Electrically polarized valence basis sets for the SBKJC effective core potential developed for calculations of dynamic polarizabilities and Raman intensities
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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 EMSL 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 Å4a.m.u.−1 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 C6H6 and about 40% reduction in the time-dependent Hartree-Fock intensities for C6F6 molecules were attained.
KeywordsRaman spectroscopy Static and dynamical polarizabilities Relativistic effects Ab initio electronic structure ECP basis set
The authors thank the National Center for High Performance Computing in São Paulo (CENAPAD-SP) for computer time. LNV thanks the National Council for Scientific and Technological Development (CNPq) for a doctoral fellowship. The basis sets can be obtained directly from the authors: contact LNV at firstname.lastname@example.org or PAMV at email@example.com.
- 3.Long DA (2002) The Raman effect: a unified treatment of the theory of Raman scattering by molecules. Wiley, LTD, ChichesterGoogle Scholar
- 4.Placzek G (1959) The Rayleigh and Raman scattering. United States Atomic Energy Commision, Lawrence Radiation Laboratory, University of California, Livermore, California, UCRL Translation No. 526 (L), PhysicsGoogle Scholar
- 7.Gaussian 98, Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Zakrzewski VG, Montgomery JA, Jr., Stratmann RE, Burant JC, Dapprich S, Millam JM, Daniels AD, Kudin KN, Strain MC, Farkas O, Tomasi J, Barone V, Cossi M, Cammi R, Mennucci B, Pomelli C, Adamo C, Clifford S, Ochterski J, Petersson GA, Ayala PY, Cui Q, Morokuma K, Salvador P, Dannenberg JJ, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Cioslowski J, Ortiz JV, Baboul AG, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Gomperts R, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Andres JL, Gonzalez C, Head-Gordon M, Replogle ES, Pople JA (1998) Gaussian, Inc., Pittsburgh PA, 2001Google Scholar
- 28.Feller D (1996) J Comput Chem 17:1571Google Scholar
- 30.Vidal LN (2004) Master Thesis. State University of Campinas, Campinas, SP, BrazilGoogle Scholar
- 35.(2005) Dalton, a molecular electronic structure program. Release 2.0, see http://www.kjemi.uio.no/software/dalton/dalton.html
- 36.Jensen HJA, Saue T, Visscher L, with contributions from Bakken V, Eliav E, Enevoldsen T, Fleig T, Fossgaard O, Helgaker TU, Lærdahl J, Larsen CV, Norman P, Olsen J, Pernpointner M, Pedersen JK, Ruud K, Sałek P, van Stralen JNP, Thyssen J, Visser O, Winther T (2004) DIRAC, a relativistic ab initio electronic structure program. Release DIRAC04.0, see http://dirac.chem.sdu.dk)
- 45.Shimanouchi T (2001) Molecular vibrational frequencies. In: NIST Chemistry WebBook, No. 69 in NIST Standard Reference Database (National Institute of Standards and Technology, Gaithersburg MD, 20899, 2001), http://webbook.nist.gov