Decomposition of Condensed Phase Energetic Materials: Interplay between Uni- and Bimolecular Mechanisms Supporting Information

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1 Decomposition of Condensed Phase Energetic Materials: Interplay between Uni- and Bimolecular Mechanisms Supporting Information a David Furman *, a Ronnie Kosloff, a Faina Dubnikova, b Sergey V. Zybin, b William A. Goddard III, a Naomi Rom, a Barak Hirshberg and *c,d Yehuda Zeiri a Fritz Haber Research Center for Molecular Dynamics, Institute of Chemistry, Hebrew University of Jerusalem, Jerusalem 91904, Israel b Materials and Process Simulation Center, California Institute of Technology, Pasadena, California c Biomedical Engineering, Ben Gurion University, Beer-Sheva 94105, Israel d Division of Chemistry, NRCN, P.O. Box 9001, Beer-Sheva 84190, Israel * furman.david@mail.huji.ac.il Figure S1: Time evolution of main species for 1800K and 3500K at 0.7V0 S1

2 Table S1: Parameters obtained by fitting an exponential function to the Potential energy time evolution curve for second stage decomposition (exothermic decay phase) and 1 st order rate model to TNT decomposition curves (endothermic step) T (K) Super cell volume τ exo (ps) Q (cal/g) t max (ps) U 0 (kcal/mol) τ endo V V V V (ps) S2

3 Scheme S1: Hydrogen transfer routes between TNT and TNT-H and the cleavage of C-NO 2 from TNT molecule missing a ring bound hydrogen. Units: kcal/mol. S3

4 Scheme S2: Reactions of TNT radical missing a NO 2 group (TNT-NO 2 ). Units: kcal/mol. S4

5 Scheme S3. Total energies for ortho hydrogen transfer (top part) and further decomposition routes (bottom part). Units: kcal/mol. S5

6 Table S2. Energy barriers and reaction energies, Functional: PBE1PBE, basis set: cc-pvdz, energy values in kcal/mol Reaction E # / E react TNT TNT TS1 C 6 H 2 (NO 2 ) 2 (NOOH)CH 3 (TNT +H )+ C 6 H 2 (NO 2 ) 3 CH 2 (TNT -H) 43.0 / 43.6 C 6 H 2 (NO 2 ) 2 (NOOH)CH 3 (ortho) C 6 H 2 (NO 2 ) 2 (NOOH)CH 3 TS2 C 6 H 2 (NO 2 ) 2 (ONOH)CH / 8.4 C 6 H 2 (NO 2 ) 2 (ONOH)CH 3 TS3 C 6 H 2 (NO 2 ) 2 CH 3 + ONOH 33.9 / 30.1 C 6 H 2 (NO 2 ) 2 (NOOH)CH 3 TS4 C 6 H 2 (NO 2 ) 2 (OH)CH 3 +NO 45.4 / C 6 H 2 (NO 2 ) 2 (NOOH)CH 3 (para) C 6 H 2 (NO 2 ) 2 (NOOH)CH 3 TS2 C 6 H 2 (NO 2 ) 2 (ONOH)CH / 10.2 C 6 H 2 (NO 2 ) 2 (ONOH)CH 3 TS3 C 6 H 2 (NO 2 ) 2 CH 3 + ONOH 35.1 / 34.3 C 6 H 2 (NO 2 ) 2 (NOOH)CH 3 TS4 C 6 H 2 (NO 2 ) 2 (OH)CH 3 +NO 47.8 / C 6 H 2 (NO 2 ) 3 CH 2 (ortho) C 6 H 2 (NO 2 ) 3 CH 2 TS5 C 6 H 2 (NO 2 ) 2 (ONO) CH / -6.0 C 6 H 2 (NO 2 ) 2 (ONO) CH 2 TS6 C 6 H 2 (NO 2 ) 2 (O) CH 2 + NO 4.4 / 1.1 C 6 H 2 (NO 2 ) 3 CH 2 (para) C 6 H 2 (NO 2 ) 3 CH 2 TS5 C 6 H 2 (NO 2 ) 2 (O) CH 2 + NO 54.3 / -0.4 Scheme S4: Total energy changes of RDX decomposition routes. Units: kcal/mol. S6

7 Table S3. DFT values of activation energies of NO 2 cleavage from TNT, RDX and PETN. For TNT ortho and para positions of NO 2 group are with respect to CH 3 group. For RDX the positions are with respect to removed H atom. Asterisk denotes a change in total energy (=bond dissociation energy) in cases where no transition state was found. - No H m/ar indicates a methylic/aromatic hydrogen deficient molecule Case E (kcal/mol) ortho / para #1 TNT TNT + NO * / 67.8 * #2 TNT + TNT + + NO / 42.1 #3 TNT - TNT - + NO / 66.4 #4 TNT-noH m TNT + TNT_noH m + NO / 89.4 * #5 TNT-noH ar TNT + TNT_noH ar + NO / 44.8 #6 RDX RDX + NO * #7 RDX + RDX + + NO #8 RDX - RDX - + NO #9 RDX -noh RDX-noH + NO / 29.4 #10 RDX + RDX RDX+H (C3N6O6H7) + RDX-H (C3N6O6H5) 50.2 #11 RDX 3 (CH2=N-NO2) 71.5 #12 RDX C3N5O4H5 + HONO 40.5 #13 PETN PETN + NO * #14 PETN + PETN + + NO #15 PETN - PETN - + NO #16 PETN -noh PETN -noh (A) + NO #17 PETN -noh PETN -noh (B) + NO For cases #13 and #14: (A) refers to NO 2 cleavage from the same chain where H is absent and (B) refers to a cleavage from a different chain S7

8 ReaxFF-lg force field parameters used in this study: 39! Number of general parameters !Overcoordination parameter !Overcoordination parameter !Valency angle conjugation parameter !Triple bond stabilisation parameter !Triple bond stabilisation parameter !C2-correction !Undercoordination parameter !Triple bond stabilisation parameter !Undercoordination parameter !Undercoordination parameter !Triple bond stabilization energy !Lower Taper-radius !Upper Taper-radius !Not used !Valency undercoordination !Valency angle/lone pair parameter !Valency angle !Valency angle parameter !Not used !Double bond/angle parameter !Double bond/angle parameter: overcoord !Double bond/angle parameter: overcoord !Not used !Torsion/BO parameter !Torsion overcoordination !Torsion overcoordination !Conjugation 0 (not used) !Conjugation !vdWaals shielding !Cutoff for bond order (*100) !Valency angle conjugation parameter !Overcoordination parameter !Overcoordination parameter !Valency/lone pair parameter !Not used !Not used !Molecular energy (not used) !Version number !Valency angle conjugation parameter 4! Nr of atoms; cov.r; valency;a.m;rvdw;evdw;gammaeem;cov.r2;# alfa;gammavdw;valency;eunder;eover;chieem;etaeem;n.u. cov r3;elp;heat inc.;n.u.;n.u.;n.u.;n.u. ov/un;val1;n.u.;val3,vval4 C S8

9 H O N ! Nr of bonds; Edis1;LPpen;n.u.;pbe1;pbo5;13corr;pbo6 pbe2;pbo3;pbo4;etrip;pbo1;pbo2;ovcorr ! Nr of off-diagonal terms; Ediss;Ro;gamma;rsigma;rpi;rpi ! Nr of angles;at1;at2;at3;thetao,o;ka;kb;pv1;pv S9

10 ! Nr of torsions;at1;at2;at3;at4;;v1;v2;v3;v2(bo);vconj;n.u;n S10

11 ! Nr of hydrogen bonds;at1;at2;at3;rhb;dehb;vhb Cutoff of bond orders used for post-analysis of molecular species: C N 0.3 C C 0.55 C O 0.65 C H 0.4 O O 0.65 N O 0.40 O H 0.4 H H 0.55 H N 0.55 N N 0.55 S11

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