Related papers: Charge Transfer in Partition Theory
Force fields uniquely assign interatomic forces for a given set of atomic coordinates. The underlying assumption is that electrons are in their quantum-mechanical ground state or in thermal equilibrium. However, there is an abundance of…
Partial atomic charges are a useful and intuitive concept for understanding molecular properties and chemical reaction mechanisms, showing how changes in molecular geometry can affect the flow of electronic charge within a molecule.…
We present an approach to electronic polarization in molecular solids treated as a set of quantum systems interacting classically. Individual molecules are dealt with rigorously as quantum-mechanical systems subject to classical external…
We illustrate the main features of a recently proposed method based on ensemble density functional theory to divide rigorously a complex molecular system into its parts [M.H. Cohen and A. Wasserman, J. Phys. Chem. A 111, 2229 (2007)]. The…
Charge transfer statistics of quantum particles is obtained by analysing the time evolution of the many-body wave function. Exploiting properly chosen gauge transformations, we construct the probabilities for transfers of a discrete number…
We study alchemical atomic energy partitioning as a method to estimate atomisation energies from atomic contributions which are defined in physically rigorous and general ways through use of the uniform electron gas as a joint reference. We…
The charge-transfer (CT) together with the polarization energy appears at second and higher orders in symmetry-adapted perturbation theory (SAPT). At present there is no theoretically compelling way of isolating the charge-transfer energy…
We show that as an electron transfers between closed-shell molecular fragments at large separation, the exact correlation potential of time-dependent density functional theory gradually develops a step and peak structure in the bonding…
Although Marcus theory is widely used to describe charge transfer in molecular systems, in its usual form it is restricted to transfer from one molecule to another. If a charge is delocalised across multiple donor molecules, this approach…
Alchemical transformations showed that perturbation theory can be applied also to changes in the atomic nuclear charges of a molecule. The alchemical path that connects two different chemical species involves the conceptualization of a…
Polarization and charge transfer are important effects which are difficult to describe using conventional force fields. Charge equilibration models can include both of these effects in large-scale molecular simulations. However, these…
The partition function, $U$, the number of available states in an atom or molecules, is crucial for understanding the physical state of any astrophysical system in thermodynamic equilibrium. There are surprisingly few {\em useful}…
Radiative charge exchange collisions between a carbon atom C(${}^3$P) and a helium ion He+, both in their ground state, are investigated theoretically. Detailed quantum chemistry calculations are carried out to obtain potential energy…
The electronic charge density plays a central role in determining the behavior of matter at the atomic scale, but its computational evaluation requires demanding electronic-structure calculations. We introduce an atom-centered,…
Charge transfer is a fundamental process that underlies a multitude of phenomena in chemistry and biology. Recent advances in observing and manipulating charge and heat transport at the nanoscale, and recently developed techniques for…
Charge transfer plays a crucial role in many processes of interest in physics, chemistry, and bio-chemistry. In many applications the size of the systems involved calls for time-dependent density functional theory (TDDFT) to be used in…
The geometry-dependent energy transfer rate from an electrically pumped inorganic semiconductor quantum well into an organic molecular layer is studied theoretically. We focus on F\"orster-type nonradiative excitation transfer between the…
Fluctuating-charge models are computationally efficient methods of treating polarization and charge-transfer phenomena in molecular mechanics and classical molecular dynamics simulations. They are also theoretically appealing as they are…
In the development of equations of state for polyatomic molecules, thermodynamic perturbation theory (TPT) is widely used to calculate the change in free energy due to chain formation. TPT is a simplification of a more general and exact…
Molecular conduction operating in dielectric solvent environments are often described using kinetic rates based on Marcus theory of electron transfer at a molecule-metal electrode interface. However, the successive nature of charge transfer…