Journal article
Combined theoretical and experimental study of the valence, Rydberg and ionic states of fluorobenzene
The Journal of chemical physics, Vol.144(20), pp.204305-204305
05/28/2016
Handle:
https://hdl.handle.net/2376/112730
PMID: 27250304
Abstract
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 X2B1 and A2A2 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 B2B2<C2B1<D2A1, a conclusion which is in agreement with most previous EOM-CCSD and other calculations. However, this symmetry ordering of the B and C states forces reconsideration of the nature of the PIRI spectrum. The coupling between these two states is induced by the a2 modes, ν
12 and ν
14 and we propose that the 141 band is observed in the B2B2 band in the PES for the first time, because of the improved resolution. This same assignment is given to the lowest energy band in the PIRI spectrum which was previously assigned as the origin band and further conclude that the entire PIRI spectrum is induced by ν
12 and ν
14. The relative intensities of the various Rydberg state peaks in the VUV absorption and REMPI spectra of fluorobenzene are very similar to those observed in the equivalent spectra of benzene.
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Details
- Title
- Combined theoretical and experimental study of the valence, Rydberg and ionic states of fluorobenzene
- Creators
- Michael H Palmer - University of EdinburghTrevor Ridley - University of EdinburghSøren Vrønning Hoffmann - Aarhus UniversityNykola C Jones - Aarhus UniversityMarcello Coreno - CNR-ISMMonica de Simone - CNR-IOM Laboratorio TASCCesare Grazioli - 9Department of Chemistry, Washington State University, Pullman, Washington 99164-4630, USATeng Zhang - University of UppsalaMalgorzata Biczysko - 9Department of Chemistry, Washington State University, Pullman, Washington 99164-4630, USAAlberto Baiardi - Scuola Normale SuperioreKirk A Peterson - Washington State University
- Publication Details
- The Journal of chemical physics, Vol.144(20), pp.204305-204305
- Academic Unit
- Chemistry, Department of
- Number of pages
- 20
- Grant note
- Elettra Synchrotron Facility PON01-01078/8 / MUIR Astrid2 synchrotron Facility 312284 / CALIPSO support grant for research PRIN 2010ERFKXL006 / PRIN 2011 DEMOCRITOS
- Identifiers
- 99900547580501842
- Language
- English
- Resource Type
- Journal article