Interpretation of the photoelectron, ultraviolet, and vacuum ultraviolet photoabsorption spectra of bromobenzene by ab initio configuration interaction and DFT computations

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 functi...

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Published inThe Journal of chemical physics Vol. 143; no. 16; p. 164303
Main Authors Palmer, Michael H., Ridley, Trevor, Hoffmann, Søren Vrønning, Jones, Nykola C., Coreno, Marcello, de Simone, Monica, Grazioli, Cesare, Zhang, Teng, Biczysko, Malgorzata, Baiardi, Alberto, Peterson, Kirk
Format Journal Article
LanguageEnglish
Published United States American Institute of Physics 28.10.2015
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ISSN0021-9606
1089-7690
1089-7690
DOI10.1063/1.4933419

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Summary: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 1A1 (higher oscillator strength) and 1B2 (lower oscillator strength) symmetries, respectively. The detailed analysis of the vibrational structure of the 22B1 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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ISSN:0021-9606
1089-7690
1089-7690
DOI:10.1063/1.4933419