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Journal of Quantitative Spectroscopy and Radiative Transfer
Article . 2019 . Peer-reviewed
License: Elsevier TDM
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Reduced matrix elements for collisionally induced transitions of 12CH4

Authors: Gamache, Robert; Rey, Michael; Vispoel, Bastien; Tyuterev, Vladimir;

Reduced matrix elements for collisionally induced transitions of 12CH4

Abstract

Abstract Reduced matrix elements (RMEs) for collisionally induced transitions are an important component of semi-classical line shape calculations. They give the quantum mechanical probability for a transition in the radiating molecule occurring due to a collision with one of the bath molecules. The RMEs for both the radiating and perturbing molecules are part of the quantum mechanical component of a semi-classical calculation. Evaluating the reduced matrix elements requires wavefunctions for the molecules in question. In this work, RMEs for ro-vibrational states of methane are evaluated using ab initio wavefunctions. These RMEs are compared with RMEs evaluated using a Hamiltonian model to the fourth order in the Td formalism. Comparisons are made for the ground and ν3 states, where the ν3 state is treated as an isolated state by an Effective Hamiltonian. The formulas for the reduced matrix elements are developed in both formalisms. The comparison shows good agreement for low angular momentum states, where the isolated state approximation should be valid. Using sum rules as a check of the RMEs revealed that all symmetry components of the wavefunctions are needed in a line shape calculation. Line shape parameters are evaluated using the ab initio RMEs for a number of ν3 transitions measured by Benner et al. [JQSRT 50, 65, 1993].

Keywords

[PHYS]Physics [physics], колебательные состояния, [PHYS.MPHY]Physics [physics]/Mathematical Physics [math-ph], волновые функции, [PHYS.MPHY] Physics [physics]/Mathematical Physics [math-ph], [PHYS] Physics [physics], [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, столкновительно-индуцированные переходы, матричные элементы, метан

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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
4
Average
Average
Average
Green
bronze