Generalized relativistic effective core potential : Gaussian expansions of potentials and pseudospinors for atoms Hg through Rn. / Mosyagin, N. S.; Titov, A. V.; Latajka, Z.
In: International Journal of Quantum Chemistry, Vol. 63, No. 6, 1997, p. 1107-1122.Research output: Contribution to journal › Article › peer-review
}
TY - JOUR
T1 - Generalized relativistic effective core potential
T2 - Gaussian expansions of potentials and pseudospinors for atoms Hg through Rn
AU - Mosyagin, N. S.
AU - Titov, A. V.
AU - Latajka, Z.
PY - 1997
Y1 - 1997
N2 - The Gaussian expansions of the generalized relativistic effective core potential (GRECP) components are reported for elements Hg through Rn. The accuracy of the analytical GRECPs is estimated by calculations of atomic transition energies with the numerical one-configurational wave functions in comparison with Dirac-Fock calculations. The results of the corresponding calculations with the RECPs of other groups are also given. An "averaged error" in the reproduction of the transition energies without the change of the occupation number of the 5d-shell is an order of magnitude smaller than that for the RECPs of other groups. As is demonstrated for the transitions with the change of the occupation number of the 5d-shell in mercury, the largest absolute error of the GRECP is only 1.5-2 times smaller than that of the energy-adjusted pseudopotential (PP) or the RECP of Ross et al. with the same space of explicitly treated electrons. However, the dispersion of these errors is 19 · 10-4 au for the energy-adjusted PP, 35 · 104 au for the RECP of Ross et al. and only 4 · 10-4 au for the GRECP. One-configurational spin-averaged calculations of the molecular properties for HgH and HgH+ are carried out and compared with the corresponding results of Häussermann et al.
AB - The Gaussian expansions of the generalized relativistic effective core potential (GRECP) components are reported for elements Hg through Rn. The accuracy of the analytical GRECPs is estimated by calculations of atomic transition energies with the numerical one-configurational wave functions in comparison with Dirac-Fock calculations. The results of the corresponding calculations with the RECPs of other groups are also given. An "averaged error" in the reproduction of the transition energies without the change of the occupation number of the 5d-shell is an order of magnitude smaller than that for the RECPs of other groups. As is demonstrated for the transitions with the change of the occupation number of the 5d-shell in mercury, the largest absolute error of the GRECP is only 1.5-2 times smaller than that of the energy-adjusted pseudopotential (PP) or the RECP of Ross et al. with the same space of explicitly treated electrons. However, the dispersion of these errors is 19 · 10-4 au for the energy-adjusted PP, 35 · 104 au for the RECP of Ross et al. and only 4 · 10-4 au for the GRECP. One-configurational spin-averaged calculations of the molecular properties for HgH and HgH+ are carried out and compared with the corresponding results of Häussermann et al.
KW - Electronic structure
KW - Gaussian approximation
KW - Heavy atoms
KW - Method of molecular calculation
KW - Relativistic pseudopotentials
UR - http://www.scopus.com/inward/record.url?scp=0346648707&partnerID=8YFLogxK
U2 - 10.1002/(SICI)1097-461X(1997)63:6<1107::AID-QUA4>3.0.CO;2-0
DO - 10.1002/(SICI)1097-461X(1997)63:6<1107::AID-QUA4>3.0.CO;2-0
M3 - Article
AN - SCOPUS:0346648707
VL - 63
SP - 1107
EP - 1122
JO - International Journal of Quantum Chemistry
JF - International Journal of Quantum Chemistry
SN - 0020-7608
IS - 6
ER -
ID: 11883452