energy density material - royal society of · pdf fileenergy density material usupplemental...

UFirst Principles Prediction of an Insensitive High

Energy Density Material

USupplemental Information

Barak Hirshberg P

1,2,*P and Chagit Denekamp P

2

1. The Fritz Haber Center for Molecular Dynamics, The Hebrew University,

Jerusalem, 91904, Israel

2. RAFAEL Ltd. P.O. Box 2250. Haifa 3102102, Israel.

*Corresponding author. UEmail U: [email protected] U1T

UTel U: +972 (4) 8795870. UFax U: +972 (4) 8794887.

1. Computational details

In order to validate our results for the gas phase properties of H3tta, the

minimum structure was also located at the MP2/cc-pVTZ P0F

1,1F

2P level of

theory. The structure obtained is very similar to the one obtained at the

B3LYP/6-31G(d) P2F

3,3F

4,4F

5P level of theory (e.g. maximal variation of 0.03 Ǻ in

bond lengths). Both structures are given below. Dimer calculations, due

to the larger number of heavy atoms, were done using the BLYP

functional P5F

6,6F

7P with the 6-31G(d) basis set. The detonation properties of

H3tta were also calculated using the Kamlet-Jacobs method P7F

8P to compare

to the more reliable EXPLO5 results.

2. Clusters Equilibrium Structure

The geometry obtained for a dimer of H3tta molecules is shown in Figure

1.

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical PhysicsThis journal is © The Owner Societies 2013

mailto:[email protected]

Figure 1 Equilibrium Geometry for the H3tta dimer at the B3LYP/6-31G(d) level of theory

The existence of the dimer was used in generating the initial geometry

for PW-DFT optimization. The initial unit cell parameters for the P1

phase were chosen in order to generate a structure of 2 dimers on top of

the other, shifted by an angle of approximately 750. The geometry used

as initial guess is shown in Figure 2.

Figure 2 Initial geometry for PW-DFT optimization shown in top view (l.h.s) and side view (r.h.s).

3. Kamlet Jecobs method The detonation properties of H3tta were also evaluated using the

Kamlet-Jacobs method. This method uses an empirical relation, given in

equation (1), between detonation velocity (D) or pressure (P) and ρ0, N,

M and Q; where ρ0 is the density of the solid, N is the number of moles


of gas released during detonation, M is the average molecular weight of

the gas released and Q is the heat of detonation. This method has been

used extensively in the literature for evaluating the performance of

possible HEDMs (for recent examples, see ref. 7a and 7b in the main

article).

(1) )3.11()(01.1

)(58.15

021

21

21

21

21

20

ρ

ρ

⋅+⋅=

⋅=

QNMD

QNMP

The initial density used in this study is the one obtained from PW-DFT

calculations for each of the crystal structures. In order to evaluate N, M

and Q the reaction presented in Figure 3 was used. Q is the heat of

detonation and is defined as the negative of the difference between the

heat of formation of the products and the heat of formation of the

explosive. This procedure resulted in values of 0.0332 mole g P

-1P, 25.7889 g

mole P

-1P for N and M, respectively. The effect of variation in the solid state

heat of formation of each phase on the detonation properties was also

tested. Q was found to be between 1129 cal g P

-1P and 1218 cal gP

-1P for the

P1 phase and between 1132 cal g P

-1P and 1221 cal g P

-1P for the P2R1R phase.

The values of D and P obtained, using equation (1), for the P1 phase are

8314-8473 msP

-1P and 316-328 kbar, respectively. For the P2R1R phase D and

P were found to be 8658-8822 msP

-1P and 353-367 kbar, respectively.

These values are in accord with the EXPLO5 results reported in the main

article.

NN N

NH

N NN

NNHNNN

NH3 19N2(g) + H2(g) + 8C(s) + CH4(g) + NH3(g)


Figure 3 Detonation reaction used to estimate N,M and Q for the Kamlet

Jacobs method.

4. Geometries

H3tta B3LYP/6-31G(d) E(RB+HF-LYP): -827.73223200 Hartree N 0.000000 0.000000 0.000000 C 0.000000 1.396816 0.000000 C -1.209678 -0.698408 0.000000 N -1.086866 2.186081 0.000000 N 1.080471 2.156949 0.000000 N 0.621973 3.440913 0.000000 N -0.665073 3.475051 0.000000 H -2.062641 1.890877 0.000000 N -1.349769 -2.034294 0.000000 N -2.408208 -0.142759 0.000000 N -3.290905 -1.181812 0.000000 N -2.676946 -2.313496 0.000000 H -0.606227 -2.731738 0.000000 C 1.209678 -0.698408 0.000000 N 1.327737 -2.014190 0.000000 N 2.436635 -0.151787 0.000000 N 2.668931 -2.259101 0.000000 N 3.342019 -1.161555 0.000000 H 2.668868 0.840861 0.000000 H3tta MP2/cc-pVDZ E(MP2): -825.56944607 Hartree N 0.000000 0.000000 0.000000 C -0.005692 0.000000 1.395432 C 1.211325 0.000000 -0.692786 N 1.086694 0.000000 2.187105 N -1.096767 0.000000 2.160984 N -0.637696 0.000000 3.443807 N 0.679506 0.000000 3.472278 H 2.064729 0.000000 1.873264 N 1.350742 0.000000 -2.034657 N 2.419851 0.000000 -0.130664 N 3.301273 0.000000 -1.169643 N 2.667327 0.000000 -2.324609 H 0.589930 0.000000 -2.724740 C -1.205633 0.000000 -0.702645 N -1.323084 0.000000 -2.030320 N -2.437436 0.000000 -0.152448 N -2.663577 0.000000 -2.274164 N -3.346834 0.000000 -1.147669 H -2.654659 0.000000 0.851475 H3tta dimer BLYP/6-31G(d) E(RB-LYP): -1655.17067252 Hartree


N 0.111285 -0.003305 0.111985 N 0.135505 -0.002177 1.486809 N 1.355108 -0.002892 -0.292215 C 1.434688 -0.001181 1.871606 H -0.729090 -0.002158 2.053750 N 2.215535 -0.001605 0.781439 N 1.911604 0.000063 3.194631 C 3.298525 0.001089 3.444525 C 1.002511 0.000226 4.272792 N 4.275787 0.001318 2.503222 N 3.859614 0.002120 4.657964 N -0.326577 -0.000764 4.152675 N 1.335814 0.001602 5.588074 N 5.490499 0.002185 3.151128 H 4.146470 0.000863 1.482889 N 5.223900 0.002717 4.430864 N -0.808404 -0.000322 5.449725 N 0.168951 0.001044 6.318729 H 2.285635 0.002765 5.982827 N -1.914523 -0.007175 -4.141710 N -2.396342 -0.006557 -2.844656 N -2.891884 -0.008333 -5.010708 C -3.725431 -0.007335 -2.964766 N -4.058742 -0.008529 -4.280045 N -4.634518 -0.007038 -1.886599 H -5.008566 -0.009391 -4.674793 C -4.157592 -0.005827 -0.563577 C -6.021440 -0.007948 -2.136485 N -2.858407 -0.004867 -0.178789 N -4.938432 -0.005423 0.526596 N -6.582536 -0.009079 -3.349920 N -6.998696 -0.007828 -1.195176 N -2.834178 -0.003871 1.196034 H -1.993818 -0.004840 -0.745740 N -4.077997 -0.004204 1.600243 N -7.946821 -0.009620 -3.122811 N -8.213412 -0.008894 -1.843073 H -6.869372 -0.007080 -0.174843

P21 unit cell geometry total energy = -850.76180336 Ry

N -0.166607070 -0.000003802 0.166599378 C -0.006759159 -0.000002246 0.335406469 C -0.157653304 -0.000004626 0.006709979 N 0.166626791 -0.000004549 0.368832529 N -0.004805951 0.000002040 0.493454257 N 0.173266776 0.000001666 0.624200523 N 0.277948076 -0.000002112 0.552265435 H 0.214902237 -0.000008311 0.278394128 N -0.297659885 -0.000003196 -0.166663874 N -0.001528408 -0.000007305 0.004846927 N -0.048836572 -0.000009352 -0.173190238 N -0.225510196 -0.000006941 -0.277927179 H -0.436401084 0.000006901 -0.215078651 C -0.335475277 -0.000000531 0.157579511 N -0.493502044 0.000000467 0.001452841 N -0.368852382 0.000000956 0.297544957 N -0.624264010 0.000001995 0.048697258


N -0.552312195 0.000002121 0.225348534 H -0.278517270 -0.000003174 0.436280906

N 0.166607070 0.499996198 -0.166599378 C 0.006759159 0.499997754 -0.335406469 C 0.157653304 0.499995374 -0.006709979 N -0.166626791 0.499995451 -0.368832529 N 0.004805951 0.500002040 -0.493454257 N -0.173266776 0.500001666 -0.624200523 N -0.277948076 0.499997888 -0.552265435 H -0.214902237 0.499991689 -0.278394128 N 0.297659885 0.499996804 0.166663874 N 0.001528408 0.499992695 -0.004846927 N 0.048836572 0.499990648 0.173190238 N 0.225510196 0.499993059 0.277927179 H 0.436401084 0.500006901 0.215078651 C 0.335475277 0.499999469 -0.157579511 N 0.493502044 0.500000467 -0.001452841 N 0.368852382 0.500000956 -0.297544957 N 0.624264010 0.500001995 -0.048697258 N 0.552312195 0.500002121 -0.225348534 H 0.278517270 0.499996826 -0.436280906 P1 unit cell geometry total energy = -850.75786668 Ry N -0.615100334 -1.443063101 -0.257211886 N -1.477554591 -0.484310810 0.142196734 N -1.303804778 -2.522775680 -0.466740202 C -2.700686348 -1.028225558 0.159495990 H -1.175960906 0.489198182 0.339459045 N -2.619152184 -2.300643400 -0.218263149 N -3.896765212 -0.384618795 0.478317506 C -5.077523547 -1.113701531 0.483402973 C -3.903988154 0.982439974 0.751752258 N -5.239276751 -2.408811472 0.136326555 N -6.249381947 -0.612906881 0.830172205 N -2.796099136 1.720414176 0.749234296 N -4.958371417 1.761948251 1.071080036 N -6.538985603 -2.720576714 0.279975172 H -4.528406445 -3.091683790 -0.160211362 N -7.123275201 -1.636276610 0.688865151 N -3.186804644 2.968306060 1.076452694 N -4.472311483 3.014484255 1.271690386 H -6.005357114 1.594929990 1.128675218 N 3.186979919 -2.968467403 -1.076214491 N 2.796417572 -1.720610939 -0.748962244 N 4.472669444 -3.014652853 -1.271726055 C 3.904174285 -0.982690136 -0.751410566 N 4.958345555 -1.762019546 -1.071462006 N 3.896917884 0.384305225 -0.478442618 H 6.005166941 -1.595294795 -1.129376476 C 2.700839818 1.027706609 -0.159230880 C 5.077585371 1.113431155 -0.483622980 N 1.477684417 0.483957150 -0.141503993 N 2.619188413 2.300189332 0.218218583 N 6.249390198 0.612707916 -0.830727512 N 5.239250401 2.408604672 -0.136817271 N 0.615264571 1.442573754 0.257783372 H 1.176301344 -0.489356760 -0.338774094 N 1.303949382 2.522243716 0.467038522 N 7.123246357 1.636161472 -0.689659059


N 6.538928062 2.720422562 -0.280523770 H 4.528471801 3.091367325 0.159946438

5. IR Spectrum

P1 Phase # mode [cm-1] [THz] IR 4 32.27 0.9674 0.0000 5 45.66 1.3688 0.0071 6 73.85 2.2140 0.0086 7 73.97 2.2175 0.6952 8 96.33 2.8879 0.0000 9 103.50 3.1029 0.1976 10 115.53 3.4636 0.0000 11 117.57 3.5246 0.0000 12 128.76 3.8603 0.0000 13 135.91 4.0744 0.0000 14 139.92 4.1948 0.1559 15 144.68 4.3375 0.0001 16 149.26 4.4748 0.0743 17 150.46 4.5108 0.0003 18 162.29 4.8654 1.9720 19 174.91 5.2436 0.0000 20 182.00 5.4563 1.5664 21 184.76 5.5391 0.4477 22 189.69 5.6867 0.0000 23 192.32 5.7657 0.7230 24 211.48 6.3400 0.0000 25 300.56 9.0105 0.0231 26 304.31 9.1229 0.0000 27 309.86 9.2894 0.0000 28 310.67 9.3136 0.0315 29 324.69 9.7340 0.2984 30 328.10 9.8362 0.0000 31 379.85 11.3876 0.0001 32 380.90 11.4192 0.1576 33 396.34 11.8818 0.0000 34 402.46 12.0655 0.9418 35 405.74 12.1638 3.5579 36 423.38 12.6925 0.0000 37 442.77 13.2738 0.0006 38 443.41 13.2932 0.3985 39 673.84 20.2011 0.0056 40 674.12 20.2095 0.4425 41 679.70 20.3769 0.5967 42 684.15 20.5104 0.0000 43 685.56 20.5525 1.0139 44 686.02 20.5664 0.0005 45 713.28 21.3836 0.0000 46 713.64 21.3943 0.0618 47 716.19 21.4710 0.2827 48 716.20 21.4712 0.1066 49 719.64 21.5742 0.6000 50 719.68 21.5755 0.0814 51 826.93 24.7907 6.2990 52 827.46 24.8067 1.5020 53 836.36 25.0736 0.0066


54 847.68 25.4129 3.6575 55 880.06 26.3836 3.4573 56 881.79 26.4353 0.0008 57 888.19 26.6272 0.0001 58 889.18 26.6570 0.3899 59 983.28 29.4780 9.3646 60 984.85 29.5249 0.2802 61 986.34 29.5697 8.0819 62 987.49 29.6041 0.0082 63 994.15 29.8039 0.0001 64 996.63 29.8781 0.0002 65 1000.40 29.9913 10.0724 66 1007.83 30.2140 0.0017 67 1016.62 30.4774 3.6633 68 1027.39 30.8004 5.4788 69 1030.32 30.8884 6.0691 70 1038.30 31.1273 0.0003 71 1042.86 31.2641 14.4369 72 1045.32 31.3378 0.0231 73 1057.04 31.6894 0.0065 74 1059.96 31.7769 1.4257 75 1067.35 31.9984 0.0105 76 1069.07 32.0500 1.1836 77 1087.51 32.6027 0.0001 78 1092.52 32.7529 0.7791 79 1115.10 33.4298 0.2940 80 1119.85 33.5724 0.0000 81 1141.52 34.2220 0.0019 82 1143.44 34.2796 0.4612 83 1151.80 34.5300 1.2066 84 1156.87 34.6822 0.0000 85 1201.14 36.0094 5.6180 86 1208.09 36.2175 0.0006 87 1209.13 36.2489 1.8807 88 1217.41 36.4969 0.0009 89 1221.40 36.6168 1.2654 90 1222.49 36.6492 0.1435 91 1304.07 39.0949 0.1004 92 1304.16 39.0979 0.5298 93 1315.25 39.4303 0.0001 94 1329.60 39.8603 0.6510 95 1345.70 40.3431 0.0010 96 1347.20 40.3881 4.8719 97 1378.13 41.3154 0.0000 98 1381.12 41.4049 0.0422 99 1431.09 42.9029 4.3892 100 1433.19 42.9661 0.0159 101 1460.43 43.7826 0.0000 102 1465.12 43.9231 0.1095 103 1527.77 45.8014 0.3213 104 1529.15 45.8429 13.4655 105 1539.27 46.1460 1.3712 106 1539.88 46.1646 37.7598 107 1563.63 46.8764 41.0880 108 1583.78 47.4804 0.0004 109 2790.25 83.6495 0.2131 110 2819.08 84.5139 160.1097 111 3175.81 95.2084 0.2468 112 3196.84 95.8388 55.4813 113 3328.67 99.7909 39.7874 114 3331.63 99.8798 0.8089


P21 Phase # mode [cm-1] [THz] IR 4 12.76 0.3826 0.0000 5 14.30 0.4288 0.0000 6 29.06 0.8713 0.0000 7 31.12 0.9328 0.0000 8 101.83 3.0526 0.0000 9 102.01 3.0582 0.0000 10 114.12 3.4211 0.3491 11 123.24 3.6948 0.0000 12 123.63 3.7062 0.0000 13 125.78 3.7709 0.0000 14 151.51 4.5422 3.4311 15 162.95 4.8852 0.0001 16 164.41 4.9290 0.0001 17 164.50 4.9315 0.0001 18 184.30 5.5252 0.0000 19 184.42 5.5289 0.0000 20 187.29 5.6149 0.9684 21 187.49 5.6207 0.9713 22 195.50 5.8608 0.0000 23 195.58 5.8632 0.0000 24 215.64 6.4648 0.0000 25 294.49 8.8286 0.0000 26 294.59 8.8316 0.0000 27 308.41 9.2458 0.0000 28 314.20 9.4196 0.0000 29 319.47 9.5774 0.0000 30 319.51 9.5787 0.0000 31 383.84 11.5073 0.0000 32 384.29 11.5208 0.0000 33 401.07 12.0238 0.8999 34 401.20 12.0276 0.9235 35 401.28 12.0301 0.0000 36 401.33 12.0316 0.0000 37 440.99 13.2207 0.5327 38 446.89 13.3975 0.0000 39 674.45 20.2196 0.0000 40 674.56 20.2228 0.0000 41 675.05 20.2375 0.0001 42 675.14 20.2402 0.0000 43 677.18 20.3013 3.0065 44 678.68 20.3464 0.0000 45 716.45 21.4787 0.0000 46 716.50 21.4802 0.0000 47 716.91 21.4924 0.0000 48 716.96 21.4940 0.0000 49 719.74 21.5772 0.0000 50 721.83 21.6399 0.5516 51 812.26 24.3510 18.4332 52 813.86 24.3989 0.0000 53 814.61 24.4214 0.0000 54 822.72 24.6644 0.0033 55 823.48 24.6872 0.0416 56 832.58 24.9602 0.0000 57 884.59 26.5192 0.5415 58 884.70 26.5227 0.5352 59 885.99 26.5613 0.0000


60 886.05 26.5632 0.0000 61 991.19 29.7150 14.8387 62 991.33 29.7194 14.6243 63 992.02 29.7400 0.0000 64 992.17 29.7444 0.0000 65 999.67 29.9693 0.0017 66 1003.88 30.0957 0.0000 67 1006.59 30.1769 0.0011 68 1014.17 30.4041 0.0000 69 1025.64 30.7478 0.0000 70 1025.72 30.7502 0.0000 71 1030.88 30.9050 3.6076 72 1030.96 30.9075 3.6599 73 1044.72 31.3198 0.0000 74 1046.04 31.3594 0.0001 75 1078.44 32.3308 1.0714 76 1078.48 32.3320 1.0782 77 1082.20 32.4436 0.0000 78 1082.26 32.4452 0.0000 79 1123.23 33.6735 0.0000 80 1124.31 33.7059 0.0000 81 1145.87 34.3522 0.2567 82 1145.98 34.3556 0.2528 83 1148.04 34.4175 0.0000 84 1148.18 34.4216 0.0000 85 1188.12 35.6189 0.0000 86 1190.86 35.7011 0.0066 87 1194.73 35.8170 1.7135 88 1195.24 35.8324 1.7081 89 1198.09 35.9180 0.0000 90 1198.61 35.9335 0.0000 91 1292.78 38.7565 0.0000 92 1293.68 38.7836 0.0002 93 1311.24 39.3101 0.0000 94 1311.73 39.3246 0.0000 95 1315.16 39.4274 1.0457 96 1315.57 39.4397 1.0235 97 1378.05 41.3128 0.0000 98 1379.40 41.3534 0.0000 99 1447.53 43.3958 1.8259 100 1447.86 43.4059 1.8702 101 1451.83 43.5247 0.0000 102 1452.15 43.5344 0.0000 103 1531.38 45.9097 0.0178 104 1532.08 45.9305 0.0000 105 1551.03 46.4988 47.9160 106 1551.99 46.5274 47.8378 107 1558.57 46.7249 0.0000 108 1559.49 46.7522 0.0000 109 3298.31 98.8808 0.0000 110 3300.34 98.9418 1.4251 111 3307.11 99.1447 79.6773 112 3308.35 99.1817 80.5253 113 3309.74 99.2235 0.0000 114 3311.03 99.2620 0.0000


1 C. Møller and M.S. Plesset Phys. Rev. 1934, 46, 618-622.

2 T.H. Dunning Jr. J. Chem. Phys. 1989, 90, 1007-1023.

3 A.D. Becke J. Chem. Phys. 1993, 98, 5648-5652.

4 P.C. Hariharan and J.A. Pople Theor. Chim. Acta 1973, 28, 213-222.

5 P.J. Stephens, F.J. Devlin, C.F. Chabalowski and M.J. Frisch J. Phys. Chem. 1994, 98, 11623-

11627.

6 A.D. Becke Phys. Rev. A 1988, 38, 3098-3100.

7 C. Lee, W. Yang and R.G. Parr Phys. Rev. B 1988, 37, 785-789.

8 M.J. Kamlet and S.J. Jacobs J. Chem. Phys. 1968, 48, 23-35.


http://publish.aps.org/search/field/author/Chr.%20M%C3%B8ller

https://samba.huji.ac.il/+CSCO+0h756767633A2F2F63686F797666752E6E63662E626574++/search/field/author/Chengteh%20Lee

energy density material - royal society of · pdf fileenergy density material usupplemental...

Documents