Assessment of Perturbative Explicitly Correlated Methods for Prototypes of Multiconfiguration Electronic Structure

Le résumé fourni par la source

The performance of the [2] S and [2] R12 universal perturbative corrections that account for one- and many-body basis set errors of single- and multiconfiguration electronic structure methods is assessed. A new formulation of the [2] R12 methods is used in which only strongly occupied orbitals are correlated, making the approach more amenable for larger computations. Three model problems are considered using the aug-cc-pVXZ (X = D,T,Q) basis sets: the electron affinity of fluorine atom, a conformational analysis of two Si 2 H 4 structures, and a description of the potential energy surfaces of the X 1 Σ g +, a 3 Π u, b 3 Σ g -, and A 1 Π u states of C 2 . In general, the [2] R12 and [2] S corrections enhance energy convergence for conventional multireference configuration interaction (MRCI) and multireference perturbation theory (MRMP2) calculations compared to their complete basis set limits. For the electron affinity of the F atom, [2] R12 electron affinities are within 0.001 eV of the experimental value. The [2] R12 conformer relative energy error for Si 2 H 4 is less than 0.1 kcal/mol compared to the complete basis set limit. The C 2 potential energy surfaces show nonparallelity errors that are within 0.7 kcal/mol compared to the complete basis set limit. The perturbative nature of the [2] R12 and [2] S methods facilitates the development of a straightforward text-based data exchange standard that connects an electronic structure code that can produce a two-particle density matrix with a code that computes the corrections. This data exchange standard was used to implement the interface between the GAMESS MRCI and MRMP2 codes and the MPQC [2] R12 and [2] S capabilities.

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