Abstract
The relaxation effect of functions of STO-3G and 6-31G* basis sets (BS) on their balance is considered in the series of LiF, BeO, BN, and C2 isoelectronic molecules. The values of parameters (exponential factors of basis functions, orbital exponents of Gaussian primitives, and contraction coefficients for the basis functions in molecules are found by the energy minimum criterion from unrestricted Hartree-Fock (UHF) calculations with a direct optimization of parameters: the simplex and Rosenbrock methods. Several optimization schemes differing in the number of parameters varied are performed. An important, from the practical viewpoint, relation between parameters of the basis functions of the sets in question is found through the mean values of Gaussian exponents. The relaxation effect on the variation of the total energy and relative errors in the calculations of interatomic distances, normal vibration frequencies, dissociation energies, and other properties of molecules are examined. The variation of the total energy upon the relaxation of STO-3G and 6-31G* basis functions (RBF) can achieve 1100 kJ/mole and 80 kJ/mole, respectively, and should be taken into account when evaluating energy characteristics, especially for the systems with high polar chemical bonds. The relaxation of STO-3G BS improves the description of molecular properties almost in all cases considered, whereas the relaxation of 6-31G* BS slightly affects its balance.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
R. S. Mulliken, J. Chem. Phys., 36, No. 12, 3428–3439 (1962).
S. Huzinaga, Comp. Phys. Rep., 2, 281–339 (1985).
E. R. Davidson and D. Feller, Chem. Rev., 86, No. 4, 661–696 (1985).
K. Hashimoto and Y. Osamura, Canad. J. Chem., 70, 547–554 (1992).
M. Urban, Collect. Czech. Chem. Communs., 38, No. 7, 2043–2053 (1973).
G. M. Loubriel and R. G. Selsby, Int. J. Quant. Chem., 8, No. 4, 547–557 (1974).
R. A. Poirier, R. Daudel, et al., ibid., 18, No. 3, 715–725 (1980).
R. A. Poirier, R. Daudel, and I. G. Csizmadia, ibid., 727–733.
A. I. Ermakov and A. E. Merkulov, Zh. Strukt. Khim., 39, No. 4, 596–601 (1998).
R. L. Longo, Int. J. Quant. Chem., 75, Nos. 4/5, 585–591 (1999).
A. I. Ermakov, A. E. Merkulov, et al., Zh. Strukt. Khim., 45, No. 6, 973–978 (2004).
A. I. Ermakov, A. E. Merkulov, et al., ibid., 979–985.
W. J. Hehre, R. F. Stewart, and J. A. Pople, J. Chem. Phys., 51, No. 6, 2657–2664 (1969).
P. C. Hariharan and J. A. Pople, Theor. Chim. Acta., 28, No. 3, 213–222 (1973).
W. U. Hehre, R. Ditchfleld, and J. A. Pople, J. Chem. Phys., 56, No. 5, 2257–2261 (1972).
J. D. Dill and J. A. Pople, ibid., 62, No. 7, 2921–2923 (1975).
J. A. Binkley and J. A. Pople, ibid., 66, No. 2, 879/880 (1977).
B. J. Lynch, Y. Zhao, and D. G. Truhlar, J. Phys. Chem. A, 107, No. 9, 1384–1388 (2003).
A. E. Merkulov, A. I. Ermakov, and V. V. Belousov, Izv. TulGU. Ser. Khim., No. 4, 209–212 (2004).
R. Krishnan, J. S. Binkley, et al., J. Chem. Phys., 72, No. 1, 650–654 (1980).
K. S. Krasnov, N. V. Filippenko, V. A. Bobkova, et al., Molecular Constants of Inorganic Compounds: Hand-book [in Russian], K. S. Krasnov (ed.), Khimiya, Leningrad (1979).
S. S. Batsanov, Structural Chemistry. Facts and Dependences [in Russian], Dialog-MGU, Moscow (2000).
L. A. Gribov, Zh. Fiz. Khim., 79, No. 4, 688–692 (2005).
A. I. Ermakov, Zh. Strukt. Khim., 33, No. 4, 3–7 (1992).
J. A. Nelder and R. Mead, Comput. J., 7, No. 4, 308–313 (1965).
H. H. Rosenbrock, ibid., 3, No. 3, 175–184 (1960).
R. M. Lewis, V. Torczon, and M. W. Trosset, J. Comput. Appl. Math., 124, Nos. 1/2, 191–207 (2000).
A. A. Granovskii, http://classic.chem.msu.su/gran/gamess/index.html.
M. W. Schmidt, K. K. Baldridge, J. A. Boatz, et al., J. Comput. Chem., 14, No. 11, 1347–1363 (1993).
V. V. Belousov, I. V. Yurova, and A. I. Ermakov, Data-Processing Technologies in Solutions of Fundamental and Applied Scientific Problems. DPTS-2005 Session. Collection of Materials [in Russian], Moscow (2005).
D. A. Zhogolev and V. B. Volkov, Methods, Algorithms and Programs for Quantum Chemical Calculations of Molecules [in Russian], Naukova Dumka, Kiev (1976).
M. V. Solodkova, A. V. Volkovich, et al., Rasplavy, No. 6, 42–50 (2004).
R. S. Mulliken, J. Chem. Phys., 23, No. 10, 1833–1840 (1955).
A. E. Reed, R. B. Weinstock, and F. Weinhold, ibid., 83, No. 2, 735–746 (1985).
Author information
Authors and Affiliations
Additional information
Original Russian Text Copyright © 2007 by A. I. Ermakov and V. V. Belousov
__________
Translated from Zhurnal Strukturnoi Khimii, Vol. 48, No. 1, pp. 12–21, January–February, 2007.
Rights and permissions
About this article
Cite this article
Ermakov, A.I., Belousov, V.V. Relaxation of STO-3G and 6-31G* basis set functions in the series of LiF isoelectronic molecules of second row elements. J Struct Chem 48, 6–15 (2007). https://doi.org/10.1007/s10947-007-0002-3
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/s10947-007-0002-3