Physical Chemistry

A system of physical chemistry. Kinetics - download pdf or read online

By Lewis

ISBN-10: 2152164164

ISBN-13: 9782152164168

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Additional info for A system of physical chemistry. Kinetics

Example text

A paired excitation function (PEF) basis set is a set of state functions obtained by the replacement of coupled spinorbital pairs {~d~d}' associated with the same spatial MO, by coupled virtual spinorbital pairs {¢ given initial state function. ¢} in a v v Let us write an initial state function, associated with an energy expression of monoconfigurational type as {I ~ .. ¢p~p ••• IK} being a basis set of Slater Determinants (SD), with the following characteristics: a) 'lK, the pair {¢ b) ¢ } appears p p in the SD basis set in the same position.

In this way the ordering principle can be fulfilled, and one can obtain any desired wavefunction. From this basic property of the coupling operator R, there can be constructed a flexible algorithm, which can be adapted to each case, even at each iteration, without extra effort. III) V I L S ( I Ii >< i I) L ieL L the first sum running over some MO subsets previously defined within each case. Finally, it should be said that the ordering principle is essential not only for the general SCF computational behaviour, but also for the application of acceleration or extrapolation procedures.

The PE framework has been chosen because, as we will show later, it satisfies these conditions. Finally, the last point of interest has been the need to obtain a PE procedure capable of studying excited states: It should be mentioned, for instance, that the mainline of computational tasks until now been carried out on a Closed Shell basis. has The present formalism will take this last situation as a particular case within the general MCPE framework. 1. Closed Shell MCPESCF Theory A discussion of the framework proposed by Veillard and Clementi and its description from a simpler point of view zation purposes.

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A system of physical chemistry. Kinetics by Lewis


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