Interpretation of the photoelectron, ultraviolet, and vacuum ultraviolet photoabsorption spectra of bromobenzene by ab initio configuration interaction and DFT computations
2015 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 143, no 16, 164303Article in journal (Refereed) Published
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
Condensed Matter Physics
IdentifiersURN: urn:nbn:se:uu:diva-268429DOI: 10.1063/1.4933419ISI: 000364235800018PubMedID: 26520509OAI: oai:DiVA.org:uu-268429DiVA: diva2:876721
FunderEU, FP7, Seventh Framework Programme, FP7/2007-2013EU, FP7, Seventh Framework Programme, 312284