Magnetic and Thermodynamic Computations for Supramolecular Assemblies between a Cr(III) and Fe(III) Single-Ion Magnet and an Fe(II) Spin-Crossover Complex.

Experimental results on two supramolecular complexes in which a Cr or Fe d-orbital single-ion magnet center is embedded between a pair of Fe spin-crossover moieties make those two complexes interesting as possible candidates for use in quantum information technologies. We report detailed computational results for their structure and electronic properties and use the resulting data to parametrize a spin Hamiltonian that facilitates comparison with experimental results and their interpretation. Consistent with experimental results on decoherence in [Fe(ox)]@[FeL], we find it to be easy-plane type while the [Cr(ox)]@[FeL] system is easy-axis type.

Reworking the Tao-Mo Exchange-Correlation Functional. III. Improved Deorbitalization Strategy and Faithful Deorbitalization.

We present a deorbitalization of the recent simplified, regularized Tao-Mo exchange functional ( 2023, 159, 214102) that is faithful to the parent functional. That is a major gain relative to our earlier deorbitalization which did poorly on molecular heats of formation ( 2023, 159, 214103). The improvement arises from augmentation of the Mejía-Rodríguez and Trickey deorbitalization strategy ( 2017, 96, 052512) to use a smoothed replacement for the reduced density Laplacian (conventionally denoted ) obtained from that Laplacian itself.

Reworking the Tao-Mo exchange-correlation functional. I. Reconsideration and simplification.

The revised, regularized Tao-Mo (rregTM) exchange-correlation density functional approximation (DFA) [A. Patra, S. Jana, and P.

Reworking the Tao-Mo exchange-correlation functional. II. De-orbitalization.

In Paper I [H. Francisco, A. C.

Orbital-Free Density Functional Theory: An Attractive Electronic Structure Method for Large-Scale First-Principles Simulations.

Kohn-Sham Density Functional Theory (KSDFT) is the most widely used electronic structure method in chemistry, physics, and materials science, with thousands of calculations cited annually. This ubiquity is rooted in the favorable accuracy vs cost balance of KSDFT. Nonetheless, the ambitions and expectations of researchers for use of KSDFT in predictive simulations of large, complicated molecular systems are confronted with an intrinsic computational cost-scaling challenge.