Molecular g-Values, Magnetic Susceptibility Anisotropies, Molecular Quadrupole Moments and the Anisotropies in the Electronic Charge Distribution in HNO₂-Cis, DNO₂-Cis, HNO₂-Trans, and DNO₂-Trans

Abstract

The rotational Zeeman effect of the trans and eis forms of nitrous acid has been studied to yield the diagonal elements of the molecular g-tensor and the anisotropics in the diagonal elements of the magnetic susceptibility tensor. The results are used to calculate the diagonal elements of the molecular electric quadrupole moment tensor and the anisotropics in the second moments of the electronic charge distribution for all four molecular species. These data are compared to the corresponding CNDO/2 values, and the CNDO/2 value for the out of plane second moment of the electronic charge distribution is used together with the experimental anisotropics in the second moments of the electronic charge distribution to derive a semiexperimental value for the molecular bulk susceptibility which is otherwise difficult to obtain. The out-of-plane minus average in-plane magnetic susceptibility anisotropy is discussed with reference to the model of localised atomic susceptibilities and it is shown that the model should be extended to include bond and bond-bond interaction contributions.

Accurate equilibrium structures of some challenging molecules: FNO, ClNO, HONO, FNO2, and N2O

“…As a further check the method was applied to trans-nitrous acid HONO, because it is known that the CCSD(T) value of the N -O bond length is much too short, see Table 1. [15] For the determination, the ground state rotational constants of Cox et al [63], the values of the gtensor of Hübner and Sutter [64] and the rovibrational corrections calculated at the CCSD(T)_ae/VTZ level [15] were used. The detailed results are given in Table S5 for three isotopologues, HONO, H 18 ON 18 O and DONO and the final result is shown in Table 1 and Table S5 of the Supplementary Material.…”