Rigidity Of The Molecular Ion H5+

Császár, Attila

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https://hdl.handle.net/2142/50799 Copy

Description

Title

Rigidity Of The Molecular Ion H5+

Author(s)

Császár, Attila

Contributor(s)

• Sarka, János
• Fábri, Csaba

Issue Date

2014-06-18

Keyword(s)

Mini-symposium: Beyond the Mass-to-Charge Ratio: Spectroscopic Probes of the Structures of Ions

Date of Ingest

• 2014-09-17T16:54:56Z
• 2015-04-14T18:40:21Z

Abstract

The in-house fourth-age quantum chemical code GENIUSH is used for the variational determination of rotational-vibrational energy levels corresponding to reduced- and full-dimensional models of H$_5^+$, a molecular ion exhibiting several strongly coupled large-amplitude motions and strong coupling between its vibrations and rotations. The quantum chemical computations are supplemented with simplified modeling efforts, including one- and two-dimensional exactly solvable models. These models help to understand the peculiar rovibrational energy-level structure computed for H$_5^+$ and its deuterated isotopologues. It is shown that while a 1D ``active torsion'' model provides proper rovibrational levels when compared to the full, 9D treatment, models excluding the torsion have limited physical significance due to the extremely strong coupling between the torsion and one of the rotations. The role the choice of the internal coordinates and the embedding of the rotational axes play in obtaining converged rovibrational results is discussed in detail. The structure of the rovibrational energy levels of H$_5^+$ proves that it is useful to view this ion as a prototypical astructural molecule: the rotational and vibrational level spacings are of the same order of magnitude and the level structure drastically deviates from that computed via perturbed rigid-rotor and harmonic-oscillator models.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Genre of Resource

Conference Paper / Presentation

Language

English

Permalink

http://hdl.handle.net/2142/50799

DOI

https://doi.org/10.15278/isms.2014.WG13

Copyright and License Information

Copyright 2014 by the authors. Licensed under a Creative Commons Attribution 4.0 International License. http://creativecommons.org/licenses/by/4.0/

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