Mixed quantum/classical investigation of the photodissociation of N H3 (Ã) and a practical method for maintaining zero-point energy in classical trajectories

David Bonhommeau, Donald G. Truhlar

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Abstract

The photodissociation dynamics of ammonia upon excitation of the out-of-plane bending mode (mode 2 with n2 =0,6 quanta of vibration) in the à electronic state is investigated by means of several mixed quantum/classical methods, and the calculated final-state properties are compared to experiments. Five mixed quantum/classical methods are tested: one mean-field approach (the coherent switching with decay of mixing method), two surface-hopping methods [the fewest switches with time uncertainty (FSTU) and FSTU with stochastic decay (FSTU/SD) methods], and two surface-hopping methods with zero-point energy (ZPE) maintenance [the FSTUSD+trajectory projection onto ZPE orbit (TRAPZ) and FSTUSD+minimal TRAPZ (mTRAPZ) methods]. We found a qualitative difference between final N H2 internal energy distributions obtained for n2 =0 and n2 >1, as observed in experiments. Distributions obtained for n2 =1 present an intermediate behavior between distributions obtained for smaller and larger n2 values. The dynamics is found to be highly electronically nonadiabatic with all these methods. N H2 internal energy distributions may have a negative energy tail when the ZPE is not maintained throughout the dynamics. The original TRAPZ method was designed to maintain ZPE in classical trajectories, but we find that it leads to unphysically high internal vibrational energies. The mTRAPZ method, which is new in this work and provides a general method for maintaining ZPE in either single-surface or multisurface trajectories, does not lead to unphysical results and is much less time consuming. The effect of maintaining ZPE in mixed quantum/classical dynamics is discussed in terms of agreement with experimental findings. The dynamics for n2 =0 and n2 =6 are also analyzed to reveal details not available from experiment, in particular, the time required for quenching of electronic excitation and the adiabatic energy gap and geometry at the time of quenching.

Original languageEnglish (US)
Article number014302
JournalJournal of Chemical Physics
Volume129
Issue number1
DOIs
StatePublished - Jan 1 2008

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