Summary
The first-order polarized basis sets PolMe are generated for elements (Me=Cu, Ag, Au) of group Ib of the periodic table by using the basis set polarization method developed in earlier papers. The performance of these basis sets is extensively tested in calculations of atomic dipole polarizabilities with particular attention given to the evaluation of the electron correlation and relativistic contributions. The extension by theg-type polarization functions (PolMe-g sets) is devised for use in accurate calculations of atomic and molecular electric properties. The (negative) electron correlation contribution to dipole polarizabilities of all elements of group Ib, as calculated at the level of the spin adapted coupled cluster method with single and double excitations and non-iterative corrections for the contribution of the T3 clusters (SA CCSD(T)), remains at the same level relative to the ROHF data. The pure relativistic correction to the ROHF results, evaluated within the quasirelativistic approximation involving the mass-velocity and Darwin corrections, is negative and rapidly increases with increase of the nuclear charge. Its large negative value is, for heavier systems, partly compensated by a positive contribution from the mixed relativistic-correlation terms. Our relativistically corrected SA CCSD(T) calculations predict the following values of the dipole polarizability in the coinage metal series: 46, 51, and 29 a.u., for Cu, Ag, and Au. The present results for Cu and Ag agree well with recent pseudopotential calculations by Schwerdtfeger and Bowmaker. However, for Au our result is by about 6 a.u. lower than that obtained by using 19-electron relativistic potentials. Several possible reasons for this discrepancy are discussed. The PolMe and PolMe-g basis sets are also used to calculate electric dipole polarizabilities of the singly positive ions of group Ib elements. The results obtained in the quasirelativistic CCSD(T) approximation are 6.6, 9.2, and 11.8 a.u. for Cu+, Ag+, and Au+, respectively. These values follow the pattern expected for the series of ions whose polarizability is dominated by the next-to-valenced shell.
Similar content being viewed by others
References
Buckingham AD (1967) Adv Chem Phys 12:107; Buckingham AD (1978) In: Pullman B (ed) Intermolecular interactions. From diatomics to polymers. Wiley, New York 1:1
Chałasiński G, Gutowski M (1988) Chem Rev 88:943
Duijneveldt-van der Rijdt JGCM, van Duijneveldt FB (1982) J Mol Struct (Theochem) 89:185
Werner H-J, Meyer W (1976) Phys Rev 13:13; Werner H-J, Meyer W (1976) Mol Phys 31:855
Sadlej AJ (1988) Coll Czech Chem Commun 53:1995, Part I of this series
Sadlej AJ (1991) Theor Chim Acta 79:123, Part II of this series
Sadlej AJ, Urban M (1991) J Mol Struct (Theochem) 234:147, Part III of this series
Sadlej AJ (1991) Theor Chim Acta 81:45, Part IV of this series
Sadlej AJ (1991) Theor Chim Acta 81:339, Part V of this series
Kellö V and Sadlej AJ (1992) Theor Chim Acta 83:351, Part VI of this series
Kellö V, Sadlej AJ (1995) Theor Chim Acta (in press), Part VIII of this series
Kellö V, Sadlej AJ (1995) Theor Chim Acta in press), (1995) J Chem Phys (in press)
Andersson K, Malmqvist P-Å, Roos BO, Sadlej AJ, Wolinski K (1990) J Phys Chem 94:5483
Andersson K, Malmqvist P-Å, Roos B (1992) J Chem Phys 96:1218
Roos BO (1987) Adv Chem Phys 69:399
Urban M, Černušák I, Kellö V, Noga J (1987) In: Wilson S (ed) Methods in computational chemistry, vol 1. Plenum Press, NY, p 117, and references therein
Neogrády P, Urban M, Hubač I (1992) J Chem Phys 97:5074
Neogrády P, Urban M, Hubač I (1994) J Chem Phys 100:3706
Neogrády P, Urban M (1995) Int J Quantum Chem (in press) and references therein
Kellö V, Sadlej AJ (1990) J Chem Phys 93:8112
Sadlej AJ, Urban M (1991) Chem Phys Lett 176:293
Andersson K, Sadlej AJ (1992) Phys Rev A 46:2356
Adamowicz L, Bartlett RJ (1987) J Chem Phys 86:6314; Adamowicz L, Bartlett RJ, Sadlej AJ (1988) J Chem Phys 88:5749
Jensen HJA, Jørgensen P, Ågren H, Olsen J (1988) J Chem Phys 88:3834; 88:5354
Bartlett RJ (1989) J Phys Chem 90:4356
Raghavachari K, Trucks GW, Pople JA, Head-Gordon M (1989) Chem Phys Lett 157:479
Lee TJ, Rendell AP, Taylor PR (1990) J Phys Chem 94:5463
Rittby M, Bartlett RJ (1988) J Phys Chem 92:3033; Watts JD, Gauss J, Bartlett RJ (1993) J Chem Phys 98:8718
Watts JD, Urban M, Bartlett RJ (1995) Theor Chim Acta 90:341
Pyykkö P (1988) Chem Rev 88:563
Cowan RD, Griffin DC (1976) J Opt Soc Am 66:1010; Martin RL (1983) J Phys Chem 87:750
Sadlej AJ, Urban M, Gropen O (1991) Phys Rev A 44:5547
Kellö V, Sadlej AJ, Faegri Jr K (1993) Phys Rev A 47:1715
Sadlej AJ (1991) J Chem Phys 95:2614
Andersson K, Blomberg MRA, Fülscher M, Kellö V, Lindh R, Malmqvist P-Å, Noga J, Olsen J, Roos BO, Sadlej AJ, Siegbahn PEM, Urban M, Widmark P-O (1991) MOLCAS system of quantum chemistry programs, release 2. Theoretical Chemistry, University of Lund, Lund Sweden and IBM Sweden
Lee TJ, Rendell AP, Rice JE (1991) TITAN, a set of electronic structure programs included in the MOLCAS system.
Huzinaga S (1971) Technical Report, Department of Chemistry, University of Alberta, Edmonton, Canada
Gropen O (1987) J Comp Chem 7:982
Woliński K, Sadlej AJ, Karlström (1991) Mol Phys 72:425
Reffenetti RC (1973) J Chem Phys 58:4452
Almlöf J, Taylor PR (1987) J Chem Phys 86:4070
Widmark P-O, Malmquist P-Å, Roos BO (1990) Theor Chim Acta 77:291
Widmark P-O, Person JB, Roos BO (1991) Theor Chim Acta 79:419
Müller W, Fleisch J, Meyer W (1984) J Chem Phys 80:3297
Balasubramanian K, Pitzer KS (1987) Adv Chem Phys 67:287 and references therein; see also Ref. [53]
Kutzelnigg W (1989) Z Phys D 11:15; (1990) 15:27
Andersson K, Borowski P, Fowler PW, Malmqvist P-Å, Roos BO, Sadlej AJ (1992) Chem Phys Lett 190:367
Schwerdtfeger P, Bowmaker GA (1994) J Chem Phys 100:4487
Teachout RR, Pack RT (1971) Atomic Data 3:195
Miller TM, Bederson B (1988) Adv At Mol Phys 25:37
Kirkwood JG (1932) Phys Z 33:57; Pople JA, Schofield P (1957) Phil Mag 2:591
Sadlej AJ (1980) Mol Phys 40:509
Dolg M, Wedig H, Stoll H, Preuss H (1987) J Chem Phys 88:866; Schwerdtfeger P, Dolg M, Schwarz WHE, Bowmaker GA, Boyd PDW (1989) 91:1762
Schwerdtfeger P, Li J, Pyykkö P (1994) Theor Chim Acta 87:313
Desclaux JP, Laaksonen L, Pyykkö P (1981) J Phys B 14:419
Faegri Jr K, Saue T, Sadlej AJ (to be published)
Fowler PW, Sadlej AJ (1991) Mol Phys 73:43
Neogrády P, Urban M, Sadlej AJ (1995) J Mol Struct (Theochem) 332:197
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Neogrády, P., Kellö, V., Urban, M. et al. Polarized basis sets for high-level-correlated calculations of molecular electric properties. Theoret. Chim. Acta 93, 101–129 (1996). https://doi.org/10.1007/BF01113551
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF01113551