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

M. A. Smialek, M. Łabuda, J. Guthmuller, S. V. Hoffmann, N. C. Jones, M. A. MacDonald, L. Zuin, Nigel J. Mason, Paulo Manuel Assis Loureiro Limão-vieira

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

The highest resolution vacuum ultraviolet photoabsorption spectrum of isobutyl formate, C5H10O2, 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.

Original languageEnglish
Pages (from-to)8647-8656
Number of pages10
JournalJournal of Physical Chemistry A
Volume119
Issue number32
DOIs
Publication statusPublished - 2015

Keywords

  • DENSITY-FUNCTIONAL THEORY
  • GAUSSIAN-BASIS SETS
  • VUV PHOTOABSORPTION
  • GAS CHROMATOGRAPHY
  • MASS SPECTROMETRY
  • CROSS-SECTION
  • ABSORPTION
  • ATOMS
  • IONIZATION
  • NITROGEN

Fingerprint Dive into the research topics of 'Valence and Ionic Lowest-Lying Electronic States of Isobutyl Formate Studied by High-Resolution Vacuum Ultraviolet Photoabsorption, Photoelectron Spectroscopy, and Ab Initio Calculations'. Together they form a unique fingerprint.

Cite this