CH4·F− revisited: full-dimensional ab initio potential energy surface and variational vibrational states

The automated development of a new ab initio full-dimensional potential energy surface (PES) is reported for the CH 4 ·F − complex using the Robosurfer program package. The new potential provides a near-spectroscopic quality description over a broad configuration range including the methane-ion diss...

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Bibliographic Details
Published in:Molecular physics 2023-06, Vol.121 (11-12)
Main Authors: Papp, Dóra, Tajti, Viktor, Avila, Gustavo, Mátyus, Edit, Czakó, Gábor
Format: Article
Language:English
Subjects:
ab initio potential energy surface
Algorithms
Methane
Potential energy
Robosurfer
spectroscopy
tunnelling splittings
variational vibrational computations
Vibrational states
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Summary:The automated development of a new ab initio full-dimensional potential energy surface (PES) is reported for the CH 4 ·F − complex using the Robosurfer program package. The new potential provides a near-spectroscopic quality description over a broad configuration range including the methane-ion dissociation, as well as isolated methane vibrations. In particular, it improves upon the earlier [Czakó, Braams, Bowman (2008)] PES over intermediate methane-fluoride distances. Full-dimensional (12D) variational vibrational computations using the new PES and the GENIUSH-Smolyak algorithm show that tunnelling splittings larger than 0.1 cm −1 appear below the top of the interconversion barrier of the four equivalent minima of the complex.
ISSN:0026-8976
1362-3028
DOI:10.1080/00268976.2022.2113565