Gaussian basis sets for use in correlated molecular calculations. IV. Calculation of static electrical response properties

Abstract

An accurate description of the electrical properties of atoms and molecules is critical for quantitative predictions of the nonlinear properties of molecules and of long-range atomic and molecular interactions between both neutral and charged species. We report a systematic study of the basis sets required to obtain accurate correlated values for the static dipole (α1), quadrupole (α2), and octopole (α3) polarizabilities and the hyperpolarizability (γ) of the rare gas atoms He, Ne, and Ar. Several methods of correlation treatment were examined, including various orders of Moller–Plesset perturbation theory (MP2, MP3, MP4), coupled-cluster theory with and without perturbative treatment of triple excitations [CCSD, CCSD(T)], and singles and doubles configuration interaction (CISD). All of the basis sets considered here were constructed by adding even-tempered sets of diffuse functions to the correlation consistent basis sets of Dunning and co-workers. With multiply-augmented sets we find that the electrical properties of the rare gas atoms converge smoothly to values that are in excellent agreement with the available experimental data and/or previously computed results. As a further test of the basis sets presented here, the dipole polarizabilities of the F− and Cl− anions and of the HCl and N2 molecules are also reported.

Efficient Temperature-Dependent Green’s Function Methods for Realistic Systems: Using Cubic Spline Interpolation to Approximate Matsubara Green’s Functions

“…Our test set is comprised of 3 closed-shell atoms: Be, Mg, Ar, 21 closed-shell molecules: 4 , HCN, CH 4 , C 2 H 4 , CO, CO 2 , H 2 CO, NH 3 , BN, H 2 O 2 , C 6 H 6 , LiH, NaH, MgH 2 , AlH, NaOH, MgO, NaF, and 4 transition metal atoms and diatomic clusters: Cd, Pd, Cu 2 , Ag 2 . The aug-cc-pVDZ [70][71][72] basis set was used for atoms, the TZ(Dunning) basis set was used for molecules except for LiH, NaH, MgH 2 , AlH, NaOH, MgO and NaF where the aug-cc-pVDZ basis set was used. For transition-metal containing compounds, a basis set with pseudopotentials ecp-sdd-DZ [73][74][75][76] was employed.…”

Relativistic four-component calculations of Buckingham birefringence using London atomic orbitals

“…We have used the u-aug-cc-pVDZ and u-aug-cc-pVTZ (''u-'' meaning uncontracted) basis sets of Dunning [90,91] for C, O and S, and the augmented all-electron u-DZ and u-TZ basis sets of Dyall [92,93] for Se and Te. The small-component basis for the DC calculations has been generated using UKB, with RKB imposed in the canonical orthonormalization step [45].…”

“…For C, O and S we have used the u-aug-cc-pVTZ (''u-'' meaning uncontracted) basis sets of Dunning [90,91], for Se and Te the augmented all-electron u-TZ basis sets of Dyall [92,93]. The basis sets employ LAO.…”

“…Also shown is the DC estimate of m Q(x, T) (a.u.) and the anisotropy Dn per unit electric field gradient (given in m 2 V -1 ) again for T = 298.15 K. For C, O and S we have used the u-aug-cc-pVTZ (''u-'' meaning uncontracted) basis sets of Dunning [90,91], for Se the augmented all-electron u-TZ basis set of Dyall [92,93] obtained by Benkova and Sadlej [97] employing the HyPolX and HyPolX_dk basis sets and including scalar relativistic effects within the two-component DouglasKroll approximation, and, for CO 2 and CS 2 , with the results of Ref. [17].…”

“…From comparison with experimentally derived data, it is therefore not possible to draw definite conclusions regarding the reliability of the various XC functionals for the mixed hyperpolarizabilities that determine the [29,30,34] have been included. For C, O and S we have used the u-aug-cc-pVDZ and u-aug-cc-pVTZ (''u-'' meaning uncontracted) basis sets of Dunning [90,91], for Se and Te the augmented allelectron u-DZ and u-TZ basis sets of Dyall [92,93]. CGO means that a common gauge origin (placed at the carbon nucleus) has been employed a Ref.…”