Assignment of photoelectron spectra of halide–water clusters: Contrasting patterns of delocalization in Dyson orbitals
Metadata Field | Value | Language |
---|---|---|
dc.contributor | Joseph V. Ortiz, jvo0001@auburn.edu | en_US |
dc.creator | Dolgounitcheva, O. | |
dc.creator | Zakrzewski, V. G. | |
dc.creator | Ortiz, J. V. | |
dc.date.accessioned | 2020-01-16T17:19:24Z | |
dc.date.available | 2020-01-16T17:19:24Z | |
dc.date.created | 2013 | |
dc.identifier | 10.1063/1.4802251 | en_US |
dc.identifier.uri | https://aip.scitation.org/doi/pdf/10.1063/1.4802251?class=pdf | en_US |
dc.identifier.uri | http://hdl.handle.net/11200/49683 | |
dc.description.abstract | Ab initio electron propagator calculations in various self-energy approximations provide accurate assignments of peaks observed in the photoelectron spectra of complexes that comprise a fluoride or chloride anion and two or three water molecules. More than one minimum structure is found in all four cases. When the halide anion is Cl−, the first three final states may be described as quasidegenerate 2P chlorine atoms coordinated to water molecules. Higher final states consist of a chloride anion juxtaposed to a positive charge that is delocalized over the water molecules. For the clusters with fluoride anions, most of the final states correspond to Dyson orbitals that are delocalized over the F and O nuclei. A variety of F–O σ and π bonding and antibonding patterns are evident in the Dyson orbitals. The assignment of low-lying spectral peaks to halide p orbital vacancies or to delocalized solvent orbitals is more valid for the chloride clusters than for the fluoride clusters, where a delocalized picture arises from strong bonding interactions between F 2p and H2O 1b1 orbitals. | en_US |
dc.format | en_US | |
dc.relation.ispartof | Journal of Chemical Physics | en_US |
dc.relation.ispartofseries | 0021-9606 | en_US |
dc.title | Assignment of photoelectron spectra of halide–water clusters: Contrasting patterns of delocalization in Dyson orbitals | en_US |
dc.type | Text | en_US |
dc.type.genre | Journal Article, Academic Journal | en_US |
dc.citation.volume | 138 | en_US |
dc.citation.issue | 16 | en_US |
dc.citation.spage | 164317-1 | en_US |
dc.citation.epage | 164317-10 | en_US |
dc.description.status | Published | en_US |
dc.description.peerreview | Yes | en_US |
dc.creator.alternate | Ortiz, Joseph V. |