Relativistic and QED corrections to one-bond indirect nuclear spin-spin couplings in X 2 2 + and X 3 2 + ions (X = Zn, Cd, Hg)

COLOMBO JOFRÉ, MARIANO T.; KOZIO?, KAROL; AUCAR, I. AGUSTÍN; GAUL, KONSTANTIN; BERGER, ROBERT; AUCAR, GUSTAVO A.

JOURNAL OF CHEMICAL PHYSICS

AMER INST PHYSICS

Año: 2022 vol. 157 p. 64103 - 64118

0021-9606

The indirect spin-spin coupling tensor, J, between mercury nuclei in systems containing this element can be of the order of a few kHz and one of the largest measured. We analyzed the physics behind the electronic mechanisms that contribute to the one-and two-bond couplings nJHg-Hg (n = 1, 2). For doing so, we performed calculations for J-couplings in the ionized X22+ and X32+ linear molecules (X = Zn, Cd, Hg) within polarization propagator theory using the random phase approximation and the pure zeroth-order approximation with Dirac-Hartree-Fock and Dirac-Kohn-Sham orbitals, both at four-component and zeroth-order regular approximation levels. We show that the "paramagnetic-like"mechanism contributes more than 99.98% to the total isotropic value of the coupling tensor. By analyzing the molecular and atomic orbitals involved in the total value of the response function, we find that the s-Type valence atomic orbitals have a predominant role in the description of the coupling. This fact allows us to develop an effective model from which quantum electrodynamics (QED) effects on J-couplings in the aforementioned ions can be estimated. Those effects were found to be within the interval (0.7; 1.7)% of the total relativistic effect on isotropic one-bond 1J coupling, though ranging those corrections between the interval (-0.4;-0.2)% in Zn-containing ions, to (-1.2;-0.8)% in Hg-containing ions, of the total isotropic coupling constant in the studied systems. The estimated QED corrections show a visible dependence on the nuclear charge Z of each atom X in the form of a power-law proportional to ZX5.