TY - JOUR
T1 - Reduced Matrix Elements for collisionally induced transitions of 12CH4
AU - Gamache, Robert
AU - Rey, Michaël
AU - Vispoel, Bastien
AU - Tyuterev, Vladimir G.
N1 - Funding Information:
The authors are pleased to acknowledge support of this research by the National Science Foundation through Grant No. AGS-1622676. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation. The support from French ANR e-PYTHEAS project, Grant 16-CE31-0005-04 and from Academic A.D.Mendeleev program of Tomsk State University, Russia, are acknowledged. We are indebted to A.Nikitin for fruitful collaboration on ab initio potential energy surfaces and stimulating discussion.
Funding Information:
The authors are pleased to acknowledge support of this research by the National Science Foundation through Grant No. AGS-1622676 . Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation. The support from French ANR e-PYTHEAS project , Grant 16-CE31-0005-04 and from Academic A.D.Mendeleev program of Tomsk State University, Russia , are acknowledged. We are indebted to A.Nikitin for fruitful collaboration on ab initio potential energy surfaces and stimulating discussion.
Publisher Copyright:
© 2019
Copyright:
Copyright 2019 Elsevier B.V., All rights reserved.
PY - 2019/9/1
Y1 - 2019/9/1
N2 - 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 T
d formalism. Comparisons are made for the ground and ν
3 states, where the ν
3 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 ν
3 transitions measured by Benner et al. [JQSRT 50, 65, 1993].
AB - 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 T
d formalism. Comparisons are made for the ground and ν
3 states, where the ν
3 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 ν
3 transitions measured by Benner et al. [JQSRT 50, 65, 1993].
UR - http://www.scopus.com/inward/record.url?scp=85067621877&partnerID=8YFLogxK
U2 - 10.1016/j.jqsrt.2019.06.010
DO - 10.1016/j.jqsrt.2019.06.010
M3 - Article
SN - 0022-4073
VL - 235
SP - 31
EP - 39
JO - Journal of Quantitative Spectroscopy and Radiative Transfer
JF - Journal of Quantitative Spectroscopy and Radiative Transfer
ER -