Quantum Chemical Study of the Low-Lying Electronic States of VSi3–/0 Clusters and Interpretation of the Anion Photoelectron Spectrum
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- 作者：Van Tan Tran ; Quoc Tri Tran
- 刊名：Journal of Physical Chemistry A
- 出版年：2016
- 出版时间：July 28, 2016
- 年：2016
- 卷：120
- 期：29
- 页码：5950-5957
- 全文大小：390K
- 年卷期：0
- ISSN：1520-5215
文摘
The geometrical and electronic structures of VSi3–/0 clusters have been investigated with the DFT, CCSD(T), and CASSCF/CASPT2 methods. The results showed that the suitable functional to identify the ground states of VSi3–/0 clusters is not the B3LYP but the BP86. At the BP86, CCSD(T), and CASPT2 levels, the ground state of the anionic cluster was the 1A′ (1A1) of tetrahedral η3-(Si3)V– isomer, while that of the neutral cluster was the 12A′ and 12A″ (12E) of the same isomer. The 12A′ and 12A″ of the tetrahedral η3-(Si3)V isomer were the results of the Jahn–Teller distortions of the 12E in C3v symmetry. All three bands in the photoelectron spectrum of the VSi3– cluster were interpreted by one-electron detachments from the 1A′ anionic ground state on the basis of the BP86, CCSD(T), and CASPT2 methods. The calculated adiabatic and vertical detachment energies were in agreement with the experimental values. The broad shape of the first band was explained by Franck–Condon factor simulations for the 1A′ → 12A′ and 1A′ → 12A″ transitions within the tetrahedral η3-(Si3)V–/0 isomers.