Periodic Reporting for period 1 - MAGSPEC (Spectra of Molecules in Strong Magnetic Fields)
Reporting period: 2018-02-15 to 2020-02-14
The relative contributions of orbital and spin effects to anapole susceptibilities were assessed both theoretically and computationally. The computations were carried out under the self-consistent field (SCF) Hartree-Fock (HF) approximation. A non-relativistic general Hartree-Fock code involving two-component orbitals was developed to enable computations in non-uniform magnetic fields which enabled assessment of spin contributions to anapole susceptibility for the first time. Spin effects on the anapole susceptibility are found to be large and have a consistent direction - they lower the second order energy for all molecules that are closed shell singlets in the absence of a field. A perturbative argument was put forward to justify trends observed in our computations. This work resulted in a publication which was chosen as Editor's Pick.
The role of electron correlation in the values of the anapole susceptibilities was studied using both wave function (HF, MP2 and coupled cluster) and density functional (DFT) approximations (LDA, KT3, TPSS, M06). A test set of 36 small molecules of varied electronic structure was employed and the susceptibility tensors computed with all the listed methods. The accuracy of the methods in computing anapole susceptibilities were assessed against the CC values. This was deemed especially important for the density functional approximations as DFT itself is not rigorous for molecules in magnetic fields. The study also prompted a proposal for generalising the definitions of diamagnetic and paramagnetic molecules. The manuscript for this work has been submitted.
In a separate study, a new ingredient for designing exchange-correlation functionals for use of DFT in magnetic fields was proposed. Instead of kinetic energy density as a scalar, a tensor , Q, was suggested which contains the usual kinetic energy density as its trace and vorticity on the off-diagonals. The natural inclusion of vorticity into the tensor form of the kinetic energy density such that functionals with Q or quantities derived from Q as ingredients would smoothly transition between computations with a field to one without suggests that the minimum level of complexity for functionals that can handle computations in magnetic fields is where the kinetic energy density is considered, ie. the so-called meta-GGA functionals. This finding fits well with our observation that TPSS, a meta-GGA functional, works very well for computing both magnetic properties as well as PES in magnetic fields. Quantities analogous to the electron localisation function (ELF) can also be derived from Q which are necessary to for designing functionals with suitable short and long rage behaviour. This work was published and selected as Editor’s Choice 2018 (72 articles out of all published in 2018), Featured article and also selected for publication as popular science article in SciLight (AIP).
The researcher participated in 5 international meetings and was an invited speaker in 2 of them. In 2 others she presented posters.