Journal article
Interpretation of the photoelectron, ultraviolet, and vacuum ultraviolet photoabsorption spectra of bromobenzene by ab initio configuration interaction and DFT computations
The Journal of chemical physics, Vol.143(16), pp.164303-164303
10/28/2015
Handle:
https://hdl.handle.net/2376/105253
PMID: 26520509
Abstract
New photoelectron, ultraviolet (UV), and vacuum UV (VUV) spectra have been obtained for bromobenzene by synchrotron study with higher sensitivity and resolution than previous work. This, together with use of ab initio calculations with both configuration interaction and time dependent density functional theoretical methods, has led to major advances in interpretation. The VUV spectrum has led to identification of a considerable number of Rydberg states for the first time. The Franck-Condon (FC) analyses including both hot and cold bands lead to identification of the vibrational structure of both ionic and electronically excited states including two Rydberg states. The UV onset has been interpreted in some detail, and an interpretation based on the superposition of FC and Herzberg-Teller contributions has been performed. In a similar way, the 6 eV absorption band which is poorly resolved is analysed in terms of the presence of two ππ* states of (1)A1 (higher oscillator strength) and (1)B2 (lower oscillator strength) symmetries, respectively. The detailed analysis of the vibrational structure of the 2(2)B1 ionic state is particularly challenging, and the best interpretation is based on equation-of-motion-coupled cluster with singles and doubles computations. A number of equilibrium structures of the ionic and singlet excited states show that the molecular structure is less subject to variation than corresponding studies for iodobenzene. The equilibrium structures of the 3b13s and 6b23s (valence shell numbering) Rydberg states have been obtained and compared with the corresponding ionic limit structures.
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Details
- Title
- Interpretation of the photoelectron, ultraviolet, and vacuum ultraviolet photoabsorption spectra of bromobenzene by ab initio configuration interaction and DFT computations
- Creators
- Michael H Palmer - School of Chemistry, University of Edinburgh, Joseph Black Building, David Brewster Road, Edinburgh EH9 3FJ, Scotland, United KingdomTrevor Ridley - School of Chemistry, University of Edinburgh, Joseph Black Building, David Brewster Road, Edinburgh EH9 3FJ, Scotland, United KingdomSøren Vrønning Hoffmann - ISA, Department of Physics and Astronomy, Aarhus University, Ny Munkegade 120, DK-8000 Aarhus C, DenmarkNykola C Jones - ISA, Department of Physics and Astronomy, Aarhus University, Ny Munkegade 120, DK-8000 Aarhus C, DenmarkMarcello Coreno - CNR-IMIP, Montelibretti, c/o Laboratorio Elettra, Trieste, ItalyMonica de Simone - CNR-IOM Laboratorio TASC, Trieste, ItalyCesare Grazioli - CNR-IOM Laboratorio TASC, Trieste, ItalyTeng Zhang - Department of Physics and Astronomy, University of Uppsala, Uppsala, SwedenMalgorzata Biczysko - National Research Council ICCOM-CNR, UOS di Pisa, Via G. Moruzzi 1, I-56124 Pisa, ItalyAlberto Baiardi - Scuola Normale Superiore, Piazza Cavalieri 7, 56126 Pisa, ItalyKirk Peterson - Department of Chemistry, Washington State University, Pullman, Washington 99164-4630, USA
- Publication Details
- The Journal of chemical physics, Vol.143(16), pp.164303-164303
- Academic Unit
- Chemistry, Department of
- Publisher
- United States
- Identifiers
- 99900547080501842
- Language
- English
- Resource Type
- Journal article