We present a new three-dimensional potential energy surface (PES) for the electronic ground state of the LiH + H reversible arrow Li + H-2 reaction and further analyze specific aspects of the lower four excited electronic states. Our reactive PESs are calculated using a CASSCF method followed by an MRCI treatment of the correlation energy. The ground-state three-dimensional surface is then fitted by using our own version of the Aguado-Paniagua interpolation form [Aguado, A.; Paniagua, M. J. Chem. Phys. 1992, 96, 1265]. A review of the previous computational work on this system, to which we compare our present findings, is given in the introduction of the paper: with respect to such earlier calculations of the ground-state PES [Dunne, L. J.; Murrell, J. N.; Jernmer, P. Chem. Phys. Lett. 2001, 336, 1], our data confirm the absence of a barrier along the path to the LiH depletion reaction and further reveal possible spurious features of the earlier computed surface which may in turn affect the resulting rates from low-energy dynamic studies of the title system.

Computing a three-dimensional electronic energy manifold for the LiH plus H (sic) Li + H-2 chemical reaction / M., Wernli; D., Caruso; Bodo, Enrico; Gianturco, Francesco Antonio. - In: JOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY, KINETICS, ENVIRONMENT, & GENERAL THEORY. - ISSN 1089-5639. - STAMPA. - 113:6(2009), pp. 1121-1128. [10.1021/jp809163g]

Computing a three-dimensional electronic energy manifold for the LiH plus H (sic) Li + H-2 chemical reaction

BODO, Enrico;GIANTURCO, Francesco Antonio
2009

Abstract

We present a new three-dimensional potential energy surface (PES) for the electronic ground state of the LiH + H reversible arrow Li + H-2 reaction and further analyze specific aspects of the lower four excited electronic states. Our reactive PESs are calculated using a CASSCF method followed by an MRCI treatment of the correlation energy. The ground-state three-dimensional surface is then fitted by using our own version of the Aguado-Paniagua interpolation form [Aguado, A.; Paniagua, M. J. Chem. Phys. 1992, 96, 1265]. A review of the previous computational work on this system, to which we compare our present findings, is given in the introduction of the paper: with respect to such earlier calculations of the ground-state PES [Dunne, L. J.; Murrell, J. N.; Jernmer, P. Chem. Phys. Lett. 2001, 336, 1], our data confirm the absence of a barrier along the path to the LiH depletion reaction and further reveal possible spurious features of the earlier computed surface which may in turn affect the resulting rates from low-energy dynamic studies of the title system.
2009
ab-initio calculations; lithium chemistry; quantum dynamics
01 Pubblicazione su rivista::01a Articolo in rivista
Computing a three-dimensional electronic energy manifold for the LiH plus H (sic) Li + H-2 chemical reaction / M., Wernli; D., Caruso; Bodo, Enrico; Gianturco, Francesco Antonio. - In: JOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY, KINETICS, ENVIRONMENT, & GENERAL THEORY. - ISSN 1089-5639. - STAMPA. - 113:6(2009), pp. 1121-1128. [10.1021/jp809163g]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/131200
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