We show that the third order cumulant correction is strongly dependent on the treatment of the solvent environment, revealing the interplay between environmental polarization and the electronic-vibrational coupling.Molecular dynamics simulations were performed to study the interfacial behavior of the pure carbon dioxide-water system and a binary 4060 mol. % gas mixture of (carbon dioxide + methane)-water at the temperatures of 275.15 K and 298.15 K and pressures near 4 MPa for CO2 and up to 10 MPa for methane. The simulations are used to study the dynamic equilibrium of the gases at the water-gas interface, to determine the z-density profiles for the gases and water, and calculate the interfacial tension γ under the different temperature/pressure conditions close to those of the formation of clathrate hydrates of these gases. At the same hydrostatic gas phase pressure, the CO2-water interface has a lower interfacial tension than the CH4-water interface. A greater number of CO2 molecules, as much as three times more than methane at the same pressure, were adsorbed at the interfacial layer, which reflects the stronger electrostatic quadrupolar and van der Waals interactions between CO2 and water molecules at the interface. Cu-CPT22 inhibitor The water surfaces are covered by less than a monolayer of gas even when the pressure of the system goes near the saturation pressure of CO2. The surface adsorbed molecules are in dynamic equilibrium with the bulk gas and with exchange between the gas and interface regions occurring repeatedly within the timescale of the simulations. The effects of the changes in the CO2-water interfacial tension with external temperature and pressure conditions on the formation of the clathrate hydrates and other CO2 capture and sequestration processes are discussed.We demonstrate that the temperature and doping dependencies of the photoluminescence (PL) spectra of a doped MoS2 monolayer have several peculiar characteristics defined by the trion radiative decay. While only zero-momentum exciton states are coupled to light, radiative recombination of non-zero momentum trions is also allowed. This leads to an asymmetric broadening of the trion spectral peak and redshift of the emitted light with increasing temperature. The lowest energy trion state is dark, which is manifested by the sharply non-monotonic temperature dependence of the PL intensity. Our calculations combine the Dirac model for the single-particle states, with parameters obtained from the first-principles calculations, and the direct solution of the three-particle problem within the Tamm-Dancoff approximation. The numerical results are well captured by a simple model that yields analytical expressions for the temperature dependencies of the PL spectra.Charge transfer rate constants were calculated for the carotenoid-porphyrin-C60 (CPC60) molecular triad dissolved in explicit tetrahydrofuran. The calculation was based on mapping the all-atom anharmonic Hamiltonian of this system onto the spin-boson Hamiltonian. The mapping was based on discretizing the spectral density from the time correlation function of the donor-acceptor potential energy gap, as obtained from all-atom molecular dynamics simulations. Different spin-boson Hamiltonians were constructed for each of the possible transitions between the three excited electronic states in two different triad conformations. The rate constants of three possible transitions were calculated via the quantum-mechanically exact Fermi's golden rule (FGR), as well as a progression of more approximate expressions that lead to the classical Marcus expression. The advantage of the spin-boson approach is that once the mapping is established, the quantum-mechanically exact FGR and the hierarchy of approximations are known in closed form. The classical Marcus charge transfer rate constants obtained with the spin-boson Hamiltonians were found to reproduce those obtained from all-atom simulations with the linearized semiclassical approximation, thereby confirming the equivalence of the two approaches for this system. Within the spin-boson Hamiltonian, we also found that the quantum-mechanically exact FGR rate constants were significantly enhanced compared to the classical Marcus theory rate constants for two out of three transitions in one of the two conformations under consideration. The results confirm that mapping to the spin-boson model can yield accurate predictions for charge transfer rate constants in a system as complex as CPC60 dissolved in tetrahydrofuran.Energy loss from hot-carrier cooling sets the thermodynamic limit for the photon-to-power conversion efficiency in optoelectronic applications. Efficient hot-electron extraction before cooling could reduce the energy loss and leads to efficient next generation devices, which, unfortunately, is challenging to achieve in conventional semiconductors. In this work, we explore hot-electron transfer in two-dimensional (2D) layered semiconductor heterostructures, which have shown great potential for exploring new physics and optoelectronic applications. Using broadband micro-area ultrafast spectroscopy, we firmly established a type I band alignment in the WS2-MoTe2 heterostructure and ultrafast (∼60 fs) hot-electron transfer from photoexcited MoTe2 to WS2. The hot-electron transfer efficiency increases with excitation energy or excess energy as a result of a more favorable continuous competition between resonant electron transfer and cooling, reaching 90% for hot electrons with 0.3 eV excess energy. This study reveals exciting opportunities of designing extremely thin absorber and hot-carrier devices using 2D semiconductors and also sheds important light on the photoinduced interfacial process including charge transfer and generation in 2D heterostructures and optoelectronic devices.We present a new method for simulating ungrounded charged metal slabs inside an electrolyte solution. The ions are free to move between the interior and exterior regions of the slab-electrolyte system. This leads to polarization of both sides of each slab, with a distinct surface charge induced on each surface. Our simulation method is based on the exact solution of the Poisson equation using periodic Green functions. To efficiently perform the calculations, we decouple the electrostatic energy due to surface polarization from that of purely Coulomb interaction between the ions. This allows us to combine a fast 3D Ewald summation technique with an equally fast calculation of polarization. As a demonstration of the method, we calculate ionic density profiles inside an electrolyte solution and explore charge neutrality violation in between charged metal slabs.