In this article we describe the OpenMolcas environment and invite the computational chemistry community to collaborate. The open-source project already includes a large number of new developments realized during the transition from the commercial MOLCAS product to the open-source platform. The paper initially describes the technical details of the new software development platform. This is followed by brief presentations of many new methods, implementations, and features of the OpenMolcas program suite. These developments include novel wave function methods such as stochastic complete active space self-consistent field, density matrix renormalization group (DMRG) methods, and hybrid multiconfigurational

In this article we describe the OpenMolcas environment and invite the computational chemistry community to collaborate. The open-source project already includes a large number of new developments realized during the transition from the commercial MOLCAS product to the open-source platform. The paper initially describes the technical details of the new software development platform. This is followed by brief presentations of many new methods, implementations, and features of the OpenMolcas program suite. These developments include novel wave function methods such as stochastic complete active space self-consistent field, density matrix renormalization group (DMRG) methods, and hybrid multiconfigurational wave function and density functional theory models. Some of these implementations include an array of additional options and functionalities. The paper proceeds and describes developments related to explorations of potential energy surfaces. Here we present methods for the optimization of conical intersections, the simulation of adiabatic and nonadiabatic molecular dynamics and interfaces to tools for semiclassical and quantum mechanical nuclear dynamics. Furthermore, the article describes features unique to simulations of spectroscopic and magnetic phenomena such as the exact semiclassical description of the interaction between light and matter, various X-ray processes, magnetic circular dichroism and properties. Finally, the paper describes a number of built-in and add-on features to support the OpenMolcas platform with post calculation analysis and visualization, a multiscale simulation option using frozen-density embedding theory and new electronic and muonic basis sets.

Benzoselenadiazole-containing inhibitors of protein kinases were constructed and their capability to emit phosphorescence in the kinase-bound state was established. Labelling of the inhibitors with a red fluorescent dye led to sensitive responsive photoluminescent probes for protein kinase CK2 that emitted red light with a long (microsecond-scale) decay time upon excitation of the probes with a pulse of near-UV light.

The facilitation of redox-neutral reactions by electrochemical injection of holes and electrons, also known as “electrochemical catalysis”, is a little explored approach that has the potential to expand the scope of electrosynthesis immensely. To systematically improve existing protocols and to pave the way toward new developments, a better understanding of the underlying principles is crucial. In this context, we have studied the Newman–Kwart rearrangement of O-arylthiocarbamates to the corresponding S-aryl derivatives, the key step in the synthesis of thiophenols from the corresponding phenols. This transformation is a particularly useful example because the conventional method requires temperatures up to 300 °C, whereas electrochemical catalysis facilitates the reaction at room temperature. A combined experimental–quantum chemical approach revealed several reaction channels and rendered an explanation for the relationship between the structure and reactivity. Furthermore, it is shown how rapid cyclic voltammetry measurements can serve as a tool to predict the feasibility for specific substrates. The study also revealed distinct parallels to photoredox-catalyzed reactions, in which back-electron transfer and chain propagation are competing pathways.

In this work, the photochemically and thermally induced isomerization of multiple donor−acceptor Stenhouse adducts (DASAs) of the first, second, and third generation is studied by means of state-of-the-art ab initio electronic structure methods leading to new insight into multiple facets of the reaction mechanism. Importantly, prior to any studies of the reaction mechanism, a set of test calculations demonstrate the suitability of the applied ADC(2) and CC2 methods in the present context. An important aspect in this regard is the availability of electronic energies and gradients under implicit consideration of solvent effects. On the basis of calculated reaction energies and barriers as well as a thorough analysis of the wave function compositions, interesting features of the reaction mechanism are deduced. For example, the closed form of second-and third-generation DASAs can be significantly stabilized by π − π interactions between the donor and acceptor termini when certain structural requirements are fulfilled. The central point of this work concerns the delicate balance between neutral and zwitterionic resonance structures that governs the relative barrier height for the crucial C 2 −C 3 and C 3 −C 4 bond rotations. Finally, a set of calculations on yet unreported derivatives highlights how this balance and hence the barrier heights can be tuned through variation of the donor−acceptor strength as well as the solvent polarity.