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.
S. A. Ndengué et al., "A New Set of Potential Energy Surfaces for HCO: Influence of Renner-Teller Coupling on the Bound and Resonance Vibrational States," Journal of Chemical Physics, vol. 144, no. 24, American Institute of Physics (AIP), Jun 2016.
The definitive version is available at http://dx.doi.org/10.1063/1.4954374
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)
Article - Journal
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