On excited states of the Au3 cluster: an ab initio study

Rusakov, Alexander A.; Zaitsevskii, Andréi

doi:10.2478/s11534-008-0101-6

Cited by 6 publications

(6 citation statements)

References 14 publications

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“…[6][7][8][9][10] Several computational studies based on different levels of theory have been performed for the electronic transitions of the gold dimer and trimer. 8,[11][12][13][14][15][16][17][18][19][20][21] In particular, recent studies carried out in the framework of the time dependent density functional theory (TDDFT) scheme, 17,18 in which the relativistic corrections are accounted for at a scalar level, clearly show two major effects of the d electrons of Au atoms on the optical properties: the quenching of the oscillator strength due to enhanced screening of the s electrons by the d electrons and the strong s-d hybridization in the low energy transitions. However, only a partial agreement has been reached with the experiment because of the absence of the spin-orbit term in the calculations.…”

Section: Introductionmentioning

confidence: 99%

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

Geethalakshmi

Ruipérez

Knecht

et al. 2012

Phys. Chem. Chem. Phys.

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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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Section: Introductionmentioning

confidence: 99%

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

Geethalakshmi

Ruipérez

Knecht

et al. 2012

Phys. Chem. Chem. Phys.

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“…It has been employed in many other studies [2][3][4][12][13][14] on TM clusters, and results were obtained which were in good agreement with the experiment; this indicated that density functional calculation is a reliable method for the study of TM clusters.…”

Section: Computational Methods and Cluster Modelmentioning

confidence: 63%

All-electron relativistic calculation on Au5X (X = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn) clusters

2010

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All-electron scalar relativistic calculations on Au 5 X (X = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn) clusters have been performed by using density functional theory with the generalized gradient approximation. Our calculation results indicate that all the lowest energy geometries of Au 5 X clusters have planar structures; the doped X atoms prefer to occupy the fourfold coordination site. Except Au 5 Fe, Au 5 Co and Au 5 Zn, for other clusters including pure Au 6 cluster, the HOMO are delocalized obviously with a contribution from all atoms in the cluster. On the contrary, the electron localization in Au 5 Zn is very strong resulting in the least stability of this cluster. Au 5 Cu cluster with six delocalized electrons being defined as magic number for two-dimensional system has the largest VIP and deepest HOMO energy level. With the substitution Au for X atoms, the metallicity of all Au 5 X clusters is reinforced.

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“…The use of a more accurate basis set when calculating gold cluster states would decrease the excited state energy spacing in the energy range considered (see, e.g., Ref. []). An increase in the size of the gold cluster will also increase the density of electronic excited states, and lower the energy of the cation states which could increase charge transfer and vibronic coupling.…”

Section: Discussionmentioning

confidence: 99%

Nonadiabatic scattering of NO off Au₃ clusters: A simple and robust diabatic state manifold generation method for multiconfigurational wavefunctions

et al. 2018

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The presence of nonadiabatic effects during the interaction of small molecules with metals has been observed experimentally for the last decades. Specially remarkable are the effects found for NO/Au, where experiments have suggested the presence of very strong vibronic coupling during the molecular scattering. However, the accurate inclusion of the nonadiabatic effects in periodic boundary conditions (PBC) theoretical methods remain an unapproachable challenge. Here, aiming to give some theoretical insight to the strong vibronic coupling, we have adopted a pragmatic point of view, taking use of an auxiliary simplified system, NO/Au3. We show the importance of nonadiabatic coupling, during the scattering of NO from a Au3 cluster, using a diabatic representation of 12 electronic states of the system, including a few charge‐transfer states. Our diabatic representation is obtained by rotating the orbital and configuration interaction (CI) vectors of a restricted active space (RAS) wavefunction. We present a strategy for extracting the best effective manifold of states relevant to the system, below some prescribed energy, directly from the RAS CI vectors. This scheme is able to disentangle a large dense manifold of adiabatic states with strong coupling and crossings. This approach is also shown to work for multireference configuration interaction (MRCI). By performing quantum propagations, we observed an increase in vibrational redistribution with increasing initial vibrational or translational energies. We suggest that these nonadiabatic effects should also be present at smaller energies in larger clusters. © 2018 Wiley Periodicals, Inc.

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On excited states of the Au3 cluster: an ab initio study

Cited by 6 publications

References 14 publications

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

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

All-electron relativistic calculation on Au5X (X = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn) clusters

Nonadiabatic scattering of NO off Au₃ clusters: A simple and robust diabatic state manifold generation method for multiconfigurational wavefunctions

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On excited states of the Au3 cluster: an ab initio study

Cited by 6 publications

References 14 publications

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

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

All-electron relativistic calculation on Au5X (X = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn) clusters

Nonadiabatic scattering of NO off Au3 clusters: A simple and robust diabatic state manifold generation method for multiconfigurational wavefunctions

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Product

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Nonadiabatic scattering of NO off Au₃ clusters: A simple and robust diabatic state manifold generation method for multiconfigurational wavefunctions