We present LayerPCM, an extension of the polarizable-continuum model coupled to real-time time-dependent density-functional theory, for efficient and accurate description electrostatic interactions between molecules multilayered dielectric substrates on which they are physisorbed. The former modeled quantum-mechanically, while latter treated as polarizable continua characterized by their consta...

Abstract Conformation analysis of dehydroascorbic acid and its bicyclic form was performed using the density functional theory. For energetically preferred conformations, ionization potentials (IP) bond dissociation enthalpies (BDE) were calculated B3LYP 6-311++G** basis set. The effects aqueous solution estimated solvation model based on (SMD) polarizable continuum (IEF-PCM). obtained results ...

A heterogeneous conductorlike solvation model (conductorlike screening model/conductorlike polarizable continuum model) that uses different local effective dielectrics for different portions of the solute cavity surface is implemented for quantum chemical Hartree-Fock and Kohn-Sham methods. A variational treatment is used to form the heterogeneous solvation operator, so a simple analytic expres...

The simplicity of dielectric continuum models has made them a standard tool in almost any Quantum Chemistry (QC) package. Despite being intuitive from a physical point of view, the actual electrostatic problem at the cavity boundary is challenging: the underlying boundary integral equations depend on singular, long-range operators. The parametrization of the cavity boundary should be molecular-...

Modeling the change in the electrostatics of organic molecules upon moving from vacuum into solvent, due to polarization, has long been an interesting problem. In vacuum, experimental values for the dipole moments and polarizabilities of small, rigid molecules are known to high accuracy; however, it has generally been difficult to determine these quantities for a polar molecule in water. A theo...

The solvation free energy difference, DG , and reorganization energy, l, of the electronic transition between the ground and first excited state of formaldehyde are investigated as a function of the solvent electronic polarizability in aqueous solution. Solvent shifts are difficult to measure experimentally for formaldehyde due to oligomer formation; shifts for acetone, which have been measured...

The hydration of Mg and Zn is examined using molecular dynamics simulations using three computational approaches of increasing complexity: the CHARMM non-polarizable force field based on the TIP3P water model, the Drude polarizable force field based on the SWM4-NDP water model, and a combined QM/MM approach in which the inner coordination sphere is represented using a high quality density funct...

The influence of a polar and polarizable environment on charge transfer processes at a conical intersection (CI) can be described by a diabatic free energy model yielding coupled surfaces as a function of both molecular coordinates and a solvent coordinate. We extend and apply this model for the S1-S0 CI in protonated Schiff bases, representing a model for retinal isomerization (Faraday Discuss...

The study of high-order absorption properties of molecules is a field of growing importance. Quantum-chemical studies can help design chromophores with desirable characteristics. Given that most experiments are performed in solution, it is important to devise a cost-effective strategy to include solvation effects in quantum-chemical studies of these properties. We here present an open-ended for...