Somogyi, W;
Yurchenko, S;
Yachmenev, A;
(2021)
Calculation of electric quadrupole linestrengths for diatomic molecules: Application to the H2, CO, HF and O2 molecules.
The Journal of Chemical Physics
10.1063/5.0063256.
(In press).
Preview |
Text
5.0063256.pdf - Accepted Version Download (4MB) | Preview |
Abstract
We present a unified variational treatment of the electric quadrupole (E2) matrix elements, Einstein coefficients, and line strengths for general open-shell diatomic molecules in the general purpose diatomic code \Duo. Transformation relations between the Cartesian representation (typically used in electronic structure calculations) to the tensorial representation (required for spectroscopic applications) of the electric quadrupole moment components are derived. The implementation has been validated against accurate theoretical calculations and experimental measurements of quadrupole intensities of 1H2 available in the literature. We also present accurate electronic structure calculations of the electric quadrupole moment functions for the X 1Σ+ electronic states of CO and HF at the CCSD(T) and MRCI levels of theory, respectively, as well for the a 1Δg - b 1Σg+ quadrupole transition moment of of O2 with MRCI level of theory. Accurate infrared E2 line lists for 12C16O and 1H19F are provided. A demonstration of spectroscopic applications is presented by simulating E2 spectra for 12C16O, 1H19F and 16O2 (Noxon a 1Δg - b 1Σg+ band).
| Type: | Article |
|---|---|
| Title: | Calculation of electric quadrupole linestrengths for diatomic molecules: Application to the H2, CO, HF and O2 molecules |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1063/5.0063256 |
| Publisher version: | https://doi.org/10.1063/5.0063256 |
| Language: | English |
| Additional information: | This version is the author accepted manuscript. For information on re-use, please refer to the publisher’s terms and conditions. |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Physics and Astronomy |
| URI: | https://discovery.ucl.ac.uk/id/eprint/10138425 |
Archive Staff Only
 |
View Item |
