Accurate electric dipole moment and polarizability for the 22 electron molecules CP−, BCl, CCl+ and PO+

Some considerations about Gaussian basis sets for electric property calculations

“…A selection of theoretical and experimental 36, 38–49 μ, $\bar{\alpha}$ , and Δα values for H 2 , N 2 , CO, HF, H 2 O, NH 3 , CH 4 ,HCN, SiO, H 2 S, PH 3 , SiH 4 , CS, CP − , HCl, BCl, Cl 2 , PN, CCl + , PO + , SiS, AlCl, P 2 , and HCP is shown in Table I. Among the numerous theoretical works on the static electric dipole moment and dipole polarizability of these molecules, only some highly accurate theoretical efforts 3–9, 14–16 that take into account electron correlation have been included.…”

“…The effects arising from the ZPVC have been investigated in a variety of papers, e.g., Refs. 5–7. The ZPVC depends on the molecule and the contribution to the static anisotropy ranges from less than 0.1 a.u.…”

“…For the electric dipole moment it is still smaller, on the order of 0.003 a.u. for CS, SiO, and SiS 7. There has been very little investigation of the effect of zero‐point averaging on the dynamic polarizability, but it is presumably of similar magnitude.…”

“…Calculations were carried out for the 24 molecules H 2 ( R HH = 0.742 Å), N 2 ( R NN = 1.094 Å), CO ( R CO = 1.128 Å), HF ( R FH = 0.917 Å), H 2 O ( R OH = 0.957 Å and θ HOH = 104.5°), NH 3 ( R NH = 1.012 Å and θ HNH = 106.7°), CH 4 ( R CH = 1.085 Å and θ HCH is T d ), HCN ( R CH = 1.063 Å and R CN = 1.154 Å), SiO ( R SiO = 1.5097 Å), H 2 S ( R SH = 1.3356 Å and θ HSH = 92.12°), PH 3 ( R PH = 1.4200 Å and θ HPH = 93.345°), SiH 4 ( R SiH = 1.4798 Å and θ HSiH is T d ), CS ( R CS = 1.5349 Å), CP − ( R CP = 1.6143 Å), HCl ( R HCl = 1.27455 Å), BCl ( R BCl = 1.7153 Å), Cl 2 ( R ClCl = 1.9878 Å), PN ( R PN = 1.4909 Å), CCl + ( R CCl = 1.5378 Å), PO + ( R PO = 1.424992 Å), SiS ( R SiS = 1.9293 Å), AlCl ( R AlCl = 2.1301 Å), P 2 ( R PP = 1.8931 Å), and HCP ( R CH = 1.069 Å and R CP = 1.540 Å) at their equilibrium geometries. Except for CP − , CCl + , and PO + 7, and HCP 35, the molecular experimental equilibrium geometries were taken from Refs. 36, 37.…”

“…The theory of electric polarizability is a key element of the rational interpretation of a wide range of phenomena, from nonlinear optics and electron scattering to phenomena induced by intermolecular interactions. The experimental determination of electric polarizabilities and hyperpolarizabilities represents a difficult task 2, but the theoretical determination of these quantities is currently a remarkably active research field 3–16. This has proved a decisive factor of progress in fields with important potential technological implications, as the simulation of fluids and also drug design.…”