Direct dynamics trajectory study of vibrational effects: can polanyi rules be generalized to a polyatomic system?

Journal of the American Chemical Society
Jianbo LiuScott L Anderson

Abstract

We present an ab initio direct dynamics trajectory study of the hydrogen abstraction reaction: H2CO+ + CD4 --> H2COD+ + CD3, with methane excited in two different distortion modes (nu4 and nu2). The trajectory simulations were able to reproduce experimental results and for the first time show how vibrational enhancement originates in reaction of small polyatomic species. Roughly equal contributions from two vibrational enhancement mechanisms were found. The "distortion" mechanism correlates the vibrational effects with vibration-induced reactant distortions, and the "velocity" mechanism correlates vibrational effects with vibrational velocities of the constituent atoms. This reaction has a reactant-like transition state and, thus, would correspond to an "early" barrier system in the context of the well-known Polanyi rules for predicting effects of vibration and collision energy. Straightforward application of these rules would predict that vibration should be ineffective in driving reaction, in disagreement with both experiment and trajectory results. Using the trajectories for guidance, we were able to construct a two-dimensional cut through the reaction potential energy surface that does suggest a predictive, Polanyi-type rule.

References

Mar 8, 2003·Science·Salai Cheettu AmmalMichel Dupuis

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Citations

Mar 26, 2008·The Journal of Chemical Physics·Jason M BoyleScott L Anderson
Feb 17, 2011·The Journal of Chemical Physics·David M BellScott L Anderson
Jun 15, 2011·The Journal of Chemical Physics·David R GlowackiJeremy N Harvey
Aug 3, 2011·The Journal of Chemical Physics·David M BellScott L Anderson
Oct 22, 2016·Journal of the American Chemical Society·Hiroaki KurouchiDaniel A Singleton
Aug 2, 2006·Physical Chemistry Chemical Physics : PCCP·Myung Hwa KimArthur G Suits
Oct 19, 2006·Physical Chemistry Chemical Physics : PCCP·Jianbo LiuScott L Anderson
May 1, 2009·Nature Chemistry·George L Barnes, William L Hase
Apr 22, 2020·Annual Review of Physical Chemistry·Bhumika Jayee, William L Hase
Mar 23, 2017·Philosophical Transactions. Series A, Mathematical, Physical, and Engineering Sciences·Xinyou Ma, William L Hase
Jul 13, 2006·The Journal of Physical Chemistry. a·Bailin Zhang, Kopin Liu
Feb 3, 2009·The Journal of Physical Chemistry. a·Jason M BoyleScott L Anderson
Jun 9, 2005·Chemical Reviews·Tom Ziegler, Jochen Autschbach
Jun 9, 2011·The Journal of Physical Chemistry. a·Jianbo LiuGhanshyam L Vaghjiani
Jan 13, 2015·The Journal of Physical Chemistry. a·Hongwei Song, Hua Guo
May 3, 2014·The Journal of Physical Chemistry. a·Joaquín Espinosa-Garcia

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