期刊
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 14, 期 24, 页码 8732-8741出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c2cp40898h
关键词
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资金
- Minister of Science and Innovation
- Eusko Jaurlaritza [GIC 07/85 IT-330-07]
- Spanish Office for Scientific Research [CTQ2011-27374]
- National Science Foundation [CHE-0808984]
- CSIC under JAE-DOC
- FSE
- University of the Basque Country UPV/EHU [IT-366-07]
- Spanish Ministerio de Ciencia e Innovacion [FIS2010-19609-C02-02]
The excited states of the gold dimer have been investigated using modern theoretical tools including the multiconfigurational exact molecular mean-field intermediate Hamiltonian Fock-space Coupled Cluster, X2Cmmf-IHFSCC, and the complete active space self-consistent field followed by second order perturbation theory, CASSCF/CASPT2. The computed optically active transitions have been benchmarked against the available experimental data and compared with time-dependent density functional theory, TDDFT, results, both in the two-and four-component schemes. We explored in great detail several spectroscopic properties such as bond lengths, potential energy surfaces (PES), vibrational frequencies and vibrational progressions of the ground and low-lying excited states. Our data show excellent agreement with the experimental measurements and present a significant improvement compared to previous ab initio calculations. They also permit a detailed investigation of the intriguing a <- X and A' <- X experimental bands that, according to our calculations, show an avoided energy level crossing. The location of this crossing is critical for a correct estimation of the vibrational progression and oscillator strengths of these two states. Moreover, among the exchange-correlation (xc) potentials, the SAOP gives the best excitation energies, followed by the hybrid B3LYP functional. Pure functionals like BLYP give by far the worst results.
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