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- Title
Electrically polarized valence basis sets for the SBKJC effective core potential developed for calculations of dynamic polarizabilities and Raman intensities.
- Authors
Vidal, Luciano; Vazquez, Pedro
- Abstract
Sadlej's electric polarization method of Gaussian basis functions was applied to the double-zeta effective core potential basis sets of Stevens, Basch, Krauss, Jasien and Cundari to generate a new augmented polarized valence double-zeta set, named as pSBKJC, which is appropriate for the calculation of dynamic polarizabilities and Raman intensities. The pSBKJC basis set was developed for the atoms of families 14-17 (from C to F, Si to Cl, Ge to Br and Sn to I). In order to assess the performance of this new basis set, these properties were compared to those evaluated using Sadlej's set, available in the online library under the name of Sadlej-pVTZ. In these tests, Hartree-Fock/pSBKJC calculations have proved to be less demanding of the computer than the Hartree-Fock/Sadlej-pVTZ ones but give results in excellent agreement with those from the Sadlej-pVTZ basis set. Since the Stevens et al. pseudopotential can represent the scalar relativistic effects, the results obtained at the Hartree-Fock/pSBKJC level show a better agreement with the results of Dirac-Hartree-Fock/Sadlej-pVTZ relativistic calculations using Dyall's spin-free Hamiltonian. When comparing Hartree-Fock/pSBKJC data of Raman scattering activities, at the excitation wavelength of 488 nm, with those of spin-free Dirac-Hartree-Fock/Sadlej-pVTZ calculations, a very good agreement is observed, where the RMS error is 8.5 Åa.m.u. and the averaged percentage error is 3.4%. In terms of computer savings in calculations of dynamic Raman intensities, a 20% reduction in the CPU time in the coupled cluster singles and doubles intensities of CH and about 40% reduction in the time-dependent Hartree-Fock intensities for CF molecules were attained.
- Subjects
POLARIZATION (Electricity); CONDUCTION bands; RAMAN effect; GAUSSIAN basis sets (Quantum mechanics); ZETA functions; PERFORMANCE evaluation; HAMILTONIAN systems
- Publication
Theoretical Chemistry Accounts: Theory, Computation, & Modeling, 2012, Vol 131, Issue 2, p1
- ISSN
1432-881X
- Publication type
Article
- DOI
10.1007/s00214-012-1111-4