Abstract

It is commonly understood that the Renner-Teller effect can strongly influence the spectroscopy of molecules through coupling of electronic states. Here we investigate the vibrational bound states and low-lying resonances of the formyl radical treating the Renner-Teller coupled X2A' and Ã2A" states using the MultiConfiguration Time Dependent Hartree (MCTDH) method. The calculations were performed using the improved relaxation method for the bound states and a recently published extension to compute resonances. A new set of accurate global potential energy surfaces were computed at the explicitly correlated multireference configuration interaction (MRCI-F12) level and yielded remarkably close agreement with experiment in this application and thus enable future studies including photodissociation and collisional dynamics. The results show the necessity of including the large contribution from a Davidson correction in the electronic structure calculations in order to appreciate the relatively small effect of the Renner-Teller coupling on the states considered here.

Department(s)

Chemistry

Research Center/Lab(s)

Center for High Performance Computing Research

Keywords and Phrases

Electronic structure; Molecular physics; Photodissociation; Positive ions; Potential energy surfaces; Quantum chemistry; Resonance, Collisional dynamics; Electronic structure calculations; Global potential energy surfaces; Multi reference configuration interactions; Multiconfiguration; Relaxation methods; Renner-Teller couplings; Renner-Teller effect, Potential energy

International Standard Serial Number (ISSN)

0021-9606

Document Type

Article - Journal

Document Version

Final Version

File Type

text

Language(s)

English

Rights

© 2016 American Institute of Physics (AIP), All rights reserved.

Publication Date

01 Jun 2016

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