A fresh look at the photoelectron spectrum of bromobenzene: A third-order non-Dyson electron propagator study
- Interdisciplinary Center for Scientific Computing, University of Heidelberg, Im Neuenheimer Feld 368, D-69120 Heidelberg (Germany)
- Daresbury Laboratory, Daresbury, Warrington, Cheshire WA4 4AD (United Kingdom)
- Synchrotron Soleil, L’Orme des Merisiers, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette Cedex (France)
The valence-shell ionization spectrum of bromobenzene, as a representative halogen substituted aromatic, was studied using the non-Dyson third-order algebraic-diagrammatic construction [nD-ADC(3)] approximation for the electron propagator. This method, also referred to as IP-ADC(3), was implemented as a part of the Q-Chem program and enables large-scale calculations of the ionization spectra, where the computational effort scales as n{sup 5} with respect to the number of molecular orbitals n. The IP-ADC(3) scheme is ideally suited for investigating low-lying ionization transitions, so fresh insight could be gained into the cationic state manifold of bromobenzene. In particular, the present IP-ADC(3) calculations with the cc-pVTZ basis reveal a whole class of low-lying low-intensity two-hole-one-particle (2h-1p) doublet and quartet states, which are relevant to various photoionization processes. The good qualitative agreement between the theoretical spectral profile for the valence-shell ionization transitions generated with the smaller cc-pVDZ basis set and the experimental photoelectron spectrum measured at a photon energy of 80 eV on the PLÉIADES beamline at the Soleil synchrotron radiation source allowed all the main features to be assigned. Some theoretical aspects of the ionization energy calculations concerning the use of various approximation schemes and basis sets are discussed.
- OSTI ID:
- 22489692
- Journal Information:
- Journal of Chemical Physics, Vol. 143, Issue 14; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
Similar Records
Propagator quantum chemical study of S-cis-(Z)-2-(2-formylethenyl)pyrrole: electronic structure and aspects of intramolecular hydrogen bond manifestation in ionization spectra
An evaluation of correlation-consistent basis sets in calculating the structure and energetics of (H{sub 3}Si){sub 2}O, H{sub 3}SiOH, and H{sub 3}SiO{sup {minus}}