Rotational Spectrum Of So3 And Theoretical Evidence For The Formation Of Rotational Energy Level Clusters In Its Vibrational Ground State

Jensen, Per

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https://hdl.handle.net/2142/50991 Copy

Description

Title

Rotational Spectrum Of So3 And Theoretical Evidence For The Formation Of Rotational Energy Level Clusters In Its Vibrational Ground State

Author(s)

Jensen, Per

Contributor(s)

• Tennyson, Jonathan
• Yurchenko, Sergei N.
• Underwood, Daniel S

Issue Date

2014-06-19

Keyword(s)

Theory and Computation

Abstract

The structure of the purely rotational spectrum of sulphur trioxide $SO_3$ is investigated using a new synthetic line list. The list combines line positions from an empirical model with line intensities determined, in the form of Einstein coefficients, from variationally computed ro-vibrational wavefunctions in conjunction with an \textit{ab initio} dipole moment surface. The empirical model providing the line positions involves an effective, Watsonian-type rotational Hamiltonian with literature parameter values resulting from least-squares fittings to observed transition frequencies. The formation of so-called rotational energy clusters at high rotational excitation are investigated. The SO$_3$ molecule is planar at equilibrium and exhibits a unique type of rotational-energy clustering associated with unusual stabilization axes perpendicular to the S--O bonds. This behaviour is characterized theoretically in the $J$ range from 100 through 250. The wavefunctions for these cluster states are analysed, and the results are compared to those of a classical analysis in terms of the rotational-energy-surface formalism.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

English

Permalink

http://hdl.handle.net/2142/50991

DOI

https://doi.org/10.15278/isms.2014.RC06

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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