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Title: A comparative study of the Au + H{sub 2}, Au{sup +} + H{sub 2}, and Au{sup −} + H{sub 2} systems: Potential energy surfaces and dynamics of reactive collisions

In order to study the Au{sup −} + H{sub 2} collision, a new global potential energy surface (PES) describing the ground electronic state of AuH{sub 2}{sup −} system is developed and compared with the PESs of the neutral [Zanchet et al., J. Chem. Phys. 132, 034301 (2010)] and cationic systems [Anaís et al., J. Chem. Phys. 135, 091102 (2011)]. We found that Au{sup −} − H{sub 2} presents a H-Au-H insertion minimum attributed to the stabilization of the LUMO 3b{sub 2} orbital, which can be considered as the preamble of the chemisorption well appearing in larger gold clusters. While the LUMO orbital is stabilized, the HOMO 6a{sub 1} is destabilized, creating a barrier at the geometry where the energy orbitals’ curves are crossing. In the anion, this HOMO is doubly occupied, while in the neutral system is half-filled and completely empty in the cation, explaining the gradual disappearance of the well and the barrier as the number of electrons decreases. The cation presents a well in the entrance channel partially explained by electrostatic interactions. The three systems’ reactions are highly endothermic, by 1.66, 2.79, and 3.23 eV for AuH, AuH{sup +}, and AuH{sup −} products, respectively. The reaction dynamics ismore » studied using quasi-classical trajectory method for the three systems. The one corresponding to the anionic system is new in this work. Collision energies between 1.00 and 8.00 eV, measured for the cation, are in good agreement with the simulated cross section for the AuH{sup +}. It was also found that the total fragmentation, in three atoms, competes becoming dominant at sufficiently high energy. Here, we study the competition between the two different reaction pathways for the anionic, cationic, and neutral species, explaining the differences using a simple model based on the topology of the potential energy surfaces.« less
Authors:
 [1] ; ;  [2] ;  [3]
  1. Facultad de Ciencias Básicas y Aplicadas, Departamento de Física, Universidad Militar Nueva Granada, Bogotá DC (Colombia)
  2. Instituto de Física Fundamental, CSIC Serrano 123, 28006 Madrid (Spain)
  3. Facultad de Ciencias, Departamento de Química-Física Aplicada, Unidad Asociada CSIC-UAM, Universidad Autónoma de Madrid, 28049 Madrid (Spain)
Publication Date:
OSTI Identifier:
22415670
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 15; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANIONS; ATOMS; CATIONS; CHEMISORPTION; COMPARATIVE EVALUATIONS; ELECTRONS; EV RANGE; GOLD; GOLD HYDRIDES; GOLD IONS; GROUND STATES; HYDROGEN; ION-MOLECULE COLLISIONS; POTENTIAL ENERGY; SURFACES