AI Article Synopsis
- Two new perturbation theories are developed using a multiconfiguration zero-order function, incorporating biorthogonal vector sets for configuration space representation.
- These theories utilize the full Fockian of a principal determinant, leading to a nondiagonal zero-order resolvent matrix and offering a generalized Møller-Plesset second-order correction.
- The computational requirements resemble those of single reference Møller-Plesset theory and are evaluated using antisymmetric product of strongly orthogonal geminal wave functions.
Article Abstract
Two perturbation (PT) theories are developed starting from a multiconfiguration (MC) zero-order function. To span the configuration space, the theories employ biorthogonal vector sets introduced in the MCPT framework. At odds with previous formulations, the present construction operates with the full Fockian corresponding to a principal determinant, giving rise to a nondiagonal matrix of the zero-order resolvent. The theories provide a simple, generalized Møller-Plesset (MP) second-order correction to improve any reference function, corresponding either to a complete or incomplete model space. Computational demand of the procedure is determined by the iterative inversion of the Fockian, similarly to the single reference MP theory calculated in a localized basis. Relation of the theory to existing multireference (MR) PT formalisms is discussed. The performance of the present theories is assessed by adopting the antisymmetric product of strongly orthogonal geminal (APSG) wave functions as the reference function.
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| http://dx.doi.org/10.1021/ct1001939 | DOI Listing |
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