Photoinduced Rydberg ionization (PIRI) spectroscopy of the {tilde B} state of the fluorobenzene cation

Journal Article · Thu Apr 15 04:00:00 EDT 1999 · Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory

DOI:https://doi.org/10.1021/jp984697a· OSTI ID:347507

Anand, R; LeClaire, J E; Johnson, P M ^[1]

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1. State Univ. of New York, Stony Brook, NY (United States). Dept. of Chemistry

Vibrationally resolved PIRI spectra of the {tilde B} state of the fluorobenzene cation via the origin, 16a, 6b, and 11 vibrational modes in the ground ionic state require a reassignment of the accepted state symmetry. On the basis of lower resolution studies, the {tilde B} {l_arrow} {tilde X} transition has been previously assigned as an electronically forbidden {sup 2}B{sub 2} {l_arrow} {sup 2}B{sub 1} transition. Vibrational analyses of the spectra observed via various ground-state nonsymmetric vibrations, particularly from the 16a vibrational mode, unambiguously locate the origin of the transition at 21,075 cm{sup {minus}1}, resulting in the reassignment of the ionic state as {sup 2}B{sub 1}. Ab initio calculations, while not conclusive, also suggest that the {tilde B} {l_arrow} {tilde X} transition is an allowed {pi} to {pi} transition.

• Sponsoring Organization: USDOE, Washington, DC (United States)
• OSTI ID: 347507
• Journal Information: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Journal Name: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory Journal Issue: 15 Vol. 103; ISSN 1089-5639; ISSN JPCAFH
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
BENZENE
ELECTRONIC STRUCTURE
ENERGY SPECTRA
ENERGY-LEVEL TRANSITIONS
EXCITED STATES
FLUORINE COMPOUNDS
PHOTOIONIZATION
SPECTROSCOPY