Guided ion beam and theoretical study of the reactions of Au{sup +} with H{sub 2}, D{sub 2}, and HD

Journal Article · Fri Jan 14 00:00:00 EST 2011 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3514899· OSTI ID:21559973

Fengxia, Li; Hinton, Christopher S; Citir, Murat; Liu, Fuyi; Armentrout, P B ^[1]

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1. Chemistry Department, University of Utah, 315 S. 1400 E. Rm 2020, Salt Lake City, Utah 84112 (United States)

Reactions of the late third-row transition metal cation Au{sup +} with H{sub 2}, D{sub 2}, and HD are examined using guided ion beam tandem mass spectrometry. A flow tube ion source produces Au{sup +} in its {sup 1}S (5d{sup 10}) electronic ground state level. Corresponding state-specific reaction cross sections for forming AuH{sup +} and AuD{sup +} as a function of kinetic energy are obtained and analyzed to give a 0 K bond dissociation energy of D{sub 0}(Au{sup +}-H) = 2.13 {+-} 0.11 eV. Quantum chemical calculations at the B3LYP/HW+/6-311+G(3p) and B3LYP/Def2TZVPP levels performed here show good agreement with the experimental bond energy. Theory also provides the electronic structures of these species and the reactive potential energy surfaces. We also compare this third-row transition metal system with previous results for analogous reactions of the first-row and second-row congeners, Cu{sup +} and Ag{sup +}. We find that Au{sup +} has a stronger M{sup +}-H bond, which can be explained by the lanthanide contraction and relativistic effects that alter the relative size of the valence s and d orbitals. Results from reactions with HD provide insight into the reaction mechanism and indicate that ground state Au{sup +} reacts largely via a direct mechanism, in concordance with the behavior of the lighter group 11 metal ions, but includes more statistical behavior than these metals as well.

• OSTI ID: 21559973
• Journal Information: Journal of Chemical Physics, Vol. 134, Issue 2; Other Information: DOI: 10.1063/1.3514899; (c) 2011 American Institute of Physics; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BINDING ENERGY
CATIONS
COPPER IONS
CROSS SECTIONS
DEUTERIUM COMPOUNDS
DISSOCIATION ENERGY
ELECTRONIC STRUCTURE
GOLD
GOLD IONS
HYDROGEN
ION BEAMS
IONIZATION POTENTIAL
ION-MOLECULE COLLISIONS
KINETIC ENERGY
MASS SPECTROSCOPY
POTENTIAL ENERGY
QUANTUM COMPUTERS
RARE EARTHS
REACTION KINETICS
SILVER IONS
BEAMS
CHARGED PARTICLES
COLLISIONS
COMPUTERS
ELEMENTS
ENERGY
HYDROGEN COMPOUNDS
ION COLLISIONS
IONS
KINETICS
METALS
MOLECULE COLLISIONS
NONMETALS
SPECTROSCOPY
TRANSITION ELEMENTS