Electron transfer with TD-Split, a linear response time-dependent method

• Published in: Chemical physics Vol. 391; no. 1; pp. 62 - 68
• Main Authors: Bartell, Lizette A., Reslan, Randa, Wall, Michael R., Kennedy, Robert D., Neuhauser, Daniel
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 24.11.2011
• Subjects: Electron-transfer; TDDFT; Electron-transfer; TDDFT
• ISSN: 0301-0104
• DOI: 10.1016/j.chemphys.2011.04.010

A simple method, time-dependent split (TD-Split) is developed for electron transfer through a TD evaluation of the lowest excitation energy from the ground state of the combined charged system. As an example, we study transfer between substituted fullerenes, primarily PCBM. Numerical linearization reduces the number of required iterations, and trends similar to experiment are found. [Display omitted] ► Electron transmission from charged-dimer transition-state excitation. ► Starting point: extended dimer charged (above-gap) homo, which is then excited. ► Excitation by real-time and linear response TD propagation. ► Analogous to two level system, but with full polarization included. ► TD-Split much larger than from static LUMO + 1–LUMO splitting for fullerene dimers. We present a simple method, time-dependent split (TD-Split) for A → B electron transfer by a TD evaluation of the lowest excitation energy from the ground state of the combined (AB) − system. As an example, we study transfer between substituted fullerenes, primarily PCBM. Electron transfer in such fullerene systems is important as it is often the bottleneck in organic solar cells. The TD-Split method is described in detail, including numerical linearization which reduces the number of required iterations, and comparison to other possible approaches. We also compare to other molecules such as C 60Me 5H, and find similar trends as experiment.