2017
DOI: 10.1021/acs.jpclett.7b01330
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Photofragmentation of Tetranitromethane: Spin-Unrestricted Time-Dependent Excited-State Molecular Dynamics

Abstract: In this study, the photofragmentation dynamics of tetranitromethane (TNM) is explored by a spin-unrestricted time-dependent excited-state molecular dynamics (u-TDESMD) algorithm based on Rabi oscillations and principles similar to trajectory surface hopping, with a midintensity field approximation. The leading order process is represented by the molecule undergoing cyclic excitations and de-excitations. During excitation cycles, the nuclear kinetic energy is accumulated to overcome the dissociation barriers in… Show more

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Cited by 21 publications
(21 citation statements)
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“…To investigate the aforementioned hypothesis, we extracted semiempirical GFN‐xTB single‐point energies of the fragmentation process from selected trajectories producing m/z 43 and m/z 44. The activation energy was computed by subtracting the energy of the most energetic structure from the energy of the optimized geometry molecular ion of tabun (taken as the zero of the energy) 53 . The energy variation along a sample trajectory generating the C 2 H 5 N + fragment ( m/z 43), shown in Figure 11, was used to estimate the activation energy.…”
Section: Resultsmentioning
confidence: 99%
“…To investigate the aforementioned hypothesis, we extracted semiempirical GFN‐xTB single‐point energies of the fragmentation process from selected trajectories producing m/z 43 and m/z 44. The activation energy was computed by subtracting the energy of the most energetic structure from the energy of the optimized geometry molecular ion of tabun (taken as the zero of the energy) 53 . The energy variation along a sample trajectory generating the C 2 H 5 N + fragment ( m/z 43), shown in Figure 11, was used to estimate the activation energy.…”
Section: Resultsmentioning
confidence: 99%
“…TDESMD calculations including spin would be a subject for future studies. 93 In addition, there are multiple channels (dissociation/ionization) and multiphoton processes in the experiments. These processes are assumed small by the present computational modeling as an approximation.…”
Section: Discussionmentioning
confidence: 99%
“…[9][10][11] TDDFT-SH has proven capable of predicting the kinetics of pericyclic ringopening and -closing reactions, [12][13][14][15][16][17][18][19][20] the reactivity of photoexcited metal oxides 21 such as perovskites 22 and titania, [23][24][25] and the branching ratios, kinetic energy distributions, and mass distributions of photodissociation reactions. 26,27 However, the majority of photochemical TDDFT-SH applications to date have included only the ground state and the first excited state. Simulations including several excited states and all nonadiabatic couplings between them have been reported, but rely on approximations with questionable validity such as the neglect of orbital relaxation 17,19,[28][29][30][31][32] or single Slater determinant models for the excited state.…”
Section: Introductionmentioning
confidence: 99%