Computational Materials Science 38 (2007) 538542 www.elsevier.

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A new method for calculation of elastic properties of anisotropic material by constant pressure molecular dynamics
Kailiang Yin
a

a,b,*

, Dinghui Zou a, Jing Zhong a, Duanjun Xu

Department of Chemical Engineering, Jiangsu Polytechnic University, Jichang Road 75, Changzhou 213016, PR China b Department of Chemistry, Zhejiang University, Hangzhou 310027, PR China Received 10 February 2005; received in revised form 18 May 2005; accepted 20 October 2005

Abstract A new method based on constant pressure molecular dynamics (MD) with the software package Materials Studio (MS) was developed to calculate the anisotropic elastic properties of 1,3,5-tri-amino-2,4,6-tri-nitrobenzene (TATB) which is a typical and widely studied explosive molecular and its single crystal is a typical triclinic lattice. Key points of the method are introduced. Firstly, a P1 periodic super cell of TATB which ab plane was designated as (0 1 0) planar of the crystal was modeled. After several xing and relaxing steps, the cell was pre-equilibrated for 500 ps and followed a 100 ps MD with trajectory at 298 K in NVT ensemble. The averaged isotropic elastic properties were calculated by MS analysis module of elastic properties (static). Secondly, NPT ensemble was chosen and dierent stresses in six dierent directions were added through many tries to keep the cell parameters uctuating around those values in NVT ensemble while performing constant pressure MD. The MS averaged isotropic elastic properties as well as elastic constant matrix of the well equilibrated NPT system were then obtained. Thirdly, dierent magnitude of compressive or tensile stress was applied to the cell in one direction and the equilibrated box lengths were averaged statistically to calculate the strains in three directions. Anisotropic tensile moduli as well as Poissons ratios were then obtained via the strainstress prole and the averaged values over those in three directions were given. Finally, the average values were compared with those in NVT or NPT ensemble to validate the titled method. Deviation within less than 20% revealed that the method can be certainly applied to the study on elastic properties of anisotropic materials. 2006 Elsevier B.V. All rights reserved.
PACS: 46.15.x Keywords: TATB; Constant pressure molecular dynamics; Anisotropic; Elastic properties

1. Introduction 1,3,5-tri-amino-2,4,6-tri-nitrobenzene (TATB) is a wellknown energetic and passive single compound explosive (SCX) [1]. SCXs are some special organic or inorganic compounds, and there have been many studies on their inter-molecular interactions for understanding their properties of condensed phase [25]. Composite explosive
* Corresponding author. Address: Department of Chemical Engineering, Jiangsu Polytechnic University, Jichang Road 75, Changzhou 213016, PR China. Tel.: +86 519 3290253; fax: +86 519 3290011. E-mail address: mat_studio@jpu.edu.cn (K. Yin).

especially polymer bonding explosive (PBX) has many advantages over the SCXs such as high safety performance, mechanical robustness as well as workability. For the composite explosives, there should be paid much attention to their interfacial actions which play an important role in their mechanic properties, sensitivities as well as assembling behaviors. It is increasingly recognized that there would be better wetting and packing between composites with more strong interfacial interaction and binding force [6]. Packing of polymer on the surface of SCX can obviously improve its safety performance and mechanical properties. The research on the improvement of SCXs mechanical properties could be performed by experimental

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or theoretical methods. As a kind of powerful theoretical methods, molecular dynamics (MD) simulation [79] can be used to calculate the mechanical properties; mainly elastic properties of materials. TATB is an anisotropic explosive with dierent mechanical property in each direction, but when applied the software package of Materials Studio (MS) [10] to carry out MD, only the isotropic elastic properties averaged in x, y and z directions of materials can be obtained. To calculate the elastic properties in one direction of such anisotropic materials, we developed a method which is similar to the experimental determination of elastic properties in one direction. This method is based on constant pressure MD and can be eectively used to calculate the elastic properties of anisotropic materials in each direction or surface. 2. Theoretic and simulation section 2.1. Calculation of the elastic properties of isotropic material by MS It is known that the static elastic properties of isotropic material are same in each direction and can be calculated by MS [11]. The method has as follows. For each conguration submitted for static elastic constants analysis, a total of 13 minimizations are performed. The rst consists of a conjugate gradients minimization of the undeformed amorphous system. The target minimum derivative for this initial step is 0.1 kcal/A. Following this initial stage, three tensile and three pure shear deformations of magnitude 0.0005 are applied to the minimized undeformed system and the system is reminimized following each deformation. The internal stress tensor is then obtained from the analytically-calculated virial and used to obtain estimates of the six columns of the elastic stiness coecients matrix. If more than a single conguration has been analyzed, the averages and standard deviations for all the elastic constants and averages for all elastic properties such as tensile or Youngs modulus (E), Poissons ratio (c), shear modulus, bulk modulus, k as well as l would be given. For an anisotropic material, the MS considers it as an isotropic material and the averaged elastic properties in each direction but not the elastic properties in one direction will be obtained. 2.2. Calculation of the elastic properties of anisotropic material by constant pressure MD To calculate the elastic properties of anisotropic materials by MS, we developed a method which is similar to the experimental determination of elastic properties in one direction. The key-point of this method is that the simulated cell must be rstly adjusted to equilibrium in NPT ensemble by applying six dierent external stress rx, ry, rz, rxy, rxz, ryz to the cell. After the sucient equilibration, dierent external stress in one direction was applied to the cell and a constant pressure MD within certain time period

was performed. By averaging the equilibrated box length in each direction, averaged la, lb, lc were obtained and then corresponding change of each of three box length Dl and the strain Dl/l0 could be calculated. By plotting the strainstress prole and tting line by least squares technique, we can calculate the tensile modulus and Poissons ratio in one direction through the slopes of three lines according to the following formula (x as the direction which external stress rx was applied to): Longitudinal strain en Lateral strain eb Dlb ; l0b Dla l0a ec Dlc l0c 1 2

rx rx 3 en Dla =l0a eb Dlb =l0b ec Poissons ratio cb Ea E a ; cc E a rx rx rx 4 Tensile or Youngs modulus Ea 2.3. Modelling and simulation methods TATB single crystal is a typical triclinic lattice with a, b, c 9.010, 9.028, 6.812 A, respectively and a, b, c 108.59, 91.82, 119.97. This explosive crystal is a sti and anisotropic material. In order to calculate the elastic properties in one direction, we performed the following: Firstly, a P1 periodic super cell of TATB with 34.06 36.0 28.838 A was constructed. The cells ab plane was designated as (0 1 0) planar of the crystal and its density was same as the original crystal (1.937 g/cm3). Several xing and relaxing steps were performed to keep the inner layers a crystal-like structure. The way has as follows. After the cell was performed constant temperature MD for 500 ps (which can be seen as a relaxing process) in case of xing those TATB molecules in the inner layers, all xations were released and the cell was relaxed again for another 500 ps. Then, in NVT ensemble at 298 K, the cell was pre-equilibrated for 500 ps and a 100 ps MD simulation was performed and the produced trajectory (T1) was collected for mechanical analysis. The hydrostatic pressure of the system was obtained from analytically-calculated virial and the averaged isotropic tensile modulus, Poissons ratio and other elastic properties were calculated by MS analysis module of elastic properties (static). Secondly, NPT ensemble was chosen and constant pressure MD was performed to obtain the elastic properties in each direction. Dierent stresses in six dierent directions were applied and adjusted to make the cells pressure same as the hydrostatic one and make the cell parameters uctuate around those values in NVT ensemble. After the system was well equilibrated by the constant pressure MD, another 100 ps trajectory (T2) of constant pressure MD was collected for analyzing MS averaged isotropic elastic properties again. Thirdly, dierent magnitude of external compressive or tensile stress was applied to the cell in each direction

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and 500 ps pre-equilibration as well as succedent 100 ps MD with trajectory (T3s) were carried out in NPT ensemble. Under each external stress, longitudinal and lateral strains were obtained by averaging statistically the changes of box length in each of three directions. The elastic properties were then obtained via the strain stress prole. Finally, the calculated anisotropic elastic properties in three directions were averaged and compared with MS isotropic elastic properties to validate the present method. 2.4. Simulation details Molecular dynamics (MD) simulations were carried out using MATERIALS STUDIO 2.2 software package (Accelrys Co.) [10]. The force eld we implemented in this work is Suns COMPASS (Condensed-phase Optimized Molecular Potentials for Atomistic Simulation Studies) [12] which is based on the earlier class II CFF9x and PCFF force elds and is the rst ab initio-based force eld that has been parameterized using extensive data for molecules in the condensed phase. The equations of motion were solved with Verlet velocity algorithm [13]. The time step of integration was set to 1 fs in all cases. The summation methods for van der Waals and Coulomb forces were all atom based (cuto, spline width and buer width was 9.5, 1.0 and 0.5 A, respectively). Initial velocities were randomly designated from Boltzmann distribution. Temperature was set to 298 K and controlling method was Andersen [14] with every 690 steps of collision frequency. The method of pressure control is Parrinello method [15]. The cell mass is set to 20.00 a.m.u. The MD trajectory was obtained by saving the coordinates and velocities of all atoms at each 100 fs (i.e. output a frame every 100 fs). MS static elastic properties were calculated by its Analysis module while the values of strain under dierent stress were obtained from analyzing the data of the corresponding trajectory (T3). 3. Results and discussion 3.1. Elastic properties and elastic constant matrix By analyzing the data in the trajectory T1, an average value of hydrostatic pressure of TATB system in equilibrated NVT ensemble was calculated by setting the analytical-virial as 17.33 GPa. The MS static isotropic elastic properties of interest are the tensile modulus (GPa), Poissons ratio, bulk modulus (GPa), shear modulus (GPa), k and m with values 1796, 0.231, 1113, 729.3, 627.3 and 729.3, respectively. Among these results, the Poissons ratio is in a reasonable range from 0 to 0.5. It demonstrates that the system has a certain deformability which can be seen from Fig. 1. The other elastic properties seem larger (means high hardness). The main reasons we explained here are that (1) the modeled system is a perfect, periodic and space-continuous crystal-like system, so the calculated Constant 2363 1122 1106 128.3 262.3 17.69 Standard 46.21 19.17 47.46 18.15 26.29 13 elastic matrix (GPa) 1123 1107 127.8 3466 1185 934.7 1186 3225 40.03 9.366 40.13 1081 366.4 478.1 93.67 260.3 178 125 deviation 19.2 25.75 37.48 12.82 12.72 9.589 matrix (GPa) 47.17 18.13 37.41 12.9 96.92 18.07 18.01 11.8 29.41 6.656 10.24 7.343 261.6 366.2 477.1 93.54 873 161.6 26.33 12.69 29.61 6.622 14.19 6.013 17.7 260 177.5 124.9 161.5 1357 13.08 8.567 10.44 7.332 5.974 11.61

Fig. 1. Illustration of TATB P1 cell after MD equilibration in NVT ensemble.

elastic properties can be seen as ideal ones and reect a kind of ideal hardness; (2) although COMPASS is a very powerful empirical force eld for the calculations of the condensed materials, its parametrization may not include such TATB molecule containing three ONO bonds. Even so, as for a new method, these data can be seen as reference values to validate the method. In NPT ensemble, when the external stresses rx, ry, rz, rxy, rxz, ryz (in GPa) applied to the cell in six directions were 47, 95, 4, 16.5, 14.8 and 32, the hydrostatic pressure of the system could be maintained at 17.33 GPa, and the cell density as well as other parameters could be kept uctuating around the aimed values (those in NVT ensemble) within less than 0.1% deviation during the constant pressure MD simulation. The averaged MS isotropic elastic properties and elastic constant matrix based on T2 have the following values: Tensile modulus: 2361 GPa, Poissons ratio: 0.273, bulk modulus: 1765 GPa, shear modulus: 940 GPa, k: 1138, m: 940.

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Fig. 2. The strainstress proles of the TATB cell in direction b and c when applied dierent extra external stress ry to the cell and after equilibration by constant pressure MD.

From the above results, we can discuss that: in the NPT ensemble, (1) both matrices show a good diagonally symmetric relationship, i.e. Cmn = Cnm, with in total 21 independent elastic constants which agrees with that of extreme anisotropic materials, and the good symmetry also means that the system had been well equilibrated by constant pressure MD; (2) there are some deviations of MS elastic properties from those in NVT ensemble, maybe due to the dierences of the cell shape and/or the simulation conditions between two systems. 3.2. Calculation of anisotropic elastic properties When applied a certain extra external stress in one direction to the cell, one longitude as well as two lateral strains could be obtained based on the formula (1) and (2) (where l0a, l0b, l0c is 33.9285, 36.0075, 28.8726 A, respectively, and Dla = la l0a) and the statistical averaged values of the box length a, b, c (la, lb, lc) which were extracted from the corresponding trajectory T3. By plotting the strainstress proles and tting them in lines by the least square method (an example was given in Fig. 2, in which the correlative coefcients R2 are 0.999 and 0.958, respectively, both show very good linear relations), the tensile modulus as well as Poissons ratio could be calculated from the slopes based on the formulas (3) and (4). The results of the calculated anisotropic tensile moduli and Poissons ratios as well as those in NVT and NPT ensembles are listed in Table 1. From the data in Table 1, we can discuss that, (1) the TATB system shows an obvious anisotropy with dierent elastic properties in three directions whereas it can not be observed from MS mechanical analysis; (2) the averaged values of tensile modulus and Poissons ratio over three directions are well comparable with MS value either in

Table 1 The calculated tensile moduli (GPa) and Poissons ratios in each direction and averaged ones as well as those isotropic average values (MS value) in NVT (a) and NPT (b) ensembles Direction a Ea 1423 cb cc 0.253 0.233 Direction b Eb 2558 ca cc 0.309 0.189 Direction c Ec 1955 ca cb 0.134 0.185 Averaged E 1979 c 0.217 MS value E 1796a c 0.231a 0.273b 2361b

NVT or NPT ensemble within less than 20% deviation, which means that the titled method can be applied to the calculation of the elastic properties of anisotropic materials. 4. Conclusion A new method was developed in the present work for calculating the elastic properties of anisotropic materials by Materials Studio software package. By applying constant pressure MD, tensile moduli and Poisson ratios in three directions a, b, c of a modeled anisotropic TATB P1 periodic system were calculated. The averaged values over three directions are well comparable with those isotropic values (referenced values) obtained by MS mechanical analysis in NVT or NPT ensemble. The results demonstrate that the titled method can be eciently applied to calculate anisotropic elastic properties. The development of this method would extend the application of MS to the study on mechanical properties of any anisotropic material. Acknowledgements The author wishes to thank the anonymous referees for their careful reading of the manuscript and their fruitful

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