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Søren Vrønning Hoffmann

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

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Standard

Interpretation of the photoelectron, ultraviolet, and vacuum ultraviolet photoabsorption spectra of bromobenzene by ab initio configuration interaction and DFT computations. / Palmer, Michael H.; Ridley, Trevor; Hoffmann, Soren Vrønning; Jones, Nykola C.; Coreno, Marcello; de Simone, Monica; Grazioli, Cesare; Zhang, Teng; Biczysko, Malgorzata; Baiardi, Alberto; Peterson, Kirk.

In: Journal of Chemical Physics, Vol. 143, No. 16, 164303, 2015.

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaperJournal articleResearchpeer-review

Harvard

Palmer, MH, Ridley, T, Hoffmann, SV, Jones, NC, Coreno, M, de Simone, M, Grazioli, C, Zhang, T, Biczysko, M, Baiardi, A & Peterson, K 2015, 'Interpretation of the photoelectron, ultraviolet, and vacuum ultraviolet photoabsorption spectra of bromobenzene by ab initio configuration interaction and DFT computations', Journal of Chemical Physics, vol. 143, no. 16, 164303. https://doi.org/10.1063/1.4933419

APA

Palmer, M. H., Ridley, T., Hoffmann, S. V., Jones, N. C., Coreno, M., de Simone, M., Grazioli, C., Zhang, T., Biczysko, M., Baiardi, A., & Peterson, K. (2015). Interpretation of the photoelectron, ultraviolet, and vacuum ultraviolet photoabsorption spectra of bromobenzene by ab initio configuration interaction and DFT computations. Journal of Chemical Physics, 143(16), [164303]. https://doi.org/10.1063/1.4933419

CBE

Palmer MH, Ridley T, Hoffmann SV, Jones NC, Coreno M, de Simone M, Grazioli C, Zhang T, Biczysko M, Baiardi A, Peterson K. 2015. Interpretation of the photoelectron, ultraviolet, and vacuum ultraviolet photoabsorption spectra of bromobenzene by ab initio configuration interaction and DFT computations. Journal of Chemical Physics. 143(16):Article 164303. https://doi.org/10.1063/1.4933419

MLA

Vancouver

Author

Palmer, Michael H. ; Ridley, Trevor ; Hoffmann, Soren Vrønning ; Jones, Nykola C. ; Coreno, Marcello ; de Simone, Monica ; Grazioli, Cesare ; Zhang, Teng ; Biczysko, Malgorzata ; Baiardi, Alberto ; Peterson, Kirk. / Interpretation of the photoelectron, ultraviolet, and vacuum ultraviolet photoabsorption spectra of bromobenzene by ab initio configuration interaction and DFT computations. In: Journal of Chemical Physics. 2015 ; Vol. 143, No. 16.

Bibtex

@article{d8a743a05a964722aba7089ad8c97f55,
title = "Interpretation of the photoelectron, ultraviolet, and vacuum ultraviolet photoabsorption spectra of bromobenzene by ab initio configuration interaction and DFT computations",
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 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. (C) 2015 AIP Publishing LLC.",
keywords = "GAUSSIAN-BASIS SETS, CORRELATED MOLECULAR CALCULATIONS, FLUOROBENZENE RADICAL-CATION, DENSITY-FUNCTIONAL THEORY, ELECTRONIC STATES, PHOTODISSOCIATION MECHANISM, VIBRONIC INTERACTIONS, EXCITATION-ENERGIES, ABSORPTION-SPECTRA, RYDBERG STATES",
author = "Palmer, {Michael H.} and Trevor Ridley and Hoffmann, {Soren Vr{\o}nning} and Jones, {Nykola C.} and Marcello Coreno and {de Simone}, Monica and Cesare Grazioli and Teng Zhang and Malgorzata Biczysko and Alberto Baiardi and Kirk Peterson",
year = "2015",
doi = "10.1063/1.4933419",
language = "English",
volume = "143",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "AMER INST PHYSICS",
number = "16",

}

RIS

TY - JOUR

T1 - Interpretation of the photoelectron, ultraviolet, and vacuum ultraviolet photoabsorption spectra of bromobenzene by ab initio configuration interaction and DFT computations

AU - Palmer, Michael H.

AU - Ridley, Trevor

AU - Hoffmann, Soren Vrønning

AU - Jones, Nykola C.

AU - Coreno, Marcello

AU - de Simone, Monica

AU - Grazioli, Cesare

AU - Zhang, Teng

AU - Biczysko, Malgorzata

AU - Baiardi, Alberto

AU - Peterson, Kirk

PY - 2015

Y1 - 2015

N2 - 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. (C) 2015 AIP Publishing LLC.

AB - 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. (C) 2015 AIP Publishing LLC.

KW - GAUSSIAN-BASIS SETS

KW - CORRELATED MOLECULAR CALCULATIONS

KW - FLUOROBENZENE RADICAL-CATION

KW - DENSITY-FUNCTIONAL THEORY

KW - ELECTRONIC STATES

KW - PHOTODISSOCIATION MECHANISM

KW - VIBRONIC INTERACTIONS

KW - EXCITATION-ENERGIES

KW - ABSORPTION-SPECTRA

KW - RYDBERG STATES

U2 - 10.1063/1.4933419

DO - 10.1063/1.4933419

M3 - Journal article

C2 - 26520509

VL - 143

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 16

M1 - 164303

ER -