Exciton transfer free energy from Car–Parrinello molecular dynamics
文献信息
Christian Schwermann, Nikos L. Doltsinis
A computational approach is presented which allows the calculation of free energies profiles for exciton transfer processes within the framework of ab initio molecular dynamics (AIMD) simulations, sampling both the electronic and the nuclear degrees of freedom. To achieve this, restraining potentials are imposed on the centres of maximally localized Wannier orbitals. The resulting quantum-mechanical orbital forces are derived analytically and implemented in an AIMD program. In analogy to classical umbrella sampling techniques, these restraints are used to control an exciton transfer by incrementally moving the Wannier centres corresponding to the electron–hole pair along a suitable reaction coordinate. The new method is applied to study exciton transfer between two stacked penta(3-methylthiophene) molecules as a function of intermolecular distance. From the resulting free energy profiles, exciton transfer rates and diffusion constants are estimated, which prove to be in line with experimental results.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.










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