Exciton transfer free energy from Car–Parrinello molecular dynamics

文献情報

出版日 2020-01-16

DOI 10.1039/C9CP06419B

インパクトファクター 3.676

著者

Christian Schwermann, Nikos L. Doltsinis

原文を見る

要旨

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.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

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