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Titolo:
Mechanistic and energetic details of adduct formation and sigma-bond activation in Zr+(H-2)(n) clusters
Autore:
Bushnell, JE; Kemper, PR; van Koppen, P; Bowers, MT;
Indirizzi:
Univ Calif Santa Barbara, Dept Chem & Biochem, Santa Barbara, CA 93106 USAUniv Calif Santa Barbara Santa Barbara CA USA 93106 Barbara, CA 93106 USA
Titolo Testata:
JOURNAL OF PHYSICAL CHEMISTRY A
fascicolo: 11, volume: 105, anno: 2001,
pagine: 2216 - 2224
SICI:
1089-5639(20010322)105:11<2216:MAEDOA>2.0.ZU;2-V
Fonte:
ISI
Lingua:
ENG
Soggetto:
MOLECULAR-HYDROGEN COMPLEXES; TRANSITION-METAL IONS; BINDING-ENERGIES; DISSOCIATION ENERGIES; H-2; LIGAND; ORIGIN; PARAMETERS; ORBITALS; 1ST-ROW;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
44
Recensione:
Indirizzi per estratti:
Indirizzo: Bowers, MT Univ Calif Santa Barbara, Dept Chem & Biochem, Santa Barbara, CA 93106 USA Univ Calif Santa Barbara Santa Barbara CA USA 93106 93106 USA
Citazione:
J.E. Bushnell et al., "Mechanistic and energetic details of adduct formation and sigma-bond activation in Zr+(H-2)(n) clusters", J PHYS CH A, 105(11), 2001, pp. 2216-2224

Abstract

The formation of Zr+(H-2)(n) clusters (n = 1-7) has been studied both experimentally and theoretically. Binding energies were determined via temperature-dependent equilibrium measurements, giving -Delta Ho degrees = 14.5 +/-0.3, 10.7 +/- 0.2, 10.1 +/- 0.3, 9.1 +/- 0.5, 9.2 +/- 0.5, 8.9 +/- 0.6, and 8.5 +/- 0.8 kcal/mol for n = 1-7, respectively. Both DFT(B3LYP) and MP2 calculations gave binding energies in excellent agreement with experiment. Zr+ appears to insert into the first H-2 to form the dihydride as predicted by theory. The rate of insertion was observed to have a negative temperature dependence and a positive pressure dependence, suggesting a cluster-assisted insertion mechanism. Interestingly, both DFT and MP2 calculations suggest that the dihydride may "uninsert" to form a pure dihydrogen cluster withn between 5 and 7.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 30/03/20 alle ore 10:17:24