engleski

On The Corellation Energy Features in Planar Heteroatomic Molecular Systems

The correlation energy in planar heteroatomic open chain polyene systems involving N, O and F atoms is considered by the CASSCF and CASPT2 methods employing a number of the cc-pVmZ (VDZ, VTZ etc.) correlation consistent basis sets. A thorough study of the smallest molecules shows that the nondynamical correlation energy is virtually independent of the quality of the basis set. In contrast, the dynamical correlation energy is very sensitive to the basis set and, in estimating reliable dynamical correlation effects for larger systems, one has to rely on adequate extrapolation formulas to obtain the infinite basis set limit. We find that a method recently proposed by Truhlar offers economical yet reasonable estimates of the complete basis set results. Investigation of the sensitivity of the results to the choice of active space and the comparison to single reference MP2 calculations indicate that such extrapolations offer a good general method for saturating the basis set in multireference calculations. Thus a simple refinement of the conventional multireference coupled cluster (MRCC) method is proposed. It is also shown that both nondynamical and dynamical correlation energies follow very simple additivity rules in linear and branched planar chain heteroatomic polyenes, making possible their prediction in very large systems without calculation.

basis-set extrapolation; Gaussian-basis sets; multireference coupled-cluster; 2nd-order perturbation-theory; total atomization energies; wave-functions; natural orbitals; model chemistry; 2nd-row atoms; cyclobutadiene

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