torsional motions be accurately described.
ACKNOWLEDGMENTS

We would like to thank Dr. Thomas D. Sewell for helpful discussions. This work was supported by a DOD MURI grant managed by the Army Research Ofce.
1 2

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Melting of RDX

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