Transport of ions through liquid-liquid interfaces is of fundamental importance to a wide variety of applications. However, since it is quite challenging for experimentalists to directly and selectively observe molecules at the interfaces, microscopic mechanisms of ion transport have been largely presumed from kinetic information. This Perspective illustrates recent examples that molecular dynamics simulations with proper free energy surfaces clarified mechanistic pictures of ion transport. The key is a proper choice of coordinates and defining/calculating free energy surfaces in multidimensional space. Once the free energy surfaces for realistic systems are available, they naturally provide new insight into the ion transport in unprecedented details, including water finger, transient ion pairing, and electron transfer.Density functional theory and time-dependent (TDDFT) calculations were carried out for recently reported bisarylselanylbenzo-2,1,3-selenadiazoles derivatives capable of producing singlet oxygen (1O2) under UV-Vis irradiation. Conformational behaviors, excitation energies, singlet-triplet energy gaps, and spin-orbit coupling constants were evaluated. The conformational analysis evidences that two different conformers have to be taken into consideration to completely describe the photophysical properties of this class of molecules. TDDFT results show that these compounds, though possessing absorption wavelengths that fall in the violet region, are characterized by singlet-triplet energy gaps greater than the energy required to excite the molecular oxygen, thus being able to produce the cytotoxic species, spin-orbit coupling constants large enough to ensure efficient singlet-triplet intersystem spin crossing, and even the highly reactive superoxide anion O2•(-) by autoionization and subsequent electron transfer to molecular oxygen in its ground state.Knowledge of how the molecular structures of ionic liquids (ILs) affect their properties at electrified interfaces is key to the rational design of ILs for electric applications. Polarizable molecular dynamics simulations were performed to investigate the structural, electrical, and dynamic properties of electric double layers (EDLs) formed by imidazolium dicyanamide ([ImX1][DCA]) at the interface with the molybdenum disulfide electrode. The effect of side chain of imidazolium on the properties of EDLs was analyzed by using 1-ethyl-3-methylimidazolium ([Im21]), 1-octyl-3-methylimidazolium ([Im81]), 1-benzyl-3-methylimidazolium ([ImB1]), and 1-(2-hydroxyethyl)-3-methylimidazolium ([ImO1]) as cations. Using [Im21] as reference, we find that the introduction of octyl or benzyl groups significantly alters the interfacial structures near the cathode because of the reorientation of cations. For [Im81], the positive charge on the cathode induces pronounced polar and non-polar domain separation. In contrast, the hydroxyl group has a minor effect on the interfacial structures. [ImB1] is shown to deliver slightly larger capacitance than other ILs even though it has larger molecular volume than [Im21]. This is attributed to the limiting factor for capacitance being the strong association between counter-ions, instead of the free space available to ions at the interface. this website For [Im81], the charging mechanism is mainly the exchange between anions and octyl tails, while for the other ILs, the mechanism is mainly the exchange of counter-ions. Analysis on the charging process shows that the charging speed does not correlate strongly with macroscopic bulk dynamics like viscosity. Instead, it is dominated by local displacement and reorientation of ions.Quantum plasmonics extends cavity quantum electrodynamics (cQED) concepts to the nanoscale, benefiting from the strongly subwavelength confinement of the plasmon modes supported by metal nanostructures. In this work, we describe in detail collective strong coupling to a plasmonic nanocavity. Similarities and differences to cQED are emphasized. We notably observe that the Rabi splitting can strongly deviate from the standard NeΔΩ1 law, where Ne is the number of emitters and ΔΩ1 is the Rabi splitting for a single emitter. In addition, we discuss the collective Lamb shift and the role of quantum corrections to the emission spectra.Most widely used density functional approximations suffer from self-interaction error, which can be corrected using the Perdew-Zunger (PZ) self-interaction correction (SIC). We implement the recently proposed size-extensive formulation of PZ-SIC using Fermi-Löwdin Orbitals (FLOs) in real space, which is amenable to systematic convergence and large-scale parallelization. We verify the new formulation within the generalized Slater scheme by computing atomization energies and ionization potentials of selected molecules and comparing to those obtained by existing FLOSIC implementations in Gaussian based codes. The results show good agreement between the two formulations, with new real-space results somewhat closer to experiment on average for the systems considered. We also obtain the ionization potentials and atomization energies by scaling down the Slater statistical average of SIC potentials. The results show that scaling down the average SIC potential improves both atomization energies and ionization potentials, bringing them closer to experiment. Finally, we verify the present formulation by calculating the barrier heights of chemical reactions in the BH6 dataset, where significant improvements are obtained relative to Gaussian based FLOSIC results.We report the implementation of a Fock-operator complete-active space self-consistent field (CAS-SCF) method combined with frozen-density embedding (FDE) into the KOALA quantum-chemistry program. The implementation is based on configuration interaction from an unrestricted reference determinant and is able to treat electronic configurations such as singlet, triplet, or quintet states embedded in a molecular environment. In order to account for possible spin polarization effects, the FDE contribution is extended to the unrestricted case. We assess the convergence obtained with the implementation at the example of a stretched lithium dimer with significant multi-reference character. The efficiency of the implementation enables the orbital optimization for 25 states in a state-average SA[S0-S10,T1-T12,Q1-Q2]-CAS(10,10)-SCF calculation for the retinal molecule using a def2-TZVP basis. The FDE ansatz leads to orbitals localized by definition on the target system, thus facilitating the orbital selection required for CAS methods in complex environments.