Ammonia activation by V sup + : Electronic and translational energy dependence

Journal Article · Thu Jan 11 04:00:00 EST 1990 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100364a034· OSTI ID:6947608

Clemmer, D E; Sunderlin, L S; Armentrout, P B ^[1]

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1. Univ. of Utah, Salt Lake City (USA)

The reaction of V{sup +} with ammonia is studied as a function of translational energy in a guided ion beam tandem mass spectrometer. The effect of electronic energy is also probed by varying the conditions for forming V{sup +}. The a{sup 3}F state of V{sup +} is found to be substantially more reactive than the a{sup 5}D ground and a{sup 5}F first excited states. The results indicate that reaction occurs primarily through a triplet H-V{sup +}-NH{sub 2} intermediate. The reactivities of the different electronic states of V{sup +} can be explained by using molecular orbital and spin conservation concepts. The thresholds for the cross sections of the endothermic reactions are interpreted to give the 298 K bond energies of D{degree}(V{sup +}-NH{sub 2}) = 3.18 {plus minus} 0.10, D{degree}(V{sup +}-NH) = 4.30 {plus minus} 0.16, and D{degree}(V{sup +}-N) = 4.65 {plus minus} 0.06, all in electronvolts. The large bond strengths of V{sup +}-NH{sub 2} and V{sup +}-NH indicate that the lone pair electrons on the nitrogen atom are involved in the metal-ligand bond.

• OSTI ID: 6947608
• Journal Information: Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 94:1; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
AMMONIA
CHARGED PARTICLES
CHEMICAL ACTIVATION
DATA
DATA ANALYSIS
ELECTRONIC STRUCTURE
EXPERIMENTAL DATA
HYDRIDES
HYDROGEN COMPOUNDS
INFORMATION
IONS
MASS SPECTROSCOPY
MEASURING INSTRUMENTS
MEASURING METHODS
NITROGEN COMPOUNDS
NITROGEN HYDRIDES
NUMERICAL DATA
SPECTROSCOPY
VANADIUM IONS