Electronic spectroscopy of the Au–Xe complex

Plowright, Richard J.; Watkins, Mark J.; Gardner, Adrian M.; Withers, Carolyn D.; Wright, Timothy G.; Breckenridge, W. H.

doi:10.1039/b818451h

Cited by 12 publications

(28 citation statements)

References 37 publications

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“…The reaction products scheme is presented in Fig. 45 Plowright et al 46 studied Au-Xe complex in their lowest states. The asymptotic energy differences of the Au ͑ 2 S, 2 D, and 2 P͒ +SiH 4 reactants directly reflect the gold atom spectroscopy.…”

Section: Resultsmentioning

confidence: 99%

Transition probabilities for the Au (S2, D2, and P2) with SiH4 reaction

Pacheco-Sánchez

Luna‐García

García-Cruz

et al. 2010

The Journal of Chemical Physics

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Transition probabilities on the interaction of the ground and the lowest excited states of gold Au ((2)S:5d(10)6s(1), (2)D:5d(9)6s(2), and (2)P:5d(10)6p(1)) with silane (SiH(4)) are studied through ab initio Hartree-Fock self-consistent field calculations, where the atom's core is represented by relativistic effective core potentials. These calculations are followed by a multiconfigurational self-consistent field study. The correlation energy is accounted for through extensive variational and perturbative second order multireference Moller-Plesset configuration interaction analysis of selected perturbations obtained by iterative process calculations using the CIPSI program package. It is found that the Au atom in the ((2)P:5d(10)6p(1)) state inserts in the Si-H bond. In this interaction its corresponding D (2)A(') potential energy surface is initially attractive and only becomes repulsive after encountering an avoided crossing with the initially repulsive C (2)A(') surface linked to the Au((2)D:5d(9)6s(2))-SiH(4) fragments. The A, B, and C (2)A(') curves derived from the Au((2)D:5d(9)6s(2)) atom interaction with silane are initially repulsive, each one of them showing two avoided crossings, while the A (2)A(') curve goes sharply downwards until it meets the X (2)A(') curve interacting adiabatically, which is linked with the Au((2)S:5d(10)6s(1))-SiH(4) moieties. The A (2)A(') curve becomes repulsive after the avoided crossing with the X (2)A('), curve. The lowest-lying X (2)A(') potential leads to the HAuSiH(3) X (2)A(') intermediate molecule. This intermediate molecule, diabatically correlated with the Au((2)P:5d(10)6p(1))+SiH(4) system which lies 3.34 kcal/mol above the ground state reactants, has been carefully characterized as have the dissociation channels leading to the AuH+SiH(3) and H+AuSiH(3) products. These products are reached from the HAuSiH(3) intermediate without any activation barrier. The Au-SiH(4) calculation results are successfully compared to experiment. Landau-Zener theory of avoided crossings is applied to these interactions considering the angle theta instead of the distance r as the reaction coordinate.

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Section: Resultsmentioning

confidence: 99%

Transition probabilities for the Au (S2, D2, and P2) with SiH4 reaction

Pacheco-Sánchez

Luna‐García

García-Cruz

et al. 2010

The Journal of Chemical Physics

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“…On the other hand, the interaction between open‐shell neutral coinage metal and rare gas atom has been studied intensively . Duncan and coworkers and Breckenridge and coworkers have investigated the electronic spectroscopy of M–Rg complexes: Au–Rg (Rg = Ne, Ar, Kr and Xe), Ag–Rg (Rg = Ar, Kr, and Xe), and Cu–Kr by means of resonance enhanced multiphoton ionization spectroscopy. Gardner et al also obtained the RCCSD(T) PECs for the X 2 ∑ + electronic states of the M–Rg (M = Cu–Au and Rg = He–Rn) complexes and derived the spectroscopic parameters and compared them with those determined experimentally.…”

Section: Introductionmentioning

confidence: 99%

Nature of closed‐ and open‐shell interactions between noble metals and rare gas atoms

Jamshidi

Eskandari

Azami

2013

Int J of Quantum Chemistry

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Interactions between noble metals and rare gases have become an interesting topic over the last few years. In this work, a computational study of the open-shell (d 10 s 1 ) and closed-shell (d 10 s and d 10 s 2 ) noble metals (M ¼ Cu, Ag, and Au) with three heaviest rare gas atoms (Rg ¼ Kr, Xe, and Rn) has been performed. Potential energy curves based on ab initio [MP2, MP4, QCISD, and CCSD(T)] and DFT functionals (M06-2X and CAM-B3LYP) were obtained for ionic and neutral AuXe complexes. Dissociation energies indicate that neutral metals have the lowest and cationic metals have the highest affinities for interaction with rare gas atoms. For the same metals, there is a continuous increase in dissociation energies (D e ) from Kr to Rn. The nature of bonding and the trend of D e and equilibrium bond lengths (R e ) have been interpreted by means of quantum theory of atoms in molecules, natural bond orbital, and energy decomposition analysis.

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“…Among these, the interaction of Ag and other coinage metals with noble gases has been the subject of numerous experimental studies. [10][11][12][13][14][15][16][17] Spectroscopic studies on these complexes have focused on the molecular absorption corresponding to the strong atomic 2 P ← 2 S transition. The understanding of the bonding of such vdW complexes can be used to improve models of atom-surface interaction and study of chemical reaction dynamics, [18][19][20] while their decay by chemical exchange, pre-dissociation, and dissociation, can be controlled by external fields.…”

Section: Introductionmentioning

confidence: 99%

Potential energy curves for the interaction of Ag($\mathbf {5}{\bm s}$5s) and Ag($\mathbf {5}{\bm p}$5p) with noble gas atoms

Loreau

Sadeghpour

Dalgarno

2013

The Journal of Chemical Physics

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We investigate the interaction of ground and excited states of a silver atom with noble gases (NG), including helium. Born-Oppenheimer potential energy curves are calculated with quantum chemistry methods and spin-orbit effects in the excited states are included by assuming a spin-orbit splitting independent of the internuclear distance. We compare our results with experimentally available spectroscopic data, as well as with previous calculations. Because of strong spin-orbit interactions, excited Ag-NG potential energy curves cannot be fitted to Morse-like potentials. We find that the labeling of the observed vibrational levels has to be shifted by one unit.

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Electronic spectroscopy of the Au–Xe complex

Cited by 12 publications

References 37 publications

Transition probabilities for the Au (S2, D2, and P2) with SiH4 reaction

Transition probabilities for the Au (S2, D2, and P2) with SiH4 reaction

Nature of closed‐ and open‐shell interactions between noble metals and rare gas atoms

Potential energy curves for the interaction of Ag($\mathbf {5}{\bm s}$5s) and Ag($\mathbf {5}{\bm p}$5p) with noble gas atoms

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