2024-03-29T01:25:13Zhttp://digital.csic.es/dspace-oai/requestoai:digital.csic.es:10261/1019172016-02-18T03:03:20Zcom_10261_115com_10261_3col_10261_368
An interpretation of the absorption and emission spectra of the gold dimer using modern theoretical tools
Geethalakshmi, K. R.
Ruipérez, Fernando
Infante, Ivan
Ministerio de Ciencia e Innovación (España)
Eusko Jaurlaritza
National Science Foundation (US)
Consejo Superior de Investigaciones Científicas (España)
Universidad del País Vasco
European Commission
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. This journal is © the Owner Societies 2012.
I.I. would like to thank the Minister of Science and Innovation for granting a Juan de la Cierva Fellowship. I.I., F.R. and J.M.U would like to thank the Eusko Jaurlaritza (GIC 07/85 IT-330-07) for financial support and the Spanish Office for Scientific Research (CTQ2011-27374). The work of M.D.M. on the gold dimer is supported by the National Science Foundation under grant No. CHE-0808984. K.R.G. acknowledges the support by CSIC under the JAE-DOC program Junta para la Ampliacion de Estudios co-financed by FSE, and in part, by the University of the Basque Country UPV/EHU (Grant No. IT-366-07), the Spanish Ministerio de Ciencia e Innovacion (Grant No. FIS2010-19609-C02-02).
Peer Reviewed
2014-09-10T08:19:46Z
2014-09-10T08:19:46Z
2012
2014-09-10T08:19:46Z
artículo
http://purl.org/coar/resource_type/c_6501
doi: 10.1039/c2cp40898H
issn: 1463-9076
e-issn: 1463-9084
Physical Chemistry Chemical Physics 14(24): 8732-8741 (2012)
http://hdl.handle.net/10261/101917
10.1039/c2cp40898H
http://dx.doi.org/10.13039/501100004837
http://dx.doi.org/10.13039/100000001
http://dx.doi.org/10.13039/501100003339
http://dx.doi.org/10.13039/501100000780
http://dx.doi.org/10.13039/501100003086
none
Royal Society of Chemistry (UK)