- A Quantitative Analysis of Light-Driven Charge Transfer Processes Using Voronoi Partitioning of Time Dependent DFT-Derived Electron Densities
- Journal of Computational Chemistry
- Volume | Issue number
- 38 | 20
- Pages (from-to)
- Document type
- Faculty of Science (FNWI)
- Van 't Hoff Institute for Molecular Sciences (HIMS)
Institute of Interdisciplinary Studies (ISS)
An analytical method is presented that provides quantitative insight into light-driven electron density rearrangement using the output of standard time-dependent density functional theory (TD-DFT) computations on molecular compounds. Using final and initial electron densities for photochemical processes, the subtraction of summed electron density in each atom-centered Voronoi polyhedron yields the electronic charge difference, QVECD. This subtractive method can also be used with Bader, Mulliken and Hirshfeld charges. A validation study shows QVECD to have the most consistent performance across basis sets and good conservation of charge between electronic states. Besides vertical transitions, relaxation processes can be investigated as well. Significant electron transfer is computed for isomerization on the excited state energy surface of azobenzene. A number of linear anilinepyridinium donor-bridge-acceptor chromophores was examined using QVECD to unravel the influence of its pi-conjugated bridge on charge separation. Finally, the usefulness of the presented method as a tool in optimizing charge transfer is shown for a homologous series of organometallic pigments. The presented work allows facile calculation of a novel, relevant quantity describing charge transfer processes at the atomic level.
- go to publisher's site
- With additional supporting information
If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library, or send a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible.