Electronic states of Cu+4, Ag+4, and Au+4: Interpretation of the optical spectra of Cu+4
10.1063/1.459814
Crossref journal-article
AIP Publishing
The Journal of Chemical Physics (317)
Abstract

Complete active space multiconfiguration self-consistent field followed by single-reference and multi-reference CI calculations which included up to 1.1 million configurations are carried out on Cu+4, Ag+4, and Au+4. The ground states of all three ions are found to be X 2B1u states with equilibrium geometries of rhombus. We compute the atomization energies of Cu+4, Ag+4, and Au+4 as 6.2, 5.2, and 7.3 eV, respectively, in agreement, with the experimental prediction for AE(Cu+4) < 6.8 eV by Jarrold and Creegan. Calculations of excited states reveal a low-lying 2B2u excited state (Te ∼ 6000–7000cm−1) for all three M+4. For Cu+4 we also studied the excited 2Ag, 2B1g, and 2B2g states. Our calculations show that the optical spectra of Cu+4 observed by Jarrold and Creegan in the 690 nm region are due to the (Cud → s)2B1g–X2B1u transition while one of the unassigned bands in the 420–490 nm region is due to the 2Ag–X2B1u transition of Cu+4 which is predominantly a valence transition. Our calculations support the complex vibronic structure of the 690 nm system.

Bibliography

Balasubramanian, K., & Das, K. K. (1991). Electronic states of Cu+4, Ag+4, and Au+4: Interpretation of the optical spectra of Cu+4. The Journal of Chemical Physics, 94(4), 2923–2927.

Authors 2
  1. K. Balasubramanian (first)
  2. K. K. Das (additional)
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Dates
Type When
Created 23 years, 1 month ago (July 26, 2002, 8:20 a.m.)
Deposited 1 year, 6 months ago (Feb. 10, 2024, 7:41 a.m.)
Indexed 1 year, 6 months ago (Feb. 10, 2024, 2:20 p.m.)
Issued 34 years, 6 months ago (Feb. 15, 1991)
Published 34 years, 6 months ago (Feb. 15, 1991)
Published Print 34 years, 6 months ago (Feb. 15, 1991)
Funders 0

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@article{Balasubramanian_1991, title={Electronic states of Cu+4, Ag+4, and Au+4: Interpretation of the optical spectra of Cu+4}, volume={94}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.459814}, DOI={10.1063/1.459814}, number={4}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Balasubramanian, K. and Das, K. K.}, year={1991}, month=feb, pages={2923–2927} }