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Title: Variational calculations of rotation-vibration spectra for small molecules of astrophysical interest
Author: Owens, A. T.
ISNI:       0000 0004 7660 269X
Awarding Body: UCL (University College London)
Current Institution: University College London (University of London)
Date of Award: 2017
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Variational calculations of rotation-vibration spectra are presented for a range of four- and five-atom molecules of atmospheric and astrophysical importance. Using state-of-the-art electronic structure methods, new nine-dimensional potential energy and dipole moment surfaces are constructed for methyl chloride (CH3Cl), silane (SiH4), and methane (CH4). The respective surfaces are rigorously evaluated against high-resolution spectroscopic data from a variety of experimental sources. The ab initio potential energy surfaces represent some of the most accurate to date, whilst intensity simulations utilizing the dipole moment surfaces show good agreement with experiment. A novel application of rotation-vibration computations is introduced to investigate the sensitivity of spectral lines to a possible space-time variation of the proton-to-electron mass ratio μ. The approach relies on finding the mass dependence of the computed energy levels and is only possible because of the remarkable accuracy of variational calculations. Highly sensitive transitions are uncovered for ammonia (NH3) and the hydronium cation (H3O+) which could lead to a tighter constraint on a varying μ. An advantage of the variational approach is that Einstein A coefficients can be determined to help guide future laboratory and astronomical observations. This thesis demonstrates the current capabilities of variational calculations of rotation-vibration spectra and highlights the challenges faced by the field.
Supervisor: Yurchenko, S. N. ; Tennyson, J. Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available