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An interpretation of the absorption and emission spectra of the gold dimer using modern theoretical tools

AuthorsGeethalakshmi, K. R. ; Ruipérez, Fernando; Infante, Ivan
Issue Date2012
PublisherRoyal Society of Chemistry (UK)
CitationPhysical Chemistry Chemical Physics 14(24): 8732-8741 (2012)
AbstractThe 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. This journal is © the Owner Societies 2012.
Identifiersdoi: 10.1039/c2cp40898H
issn: 1463-9076
e-issn: 1463-9084
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