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

Lianqing Zheng and Donald L. Thompson

Citation: The Journal of Chemical Physics 125, 084505 (2006); doi: 10.1063/1.2238860
View online: http://dx.doi.org/10.1063/1.2238860
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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 flexible force
field 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 insufficient 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 sufficiently 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 sufficiently high heating rate, the system can exist for significant 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
significant changes in the dihedral angles. The molecular conformation of RDX changes from AAE
to EEE upon melting. The ramification of this for formulating force fields 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 difficult. 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
field 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 flexible models of nitromethane, concluding that the melting point is predicted equally well with either model. The molecular
structure does not undergo significant change upon melting.8
In a study of a somewhat larger, more flexible 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

Electronic mail: thompsondon@missouri.edu

0021-9606/2006/1258/084505/9/$23.00

crystals of larger, floppier 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,
flexible molecule.
Figure 1 shows the molecular configuration of -RDX;
the labeling of the atoms will be used in subsequent discus-

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

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L. Zheng and D. L. Thompson

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 first 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 first 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
confirm 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 field

The fully flexible force field developed by Smith and

Bharadwaj23 SB was used for the simulations. This force
field was at first 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 field
to study the physical properties of crystalline and liquid
HMXs, such as density, lattice parameters,25 elastic
properties,26 shear viscosity coefficient,27 and thermal
conductivity.28 Based on the similarities of the molecular

structures of HMX and RDX, we assume that the force field

realistically describes RDX without any modifications except
for the atomic partial charges. The total potential energy
Utotal of this force field 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

i=1 j=i+1

Utotal =

kc

q iq j
Cij
+ Aij exp BijRij 6
Rij
Rij

Ks
KB
r r02 +
0 2
2
2
angles

bonds

proper dihedrals

outofplane bends

KT
1 cosn
2
KO 2
,
2

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 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 configuration of each simulation was the last
configuration 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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J. Chem. Phys. 125, 084505 2006

Melting of RDX

To monitor the changes in the system with increasing

temperature, we define translational T and orientational
O order parameters,
N

rref
1 m
i ri
=
cos 2 ref 2

Nm i=1
ri
T

and
N

1 m
ref
=
2 .
nCCC,i . nCCC,i
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 defined
as
ref
.
cosi = nCCC,i nCCC,i

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 fitting the isotherm up to 4 GPa to
the third-order Birch-Murnaghan equation35

3
PV = B
2

V
V0

V
V0

7/3

V
V0

5/3

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.

The density and diffusion coefficient 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 coefficient 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 field that is a combination of
the generalized AMBER Ref. 38 intramolecular interactions
and the Sorescu-Rice-Thompson SRT force field.29 The
AMBER-SRT force field predicts 439 K for the thermodynamic melting point, in reasonable agreement with the mea-

3
1 4 B
4

2/3

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 fitting 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 coefficient of RDX as functions of temperature. The rate of heating was 10 K / 50 ps 2.0 1011 K / s.

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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 bd 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 field, 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 coefficient. 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 significant 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 field, and we will refer to it as RDX-SB. There are
insufficient 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 field. Though the
difference of the densities of the two solid phases is quite
small, the unit cell edge lengths differ significantly, 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 significant orientational changes occur in
the solid-solid phase transition. The orientational fluctuations
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 significant 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 fluctuations also significantly increase from about 0.05 to about
0.125 2. These results show that there is significant thermal fluctuation 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

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.

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 first 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. 8a. 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.

J. Chem. Phys. 125, 084505 2006

FIG. 9. Plots of the logarithm of the orientational and translational order

parameters vs the simulation time at 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. 8b. When the temperature is increased to the melting temperature, the supercell
volume begins to expand abruptly see Fig. 8c, and the
order parameters are found to drop quickly see Fig. 8d.
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 final
value of 0.35 while the translational order parameter seems
to reach an equilibrium value of 0.77, well above the final
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 figure 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 final
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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J. Chem. Phys. 125, 084505 2006

L. Zheng and D. L. Thompson

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 significant 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 flat peak ranging between 50 after the
RDX crystal is melted see Fig. 11a. This indicates that the
ring structure of RDX in the liquid phase changes significantly 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. 11b. When RDX

melts the peak widths in the distributions become much
larger at least twice those for crystalline RDX and the peak
heights decrease significantly. There is a shoulder at 135
on the distribution for the liquid phase. Figure 11c 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 define 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. 12a shift slightly, from 180 to 160, while the
N1C3N3N6 and N1C1N2N5 dihedral angles undergo
more pronounced changes see Figs. 12b and 12c. 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 flexible
Smith and Bharadwaj force field.23 The purpose of the study
was to investigate molecular and structural changes that occur during the melting of a large, flexible molecule. The
molecular structure of RDX see Fig. 1 is a flexible sixmember ring with three nitro groups attached at alternating
ring atomsthus, it should be fairly representative of large,
complex, floppy 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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Melting of RDX

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.

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

Peak position deg

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

510 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

a
a
a
a
a
a

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

Peak position deg

Dihedral
angle

480 K

490 K

510 K

H1C1N1N4
H2C1N1N4
H1C1N2N5
H2C1N2N5
H3C2N2N5
H4C2N2N5
H3C2N3N6
H4C2N3N6
H5C3N3N6
H6C3N3N6
H5C3N1N4
H6C3N1N4
C1N1N4O1
C1N1N4O2
C3N1N4O1
C3N1N4O2
C1N2N5O3
C1N2N5O4
C2N2N5O3
C2N2N5O4
C2N3N6O5
C2N3N6O5
C3N3N6O5
C3N3N6O6

82
40
130
0
0
140
39
157
154
33
80
35
180
0
0
180
180
0
10
170
15
165
165
16

87
33
157
43
47
161
0
126
102
0
78
42
180
0
0
180
162
20
20
160
0
180
180
0

65
55
65
53
52
66
53
66
62
58
62
55
180
0
0
180
180
0
0
180
0
180
180
0

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

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
coefficient, 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 sufficiently 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 sufficiently 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 significant changes in the dihedral angles. The distributions of the dihedral angles generally become much broader and flatter and the peak positions
shift upon melting. The molecular conformation of RDX
changes from AAE to EEE upon melting. The ramification of

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084505-8

J. Chem. Phys. 125, 084505 2006

L. Zheng and D. L. Thompson

FIG. 13. Color Molecular configurations 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 fields 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 Office.
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