Combined theoretical and experimental study of the valence, Rydberg and ionic states of fluorobenzene

Journal Article · Sat May 28 00:00:00 EDT 2016 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4949548· OSTI ID:22657818

Ridley, Trevor ^[1]; Coreno, Marcello ^[2]; Grazioli, Cesare ^[3]; Zhang, Teng ^[4]; others, and

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1. School of Chemistry, University of Edinburgh, Joseph Black Building, David Brewster Road, Edinburgh, Scotland EH9 3FJ (United Kingdom)
2. CNR-ISM, Basovizza Area Science Park, 1-34149 Trieste (Italy)
3. CNR-IOM Laboratorio TASC, Trieste (Italy)
4. Department of Physics and Astronomy, University of Uppsala, Uppsala (Sweden)

New photoelectron spectra (PES) and ultra violet (UV) and vacuum UV (VUV) absorption spectra of fluorobenzene recorded at higher resolution than previously, have been combined with mass-resolved (2 + 1) and (3 + 1) resonance enhanced multiphoton ionization (REMPI) spectra; this has led to the identification of numerous Rydberg states. The PES have been compared with earlier mass-analyzed threshold ionization and photoinduced Rydberg ionization (PIRI) spectra to give an overall picture of the ionic state sequence. The analysis of these spectra using both equations of motion with coupled cluster singles and doubles (EOM-CCSD) configuration interaction and time dependent density functional theory (TDDFT) calculations have been combined with vibrational analysis of both the hot and cold bands of the spectra, in considerable detail. The results extend several earlier studies on the vibronic coupling leading to conical intersections between the X{sup 2}B{sub 1} and A{sup 2}A{sub 2} states, and a further trio (B, C, and D) of states. The conical intersection of the X and A states has been explicitly identified, and its structure and energetics evaluated. The energy sequence of the last group is only acceptable to the present study if given as B{sup 2}B{sub 2}

• OSTI ID: 22657818
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 20 Vol. 144; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ABSORPTION SPECTRA
COUPLING
DENSITY FUNCTIONAL METHOD
EQUATIONS OF MOTION
EXPERIMENTAL DATA
FAR ULTRAVIOLET RADIATION
PHOTOELECTRON SPECTROSCOPY
RYDBERG STATES
TIME DEPENDENCE