uu.seUppsala University Publications
Change search
ReferencesLink to record
Permanent link

Direct link
Interpretation of the photoelectron, ultraviolet, and vacuum ultraviolet photoabsorption spectra of bromobenzene by ab initio configuration interaction and DFT computations
Univ Edinburgh, Sch Chem, Edinburgh EH9 3FJ, Midlothian, Scotland..
Univ Edinburgh, Sch Chem, Edinburgh EH9 3FJ, Midlothian, Scotland..
Aarhus Univ, Dept Phys & Astron, ISA, DK-8000 Aarhus C, Denmark..
Aarhus Univ, Dept Phys & Astron, ISA, DK-8000 Aarhus C, Denmark..
Show others and affiliations
2015 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 143, no 16, 164303Article in journal (Refereed) Published
Abstract [en]

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 super-position 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 pi pi* states of (1)A(1) (higher oscillator strength) and B-1(2) (lower oscillator strength) symmetries, respectively. The detailed analysis of the vibrational structure of the 2(2)B(1) 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 3b(1)3s and 6b(2)3s (valence shell numbering) Rydberg states have been obtained and compared with the corresponding ionic limit structures.

Place, publisher, year, edition, pages
2015. Vol. 143, no 16, 164303
National Category
Condensed Matter Physics
URN: urn:nbn:se:uu:diva-268429DOI: 10.1063/1.4933419ISI: 000364235800018PubMedID: 26520509OAI: oai:DiVA.org:uu-268429DiVA: diva2:876721
EU, FP7, Seventh Framework Programme, FP7/2007-2013EU, FP7, Seventh Framework Programme, 312284
Available from: 2015-12-04 Created: 2015-12-04 Last updated: 2015-12-04Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full textPubMed

Search in DiVA

By author/editor
de Simone, MonicaZhang, Teng
By organisation
Molecular and condensed matter physics
In the same journal
Journal of Chemical Physics
Condensed Matter Physics

Search outside of DiVA

GoogleGoogle Scholar
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

Altmetric score

Total: 412 hits
ReferencesLink to record
Permanent link

Direct link