Vibrational—rotational dependence of molecular properties. Electric field gradients for HCl, LiCl, NaCl and KCl

Abstract

The vibrational—rotational dependence of the nuclear quadrupole coupling constant (NQCC) for the isotopes 2H, 7Li, 23Na, 39K, and 35Cl is analysed in detail for the diatomic Group 1 chlorides HCl, LiCl, NaCl and KCl. The potential energy curves were calculated pointwise by using coupled cluster techniques. The electric field gradients (EFGs) and dipole moments were obtained analytically from a QCISD procedure using the Z vector method. Generally the calculated spectroscopic properties are in very good agreement with experimental data. Relativistic effects taken into account by a coupled cluster Douglas—Kroll procedure can safely be neglected for the electric field gradients up to potassium. The Inglis model which explains the trend and magnitudes of EFGs within an ionic model of weakly polarized atoms is analysed. According to this model the derivatives of the EFG, ∂ n q(R)/∂R n, with respect to the internuclear distance R should show alternating sign behaviour with increasing power n. Hence, the mechanical anharmonicity (deviation from Hooke's law potential) and the electrical anharmonicity (curvature of q(R)) are of different sign, and we expect partial cancellation of anharmonicity effects in the vibrational dependence of the NQCCs. Nevertheless, a perturbative vibrational—rotational analysis reveals a strong dependence of the chlorine and Group 1 element NQCCs on the vibrational level due to dominating mechanical anharmonicity.