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Electronic excitations in homopolyatomic bismuth cations: spectroscopic measurements in molten salts and an ab initio CI-singles study

Electronic excitations in homopolyatomic bismuth cations: spectroscopic measurements in molten salts and an ab initio CI-singles study
Electronic excitations in homopolyatomic bismuth cations: spectroscopic measurements in molten salts and an ab initio CI-singles study
The electronic excitations of the low-valence bismuth cluster cations Bi53+, Bi82+, and Bi95+ have been studied with experimental and theoretical techniques. The UV-visible spectra of the bismuth ions were measured in acidic chloroaluminate melts (mixture of 1-methyl-3-benzyl imidazolium chloride and AlCl3). The spectra of the Bi53+ and Bi82+ ions agree fairly well with previous reports, but also revealed additional low-energy absorptions. Ab initio methods were employed to assign the experimentally observed electronic transitions of these homopolyatomic bismuth cations. Structures were optimized at the RHF, MP2, and B3LYP levels of theory by using split-valence LANL2DZ basis sets that were augmented with one and two sets of pure d functions. The computed structures agree well with the results of neutron diffraction analyses of melts. Electronically excited states of the three clusters were treated by using the CI-Singles theory. The results of these calculations were used to explain the observed UV-visible spectra. The observed electronic excitations in the UV-visible range are all found to result from transitions involving the molecular orbitals formed by 6p-atomic-orbital overlap. This leads to the necessity of using basis sets that include d-type functions, which allow for an adequate description of the bonding that results from such p-orbital overlap. Spin-orbit coupling becomes increasingly important with increasing atomic number and its consideration is necessary when describing the electronic transitions in clusters of heavy atoms. The calculations show that singlet-triplet transitions, which are made accessible by strong spin-orbit coupling, are responsible for some of the observed absorptions
0947-6539
1078-1086
Day, Graeme
e3be79ba-ad12-4461-b735-74d5c4355636
Glaser, Rainer
c209af9f-73ef-471a-a058-eb75fdad418e
Shimomura, Noriyuki
d3af203b-c563-4e39-91eb-b05020c55726
Takamuku, Atsushi
30a16da7-0d7b-428a-a5f4-99e2f94b4daf
Ichikawa, Kazuhiko
77b134b1-5055-45e7-9d45-e7e9a6d2c087
Day, Graeme
e3be79ba-ad12-4461-b735-74d5c4355636
Glaser, Rainer
c209af9f-73ef-471a-a058-eb75fdad418e
Shimomura, Noriyuki
d3af203b-c563-4e39-91eb-b05020c55726
Takamuku, Atsushi
30a16da7-0d7b-428a-a5f4-99e2f94b4daf
Ichikawa, Kazuhiko
77b134b1-5055-45e7-9d45-e7e9a6d2c087

Day, Graeme, Glaser, Rainer, Shimomura, Noriyuki, Takamuku, Atsushi and Ichikawa, Kazuhiko (2000) Electronic excitations in homopolyatomic bismuth cations: spectroscopic measurements in molten salts and an ab initio CI-singles study. Chemistry - A European Journal, 6 (6), 1078-1086. (doi:10.1002/(SICI)1521-3765(20000317)6:6<1078::AID-CHEM1078>3.0.CO;2-R).

Record type: Article

Abstract

The electronic excitations of the low-valence bismuth cluster cations Bi53+, Bi82+, and Bi95+ have been studied with experimental and theoretical techniques. The UV-visible spectra of the bismuth ions were measured in acidic chloroaluminate melts (mixture of 1-methyl-3-benzyl imidazolium chloride and AlCl3). The spectra of the Bi53+ and Bi82+ ions agree fairly well with previous reports, but also revealed additional low-energy absorptions. Ab initio methods were employed to assign the experimentally observed electronic transitions of these homopolyatomic bismuth cations. Structures were optimized at the RHF, MP2, and B3LYP levels of theory by using split-valence LANL2DZ basis sets that were augmented with one and two sets of pure d functions. The computed structures agree well with the results of neutron diffraction analyses of melts. Electronically excited states of the three clusters were treated by using the CI-Singles theory. The results of these calculations were used to explain the observed UV-visible spectra. The observed electronic excitations in the UV-visible range are all found to result from transitions involving the molecular orbitals formed by 6p-atomic-orbital overlap. This leads to the necessity of using basis sets that include d-type functions, which allow for an adequate description of the bonding that results from such p-orbital overlap. Spin-orbit coupling becomes increasingly important with increasing atomic number and its consideration is necessary when describing the electronic transitions in clusters of heavy atoms. The calculations show that singlet-triplet transitions, which are made accessible by strong spin-orbit coupling, are responsible for some of the observed absorptions

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Published date: March 2000
Organisations: Computational Systems Chemistry

Identifiers

Local EPrints ID: 343467
URI: https://eprints.soton.ac.uk/id/eprint/343467
ISSN: 0947-6539
PURE UUID: 83ba5658-a3c0-41e7-b755-02f6bd0e521a
ORCID for Graeme Day: ORCID iD orcid.org/0000-0001-8396-2771

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Date deposited: 19 Oct 2012 13:55
Last modified: 06 Jun 2018 12:28

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