Theoretical rovibrational line intensities in the electronic ground state of ozone

Diehr, Matthieu, Rosmus, Pavel, Carter, Stuart and Knowles, Peter James ORCID: https://orcid.org/0000-0003-4657-6331 2004. Theoretical rovibrational line intensities in the electronic ground state of ozone. Molecular Physics 102 (21-22) , pp. 2181-2189. 10.1080/00268970410001722993

Full text not available from this repository.

Abstract

First-principles calculations of absolute line intensities and rovibrational energies of ozone (16O3) are reported using potential energy and electric dipole moment functions calculated by the internally contracted MRCI approach. The rovibrational energies and eigenfunctions (up to about 8500 cm−1 and J = 64) were obtained variationally with an exact Hamiltonian in internal valence coordinates. More than 4.8 × 106 electric dipole transition matrix elements were calculated for the absolute rovibrational line intensities. They are compared with the values of the HITRAN database. The purely rotational absolute line intensities in the (000) state and the rovibrational intensities for the (001)–(000) band agree to within about 0.3 to 1% for the (010)–(000) band to within about 3 to 4%. Excellent agreement with experiment is also achieved for low-lying overtone and combination bands. Inconsistencies are found for the (100)–(000) band overlapping with the antisymmetric stretching fundamental and also for the (002)–(000) antisymmetric stretching overtone. The generated dipole moment function can be used for predicting the absorption intensities in any of the heavier isotopomers, hot bands or the rates of spontaneous emission.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Subjects:	Q Science > QD Chemistry
Last Modified:	18 Oct 2022 12:23
URI:	https://orca.cardiff.ac.uk/id/eprint/9633

Citation Data

Cited 8 times in Scopus. View in Scopus. Powered By Scopus® Data

Actions (repository staff only)

Edit Item