Abstract
A practical Hartree-Fock theory of atomic and molecular electronic structure is developed for individual electronically excited states that does not involve off-diagonal Lagrange multipliers. An easily implemented method for taking the orthogonality constraints into account, which has been proposed earlier by one of us, is used to impose the orthogonality of the Hartree-Fock excited state wave function of interest to states of lower energy. The applicability of systematic sequence of even-tempered basis sets with the orbital exponents, ζp, defined by the geometric series ζp = aβp is examined in Hartree-Fock energy calculations for excited states which have the same spatial and spin symmetry as the ground state. It is shown that a simple reoptimization of the a and β parameters leads to a sequence of even-tempered basis sets capable of supporting high accuracy for excited state energies of some simple atoms.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
E.R. Davidson and D.F. Feller, Chem. Rev. 86, 681 (1986)
S. Wilson, Adv. Chem. Phys. 67, 439 (1987)
S. Wilson, in: New Methods in Quantum Theory, Ed. C.A. Tsipis, V.S. Popov, D.R. Herschbach and J.S. Avery, NATO ASI Series 3, V.8, p. 437–461, Kluwer Academic Publishers, Dordrecht, 1996
S. Wilson, in Handbook of Molecular Physics and Quantum Chemistry, 2, Molecular Electronic Structure, ed. S. Wilson, P.F. Bernath and R. McWeeny, Wiley, Chichester (2003)
T.H. Dunning, Jr., J. Chem .Phys. 90, 1007 (1989)
J. Almlof and P.R. Taylor, J.Chem.Phys. 86, 4070 (1987)
T. Helgaker and P.R. Taylor, in: Modern Electronic Structure Theory, Part 11, Ed. D. Yarkony, pp. 727–856, World Scientific (1995)
R.S. Raffenetti and K. Rudenberg, J. Chem. Phys. 59, 5978 (1973).
M.W. Schmidt and K. Rudenberg, J. Chem. Phys. 71, 3951 (1979)
E.S. Kryachko and S. Wilson, Int.J.Quant.Chem. 93, 112 (2003)
J. Kobus, D. Moncrieff and S. Wilson, J. Comp. Meth. Sci. & Eng. 4, 611 (2004)
D. Moncrieff and S. Wilson, J. Phys. B: At. Mol. Opt. Phys. 29, 6009 (1996)
D. Moncrieff and S. Wilson, J. Phys. B: At. Mol. Opt. Phys. 28, 4007 (1995)
D. Moncrieff and S. Wilson, J. Phys. B: At. Mol. Opt. Phys. 29, 2425 (1996)
H.M. Quiney, I.P. Grant and S. Wilson, J. Phys. B: At. Mol. Opt. Phys. 23, L271 (1990)
H.M. Quiney, V.N. Glushkov and S. Wilson, Int. J. Quantum Chem. 89, 227 (2002)
H. Shull and P.-O. Löwdin, Phys.Rev. 110, 1466 (1958)
K. Anderssom and B.O. Roos, in: Modern Electronic Structure Theory, Part 11, Ed. D. Yarkony, pp. 55–109, World Scientific (1995)
K. Morokuma and S. Iwata, Chem. Phys. Lett. 16, 195 (1972)
R. McWeeny, Molec. Phys. 28, 1273 (1974)
J. Mrozek and A. Golebiewski, Int. J. Quant. Chem. 12, 207 (1977)
E.R.Davidson, L.Z. Stenkamp CF Int.J.Quant.Chem. (Symp). 10, 21.(1976)
E.R. Davidson and E.L. McMurchie, in: Excited States 5, 1 (1985)
R. Colle, A. Fortunelli and O. Salwetti, Theor. Chim. Acta. 71, 467 (1987)
N. Gidopoulos and A. Theophilou, Phil. Mag. 69, 1067 (1994)
A. Theophilou, J. Phys. C, 12, 5419 (1979)
N. Gidopoulos, V.N. Glushkov and S. Wilson, Proc.R. Soc. Lond. A., 457, 1657 (2002)
V.N. Glushkov, A.Ya. Tsaune and Z. Vychisl, Matem. & Mat. Phys. 25, 298 (1985)
V.N. Glushkov, Opt. Spectrosc. 93, 15 (2002)
V.N. Glushkov, J. Math. Chem. 31, 91 (2002)
V.N. Glushkov and A.Ya. Tsaune, Opt. Spectrosc. 87, 267 (1999)
M. Cohen and P.S. Kelly, Can. J. Phys. 43, 1867 (1965)
H. Tatewaki, T. Koga, Y. Sakai and A.J. Thakkar, J. Chem. Phys. 101, 4945 (1994)
V.N. Glushkov, Chem. Phys. Lett. 273, 122 (1997)
V.N. Glushkov, Int. J. Quant. Chem. 99, 236 (2004)
P.E. Gill and M. Murray, Numerical methods for constrained optimization, London. Academic Press (1978)
V.N. Glushkov, Chem. Phys. Lett. 287, 189 (1998)
C. Froese, J. Chem. Phys. 47, 4010 (1967)
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2006 Springer
About this paper
Cite this paper
GLUSHKOV, V., WILSON, S. (2006). EXCITED STATE SELF-CONSISTENT FIELD THEORY USING EVEN-TEMPERED PRIMITIVE GAUSSIAN BASIS SETS. In: JULIEN, JP., MARUANI, J., MAYOU, D., WILSON, S., DELGADO-BARRIO, G. (eds) Recent Advances in the Theory of Chemical and Physical Systems. Progress in Theoretical Chemistry and Physics, vol 15. Springer, Dordrecht. https://doi.org/10.1007/1-4020-4528-X_4
Download citation
DOI: https://doi.org/10.1007/1-4020-4528-X_4
Publisher Name: Springer, Dordrecht
Print ISBN: 978-1-4020-4527-1
Online ISBN: 978-1-4020-4528-8
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)