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Valence and Ionic Lowest-Lying Electronic States of Isobutyl Formate Studied by High-Resolution Vacuum Ultraviolet Photoabsorption, Photoelectron Spectroscopy, and Ab Initio Calculations

Śmiałek, M.A., Łabuda, M., Guthmuller, J., Hoffmann, S.V., Jones, N.C., MacDonald, M.A., Zuin, L., Mason, Nigel, Limão-Vieira, P. (2015) Valence and Ionic Lowest-Lying Electronic States of Isobutyl Formate Studied by High-Resolution Vacuum Ultraviolet Photoabsorption, Photoelectron Spectroscopy, and Ab Initio Calculations. Journal of Physical Chemistry A, 119 (32). pp. 8647-8656. ISSN 1089-5639. (doi:10.1021/acs.jpca.5b06053) (The full text of this publication is not currently available from this repository. You may be able to access a copy if URLs are provided) (KAR id:74685)

The full text of this publication is not currently available from this repository. You may be able to access a copy if URLs are provided. (Contact us about this Publication)
Official URL
http://dx.doi.org/10.1249/MSS.0b013e31822cb0d2

Abstract

The highest resolution vacuum ultraviolet photoabsorption spectrum of isobutyl formate, C<inf>5</inf>H<inf>10</inf>O<inf>2</inf>, yet reported is presented over the energy range 4.5-10.7 eV (275.5-118.0 nm) revealing several new spectral features. Valence and Rydberg transitions and their associated vibronic series observed in the photoabsorption spectrum have been assigned in accordance with new ab initio calculations of the vertical excitation energies and oscillator strengths. Calculations have also been carried out to determine the ionization energies and fine structure of the lowest ionic state of isobutyl formate and are compared with a newly recorded photoelectron spectrum (from 9.0 to 27.0 eV). The value of the first ionization energy was determined to be 10.508 eV (adiabatic) and 10.837 eV (vertical). New vibrational structure is observed in the first photoelectron band, predominantly resulting from C-O and Ci=O stretches of the molecule. The photoabsorption cross sections have been used to calculate the photolysis lifetime of isobutyl formate in the upper stratosphere (20-50 km), indicating that the hydroxyl radical processes will be the main loss process for isobutyl formate.

Item Type: Article
DOI/Identification number: 10.1021/acs.jpca.5b06053
Uncontrolled keywords: Electronic states, Ionization, Ionization of gases, Photoelectron spectroscopy, Photoelectrons, Photoionization, Photolysis, Photons, Radiation, Ab initio calculations, Oscillator strengths, Photoabsorption cross sections, Photoabsorption spectra, Photoelectron spectrum, Vacuum ultraviolets, Vertical excitation energy, Vibrational structures, Calculations, formic acid derivative, ion, chemical model, chemistry, ultraviolet spectrophotometry, vacuum, vibration, X ray photoelectron spectroscopy, Formates, Ions, Models, Chemical, Photoelectron Spectroscopy, Spectrophotometry, Ultraviolet, Vacuum, Vibration
Divisions: Faculties > Sciences > School of Physical Sciences
Depositing User: Nigel Mason
Date Deposited: 11 Jul 2019 08:40 UTC
Last Modified: 11 Jul 2019 08:43 UTC
Resource URI: https://kar.kent.ac.uk/id/eprint/74685 (The current URI for this page, for reference purposes)
Mason, Nigel: https://orcid.org/0000-0002-4468-8324
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