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Article Dans Une Revue Journal of Chemical Theory and Computation Année : 2012

An Efficient and Accurate Formalism for the Treatment of Large Amplitude Intramolecular Motion

Résumé

We propose a general approach to describe Large Amplitude Motions (LAM) with multiple Degrees Of Freedom (DOF) in molecules or reaction intermediates, which is useful for the computation of thermochemical or kinetic data. The kinetic part of the LAM Lagrangian is derived using a Z-matrix internal coordinate representation within a new numerical procedure. This derivation is exact for a classical system, and the uncertainties on the prediction of observable quantities largely arise from uncertainties on the LAM Potential Energy Surface (PES). In order to rigorously account for these uncertainties, we present an approach based on Bayesian theory to infer a parametrized physical model of the PES using ab initio calculations. This framework allows a quantification of uncertainties associated with a PES model, as well as a propagation scheme for the final quantity of interest. A selection and generalization of some treatments accounting for the coupling of the LAM with other internal or external degrees of freedom are also presented. Finally, we discuss and validate the approach with two applications: the calculation of the partition function of the 1,3-butadiene, and the calculation of the high-pressure reaction rate of the CH$_3$ + $H$ → CH$_4$ recombination.
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hal-01761329 , version 1 (09-04-2018)

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Guillaume Reinisch, Kenji Miki, G. Vignoles, Bryan M Wong, Chris B. Simmons. An Efficient and Accurate Formalism for the Treatment of Large Amplitude Intramolecular Motion. Journal of Chemical Theory and Computation, 2012, 8, pp.2713 - 2724. ⟨10.1021/ct300278x⟩. ⟨hal-01761329⟩
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