Quantum mechanical reactive scattering by a multiconfigurational time-dependent self-consistent field (MCTDSCF) approach
1990; Elsevier BV; Volume: 171; Issue: 1-2 Linguagem: Inglês
10.1016/0009-2614(90)80057-k
ISSN1873-4448
AutoresAudrey Dell Hammerich, Ronnie Kosloff, Mark A. Ratner,
Tópico(s)Advanced Chemical Physics Studies
ResumoThe major obstacle to the description of systems containing a large number of degrees of freedom is the exponential increase of computational time and effort with dimensionality. A strategy is presented to overcome this obstacle as well as the shortcoming of the omission of correlations, while still maintaining the simplicity and strengths of a mean-field description, based upon identifying the crucial dynamical correlations and incorporating them with multiconfigurations. The collinear reactive scattering of H + H2 illustrates the techniques involved and their adaptability, flexibility, and breadth of applicability. MCTDSCF simulations, constructed from time-dependent variational principles, are compared with the numerically exact solution of the Schrödinger equation; agreement is found.
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