Property evaluation and orbital relaxation in coupled cluster methods
| Autor: | Rodney J. Bartlett, Hideo Sekino, Edward A. Salter |
|---|---|
| Rok vydání: | 1987 |
| Předmět: |
Coupling constant
Electronic correlation Chemistry Ab initio General Physics and Astronomy Dipole Coupled cluster Atomic orbital Polarizability Physics::Atomic and Molecular Clusters Physics::Atomic Physics Physics::Chemical Physics Physical and Theoretical Chemistry Atomic physics Hyperfine structure |
| Zdroj: | The Journal of Chemical Physics. 87:502-509 |
| ISSN: | 1089-7690 0021-9606 |
| DOI: | 10.1063/1.453596 |
| Popis: | Molecular electronic properties such as dipole moments, polarizabilities and hyperpolarizabilities and quadrupole moments and polarizabilities, and spin properties such as hyperfine splitting constants and nuclear magnetic coupling constants are predicted by ab initio coupled cluster (CC) methods for a variety of molecules. We compare the results of property evaluation using orbitals that have been allowed to relax in the presence of the perturbation and results obtained using nonrelaxed orbitals. It is demonstrated numerically, and proven formally, that the coupled cluster singles and doubles (CCSD) model using nonrelaxed orbitals is able to include most of the relaxation effects for the evaluation of first‐ and second‐order properties. Thus there is little reason to perform coupled (perturbed) Hartree–Fock calculations as a precursor to correlated CCSD calculations of such properties. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|