Abstract
Specific features of application of the Hartree-Fock method with the orthogonality restrictions proposed earlier (V. N. Glushkov, Chem. Phys. Lett. 287, 189 (1998)) to calculations of energies of highly excited electronic states of the same symmetry are studied. Different schemes are discussed that allow one to avoid the variational collapse in constructing determinant wave functions for excited states. The accuracy of the method is demonstrated for the example of calculation of more than 30 excited states of He and Li atoms.
Similar content being viewed by others
References
B. M. Smirnov, Excited Atoms (Energoizdat, Moscow, 1982).
D. I. Lyakh, M. Musial, V. F. Lotrich, and R. J. Bartlett, Chem. Rev. 112, 182 (2012).
C. Sousa, S. Tosoni, and F. Illas, Chem. Rev. 113, 44 (2013).
V. N. Glushkov, Opt. Spectrosc. 99, 684 (2005).
V. N. Glushkov, J. Chem. Phys 126, 174106 (2007).
F. A. Evangelista, R. Shushkov, and J. C. Tully, J. Phys. Chem. A 113, 690 (2013).
R. J. Damburg and V. V. Kolosov, in Rydberg States of Atoms and Molecules, Ed. by R. F. Stebbings and F. B. Dunning (Cambridge Univ. Press, Cambridge, 1983), Chap. 2, pp. 31–71.
I. I. Beterov, I. I. Ryabtsev, D. B. Tretyakov, and V. M. Entin, Phys. Rev. A 79, 052504 (2009).
A. A. Zembekov and G. K. Ivanov, in Theoretical Problems of Chemical Physics (Nauka, Moscow, 1982), pp. 142–158 [in Russian].
Chen Chao, Chinese J. Phys. 52, 238 (2014).
V. N. Glushkov and A. Ya. Tsaune, Zh. Vych. Mat. Mat. Fiz. 25, 298 (1985).
V. N. Glushkov, Opt. Spectrosc. 93(1), 11 (2002).
V. N. Glushkov, J. Math. Chem. 31, 91 (2002).
K. Morokuma and S. Iwata, Chem. Phys. Lett. 16, 195 (1972).
R. Mc Weeny, Mol. Phys. 28, 1273 (1974).
E. R. Davidson and L. Z. Stenkamp, Int. J. Quant. Chem. (Symp.) 10, 21 (1976).
V. V. Murakhtanov, L. N. Mazalov, and T. I. Guzhavina, Zh. Strukt. Khim. 22, 22 (1981).
E. R. Davidson and E. L. McMurchie, Exc. States 5, 1 (1985).
E. I. Cheglokov, Yu. M. Lirmak, and A. F. Terpugova, Izv. Vyssh. Uchebn. Zaved., Fiz., No. 10, 55 (1985).
R. Colle, A. Fortunelly, and O. Salvetti, Theor. Chim. Acta 71, 467 (1987).
R. Colle, A. Fortunelli, and O. Salwetti, Theor. Chim. Acta 75, 323 (1987).
M. Tassi, I. Theophilou, and S. Thanos, Int. J. Quant. Chem 113, 690 (2013).
A. T. B. Gilbert, N. A. Besley, and P. M. W. Gill, J. Phys. Chem. A 112, 13164 (2008).
G. M. J. Barsa, A. T. B. Gilbert, and P. M. W. Gill, J. Chem. Phys. 141, 111104 (2014).
H. Tatewaki, T. Koga, Y. Sakai, and A. J. Thakkar, J. Chem. Phys. 101, 4945 (1994).
C. Froese, J. Chem. Phys. 4, 4010 (1967).
V. N. Glushkov, Chem. Phys. Lett. 287, 189 (1998).
V. N. Glushkov and X. Assfeld, J. Chem. Phys. 132, 204106 (2010).
V. N. Glushkov and A. Ya. Tsaune, Opt. Spectrosc. 101(3), 516 (2006).
V. N. Glushkov and X. Assfeld, J. Comp. Chem. 33, 2058 (2012).
V. N. Glushkov and N. V. Mogilevskaya, Opt. Spectrosc. 114(2), 79 (2013).
V. N. Staroverov and V. N. Glushkov, J. Chem. Phys. 133, 244104 (2010).
H. Shull and P.-O. Löwdin, Phys. Rev. 110, 1466 (1958).
N. Gidopoulos and A. Theophilou, Phil. Mag. 69, 1067 (1994).
J. I. A. Deng, A. T. B. Gilbert, and P. M. W. Gill, Int. J. Quantum Chem. 109, 1915 (2009).
B. Shi, Commun. Comput. Chem. 2, 69 (2014).
A. Burgers, D. Wintgen, and J.-M. Rost, J. Phys. B: At. Mol. Opt. Phys. 28, 3163 (1995).
M. Puchalski, D. Kedziera, and K. Pachucki, Phys. Rev. A 28, 062509 (2010).
Author information
Authors and Affiliations
Corresponding author
Additional information
Original Russian Text © V.N. Glushkov, 2015, published in Optika i Spektroskopiya, 2015, Vol. 119, No. 1, pp. 3–8.
Rights and permissions
About this article
Cite this article
Glushkov, V.N. Orthogonality of determinant functions in the Hartree-Fock method for highly excited electronic states. Opt. Spectrosc. 119, 1–6 (2015). https://doi.org/10.1134/S0030400X15070115
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S0030400X15070115