Understanding and quantifying the impact of solute-solvent van der Waals interactions on the selectivity of asymmetric catalytic transformations.

The majority of enantioselective organocatalytic reactions occur in apolar or weakly polar organic solvents. Nevertheless, the influence of solute-solvent van der Waals forces on the relative kinetics of competitive pathways remains poorly understood. In this study, we provide a first insight into the nature and strength of these interactions at the transition state level using advanced computational tools, shedding light into their influence on the selectivity.

A trimetallic bismuth(I)-based allyl cation.

The chemistry of low-valent bismuth compounds has recently unlocked new concepts in catalysis and unique electronic structure fundamentals. In this work, we describe the synthesis and characterization of a highly reduced bismuth salt featuring a cationic core based on three contiguous Bi(I) centres. The triatomic bismuth-based core exhibits an electronic configuration that mimics the canonical description of the archetypical carbon-based π-allyl cation.

Extended Active Space Ab Initio Ligand Field Theory: Applications to Transition-Metal Ions.

Ligand field theory (LFT) is one of the cornerstones of coordination chemistry since it provides a conceptual framework in which a great many properties of d- and f-element compounds can be discussed. While LFT serves as a powerful qualitative guide, it is not a tool for quantitative predictions on individual compounds since it incorporates semiempirical parameters that must be fitted to experiment. One way to connect the realms of first-principles electronic structure theory that has emerged as particularly powerful over the past decade is the ab initio ligand field theory (AILFT).

General Spin-Restricted Open-Shell Configuration Interaction Approach: Application to Metal K-Edge X-ray Absorption Spectra of Ferro- and Antiferromagnetically Coupled Dimers.

In this work, we present a generalized implementation of the previously developed restricted open-shell configuration interaction singles (ROCIS) family of methods. The new method allows us to treat high-spin (HS) ferro- as well as antiferromagnetically (AF) coupled systems while retaining the total spin as a good quantum number. To achieve this important and nontrivial goal, we employ the machinery of the iterative configuration expansion (ICE) method, which is able to tackle general configuration interaction (CI) problems on the basis of spin-adapted configuration state functions (CSFs).