Valence and lowest Rydberg electronic states of phenol investigated by synchrotron radiation and theoretical methods

P Limão-Vieira; D Duflot; F Ferreira da Silva; E Lange; N C Jones; S V Hoffmann; M A Śmiałek; D B Jones; M J Brunger

doi:10.1063/1.4955334

Valence and lowest Rydberg electronic states of phenol investigated by synchrotron radiation and theoretical methods

J Chem Phys. 2016 Jul 21;145(3):034302. doi: 10.1063/1.4955334.

Authors

P Limão-Vieira¹, D Duflot², F Ferreira da Silva¹, E Lange¹, N C Jones³, S V Hoffmann³, M A Śmiałek⁴, D B Jones⁵, M J Brunger⁵

Affiliations

¹ Laboratório de Colisões Atómicas e Moleculares, CEFITEC, Departamento de Física, Faculdade de Ciências e Tecnologia, Universidade NOVA de Lisboa, 2829-516 Caparica, Portugal.
² Univ. Lille, UMR 8523-Physique des Lasers Atomes et Molécules, F-59000 Lille, France.
³ ISA, Department of Physics and Astronomy, Aarhus University, Ny Munkegade 120, DK-8000 Aarhus C, Denmark.
⁴ Department of Control and Power Engineering, Faculty of Ocean Engineering and Ship Technology, Gdańsk University of Technology, Gabriela Narutowicza 11/12, 80-233 Gdańsk, Poland.
⁵ School of Chemical and Physical Sciences, Flinders University, GPO Box 2100, Adelaide, SA 5001, Australia.

PMID: 27448882
DOI: 10.1063/1.4955334

Abstract

We present the experimental high-resolution vacuum ultraviolet (VUV) photoabsorption spectra of phenol covering for the first time the full 4.3-10.8 eV energy-range, with absolute cross sections determined. Theoretical calculations on the vertical excitation energies and oscillator strengths were performed using time-dependent density functional theory and the equation-of-motion coupled cluster method restricted to single and double excitations level. These have been used in the assignment of valence and Rydberg transitions of the phenol molecule. The VUV spectrum reveals several new features not previously reported in the literature, with particular reference to the 6.401 eV transition, which is here assigned to the 3sσ/σ(∗)(OH)←3π(3a″) transition. The measured absolute photoabsorption cross sections have been used to calculate the photolysis lifetime of phenol in the earth's atmosphere (0-50 km).