Systematic Sequences Of Geometric Relativistic Basis Sets. I:s- And P-block Elements Up To Xe

In this work a scheme for constructing systematic sequences of relativistic SCF basis sets at a reasonable computational cost is presented and applied to atoms of the s- and p-block up to Xe. This scheme, which couples simplex optimization and the use of geometric series given by four-term polynomial expressions for the logarithm of the exponents, allows for the construction of basis sets that exhibit very regular patterns of convergence to the numerical reference values of atomic total energies, spinor energies and radial expectation values. This regularity, together with the broad range of basis set sizes presented, enables these sets to be used as building blocks for basis sets applicable in both routine and benchmark relativistic calculations on atomic and molecular systems. © Springer-Verlag 2006.1155398409Visscher, L., Visser, O., Aerts, P.J.C., Merenga, H., Nieupoort, W.C., (1994) Comput Phys Commun, 81, p. 120Saue, T., Olsen, J., Faegri Jr., K., Helgaker, T., (1997) Mol Phys, 91, p. 937Yanai, T., Nakajima, T., Ishikawa, Y., Hirao, K., (2001) J Chem Phys, 114, p. 6526Dyall, K.G., (1998) Theor Chem Acc, 99, p. 366Dyall, K.G., (2002) Theoretical Chem Acc, 104, p. 335Dyall, K.G., (2004) Theoretical Chem Acc, 112, p. 403Faegri Jr., K., (2001) Theoretical Chem Acc, 105, p. 252Faegri, K., Chem Phys, 311, p. 25. , 200Koga, T., Tatewaki, H., Matsuoka, O., (2001) J Chemi Phys, 115, p. 3561Koga, T., Tatewaki, H., Matsuoka, O., (2002) J Chem Phys, 117, p. 7813Tatewaki, H., Watanabe, Y., (2004) J Chem Phys, 121, p. 4528Dykstra, C.E., Ab initio calculation of the structures and properties of molecules (1988) Studies in Physical and Theoretical Chemistry, 58. , 1st edn. Elsevier, AmsterdamHelgaker, T., Jorgensen, P., Olsen, J., (2000) Molecular Electronic-structure Theory, , Wiley, NewyorkSchmidt, M.W., Ruedemberg, K., (1779) J Chem Phys, 71, p. 3951Feller, D.F., Ruedemberg, K., (1979) Theor Chim Acta, 51, p. 231Gomes, A.S.P., (2001), http://biq.iqm.unicamp.br/arquivos/teses/ficha44864.htm, MSc Dissertation. Universidade Estadual de Campinas, Campinas, SPKlobukowski, M., (1993) Chem Phys Lett, 214, p. 166Klobukowski, M., (1994) Can J Chem, 72, p. 1741Neider, J.A., Mead, R., (1965) Comput J, 7, p. 308Andrae, D., (2000) Phys Rep, 336, p. 413Press, W.H., Teukowsky, S.A., Vetterling, W.T., Flannery, B.P., (1995) Numerical Recipes in C, 2nd Edn., , Oxford University PressOrwant, J., Wall, L., Christiansen, T., (2000) Programming Perl, 3rd Edn., , O'Reilly, SebastopolMatsuoka, O., Watanabe, Y., (2001) Comput Phys Commun, 139, p. 218Dyall, K.G., Visscher, L., (1997) At Data Nucl Data Tables, 67, p. 207Tatewaki, H., Watanabe, Y., (2003) J Computa Chem, 24, p. 1823Tatewaki, H., Koga, T., Mochizuki, Y., (2003) Chem Phys Lett, 375, p. 399Petersson, G.A., Zhong, S., Montgomery, J.A., Frisch, M.J., (2003) J Chem Phys, 118, p. 110