Comparisons of classical chemical dynamics simulations of the unimolecular decomposition of classical and quantum microcanonical ensembles

Paranjothy Manikandan, William L. Hase

Research output: Contribution to journalArticlepeer-review

15 Scopus citations

Abstract

Previous studies have shown that classical trajectory simulations often give accurate results for short-time intramolecular and unimolecular dynamics, particularly for initial non-random energy distributions. To obtain such agreement between experiment and simulation, the appropriate distributions must be sampled to choose initial coordinates and momenta for the ensemble of trajectories. If a molecules classical phase space is sampled randomly, its initial decomposition will give the classical anharmonic microcanonical (RRKM) unimolecular rate constant for its decomposition. For the work presented here, classical trajectory simulations of the unimolecular decomposition of quantum and classical microcanonical ensembles, at the same fixed total energy, are compared. In contrast to the classical microcanonical ensemble, the quantum microcanonical ensemble does not sample the phase space randomly. The simulations were performed for CH 4, C 2H 5, and Cl - - -CH 3Br using both analytic potential energy surfaces and direct dynamics methods. Previous studies identified intrinsic RRKM dynamics for CH 4 and C 2H 5, but intrinsic non-RRKM dynamics for Cl - - -CH 3Br. Rate constants calculated from trajectories obtained by the time propagation of the classical and quantum microcanonical ensembles are compared with the corresponding harmonic RRKM estimates to obtain anharmonic corrections to the RRKM rate constants. The relevance and accuracy of the classical trajectory simulation of the quantum microcanonical ensemble, for obtaining the quantum anharmonic RRKM rate constant, is discussed.

Original languageEnglish
Article number184110
JournalJournal of Chemical Physics
Volume136
Issue number18
DOIs
StatePublished - May 14 2012

Fingerprint Dive into the research topics of 'Comparisons of classical chemical dynamics simulations of the unimolecular decomposition of classical and quantum microcanonical ensembles'. Together they form a unique fingerprint.

Cite this