In a previous article we have introduced an alternative perturbation scheme to the traditional one starting from the harmonic oscillator, rigid rotator Hamiltonian, to find approximate solutions of the spectral problem for rotation-vibration molecular Hamiltonians. The convergence of our method for the methane vibrational ground state rotational energy levels was quicker than that of the traditional method, as expected, and our predictions were quantitative. In this second article, we study the convergence of the ab initio calculation of effective dipole moments for methane within the same theoretical frame. The first order of perturbation when applied to the electric dipole moment operator of a spherical top gives the expression used in previous spectroscopic studies. Higher orders of perturbation give corrections corresponding to higher centrifugal distortion contributions and are calculated accurately for the first time. Two potential energy surfaces of the literature have been used for solving the anharmonic vibrational problem by means of the vibrational mean field configuration interaction approach. Two corresponding dipole moment surfaces were calculated in this work at a high level of theory. The predicted intensities agree better with recent experimental values than their empirical fit. This suggests that our ab initio dipole moment surface and effective dipole moment operator are both highly accurate.
Skip Nav Destination
,
Article navigation
7 May 2012
Research Article|
May 04 2012
Ab initio calculation of the rotational spectrum of methane vibrational ground state Available to Purchase
P. Cassam-Chenaï;
P. Cassam-Chenaï
a)
1Laboratoire J. A. Dieudonné, UMR 6621 du CNRS,
Faculté des Sciences
, Parc Valrose, 06108 Nice Cedex 2, France
Search for other works by this author on:
J. Liévin
J. Liévin
2
Université Libre de Bruxelles
, Service de Chimie quantique et Photophysique, CP 160/09, 50 Av. F.D. Roosevelt, B-1050 Bruxelles, Belgium
Search for other works by this author on:
P. Cassam-Chenaï
1,a)
J. Liévin
2
1Laboratoire J. A. Dieudonné, UMR 6621 du CNRS,
Faculté des Sciences
, Parc Valrose, 06108 Nice Cedex 2, France
2
Université Libre de Bruxelles
, Service de Chimie quantique et Photophysique, CP 160/09, 50 Av. F.D. Roosevelt, B-1050 Bruxelles, Belgium
a)
Electronic mail: [email protected].
J. Chem. Phys. 136, 174309 (2012)
Article history
Received:
December 20 2011
Accepted:
April 06 2012
Citation
P. Cassam-Chenaï, J. Liévin; Ab initio calculation of the rotational spectrum of methane vibrational ground state. J. Chem. Phys. 7 May 2012; 136 (17): 174309. https://doi.org/10.1063/1.4705278
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
The Amsterdam Modeling Suite
Evert Jan Baerends, Nestor F. Aguirre, et al.
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
Light–matter interaction at the nano- and molecular scale
Kaifeng Wu, Chufeng Zhang, et al.
Related Content
Ab initio MRSDCI study on the low-lying electronic states of the lithium chloride molecule (LiCl)
J. Chem. Phys. (August 2012)
Accurate ab initio quartic force fields for NH 2 − and CCH − and rovibrational spectroscopic constants for their isotopologs
J. Chem. Phys. (September 2009)
Carbon chains of type C 2 n + 1 N − ( n = 2 – 6 ) : A theoretical study of potential interstellar anions
J. Chem. Phys. (July 2008)
Full-dimensional potential energy surfaces of ground (X̃2 A′) and excited (Ã2 A″) electronic States of HCO and absorption spectrum
Chin. J. Chem. Phys. (April 2022)
First fully ab initio potential energy surface of methane with a spectroscopic accuracy
J. Chem. Phys. (September 2016)