A global view of isotopic effects on ro-vibrational spectra of six-atomic molecules: a case study of eleven ethylene species

• Published in: Physical chemistry chemical physics : PCCP 2020-02, Vol.22 (6), p.324-3216
• Main Authors: Viglaska-Aflalo, Dominika, Rey, Michaël, Nikitin, Andrei, Delahaye, Thibault
• Format: Article
• Language: English
• Subjects: Atomic and Molecular Clusters; Broken symmetry; Chemical Sciences; Deuteration; Dipole moments; Ethylene; Molecular spectra; Physics; Potential energy; Vibrational spectra
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/c9cp06383h

In this work, we present a global view of the impact of isotopic substitutions on the spectra of eleven ethylene isotopologues obtained from variational calculations using accurate ab initio potential energy and dipole moment surfaces. This may lead to some important changes in the molecular spectra due to symmetry breaking effects lowering the initial D 2h symmetry of 12 C 2 H 4 (&z.tbd; 12 CH 2 12 CH 2 ) to C 2v , C 2h or C s . For the very first time, we report ab initio predictions for 12 C 2 D 4 (&z.tbd; 12 CD 2 12 CD 2 ) and three C s species: 12 CHD 13 CH 2 , 13 CHD 12 CH 2 and 12 C 2 HD 3 (&z.tbd; 12 CD 2 12 CHD). To this end, we have considered the normal-mode approach based on our reduced Eckart-Watson Hamiltonian combined with ethylene ab initio surfaces. This work will contribute to the complete theoretical studies of the deuterated and 13 C-enriched ethylene isotopologues. A total of 1252 vibrational levels are computed and all the corresponding transitions in the energy range of ≤3100 cm −1 are predicted and compared to 151 bands assigned from experimental spectra analyses. Complete theoretical description of isotopic effects on the rotationally resolved spectra of 11 ethylene isotopologues.