A Quantitative Analysis of Light-Driven Charge Transfer Processes Using Voronoi Partitioning of Time Dependent DFT-Derived Electron Densities

作者：Rombouts Jeroen A; Ehlers Andreas W^*; Lammertsma Koop^*

来源：Journal of Computational Chemistry, 2017, 38(20): 1811-1818.

DOI：10.1002/jcc.24822

• time-dependent density functional theory
• atomic charges
• charge analysis
• molecular design

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, Q(VECD). This subtractive method can also be used with Bader, Mulliken and Hirshfeld charges. A validation study shows Q(VECD) 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 Q(VECD) 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.

• 出版日期2017-7-30