Guided ion beam and theoretical studies of the reaction of Ag{sup +} with CS{sub 2}: Gas-phase thermochemistry of AgS{sup +} and AgCS{sup +} and insight into spin-forbidden reactions

Journal Article · Thu Jan 14 00:00:00 EST 2010 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3285837· OSTI ID:21559826

Armentrout, P B ^[1]; Kretzschmar, Ilona ^[2]

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1. Department of Chemistry, University of Utah, 314 S. 1400 E. Rm 2020, Salt Lake City, Utah 84112 (United States)
2. Department of Chemical Engineering, The City College of New York, New York, New York 10031 (United States)

The gas-phase reactivity of the atomic transition metal cation, Ag{sup +}, with CS{sub 2} is investigated using guided-ion beam mass spectrometry. Endothermic reactions forming AgS{sup +} and AgCS{sup +} are observed but are quite inefficient. This observation is largely attributed to the stability of the closed shell Ag{sup +}({sup 1}S,4d{sup 10}) ground state, but is also influenced by the fact that the reactions producing ground state AgS{sup +} and AgCS{sup +} products are both spin forbidden. Analysis of the kinetic energy dependence of the cross sections for formation of these two products yields the 0 K bond energies of D{sub 0}(Ag{sup +}-S)=1.40{+-}0.12 eV and D{sub 0}(Ag{sup +}-CS)=1.98{+-}0.14 eV. Quantum chemical calculations are used to investigate the electronic structure of the two product ions as well as the potential energy surfaces for reaction. The primary mechanism involves oxidative addition of a CS bond to the metal cation followed by simple Ag-S or Ag-CS bond cleavage. Crossing points between the singlet and triplet surfaces are located near the transition states for bond activation. Comparison with analogous work on other late second-row transition metal cations indicates that the location of the crossing points bears directly on the efficiency of these spin-forbidden processes.

• OSTI ID: 21559826
• Journal Information: Journal of Chemical Physics, Vol. 132, Issue 2; Other Information: DOI: 10.1063/1.3285837; (c) 2010 American Institute of Physics; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BINDING ENERGY
CARBON SULFIDES
CATIONS
CESIUM SULFIDES
CHEMICAL ANALYSIS
CHEMICAL BONDS
CLEAVAGE
CROSS SECTIONS
ELECTRONIC STRUCTURE
GROUND STATES
ION BEAMS
IONIZATION POTENTIAL
ION-MOLECULE COLLISIONS
KINETIC ENERGY
MASS SPECTROSCOPY
POTENTIAL ENERGY
SILVER
SILVER IONS
SPIN
SURFACES
ALKALI METAL COMPOUNDS
ANGULAR MOMENTUM
BEAMS
CARBON COMPOUNDS
CESIUM COMPOUNDS
CHALCOGENIDES
CHARGED PARTICLES
COLLISIONS
ELEMENTS
ENERGY
ENERGY LEVELS
ION COLLISIONS
IONS
METALS
MICROSTRUCTURE
MOLECULE COLLISIONS
PARTICLE PROPERTIES
SPECTROSCOPY
SULFIDES
SULFUR COMPOUNDS
TRANSITION ELEMENTS