Effect of varying the TD-lc-DFTB range-separation parameter on charge and energy transfer in a model...

Atomistic modeling of energy and charge transfer at the heterojunction of organic solar cells is an active field with many remaining outstanding questions owing, in part, to the difficulties in performing reliable photodynamics calculations on very large systems. One approach to being able to overcome these difficulties is to design and apply an appropriate simplified method. Density-functional tight binding (DFTB) has become a popular form of approximate density-functional theory based on a minimal valence basis set and neglect of all but two center integrals. We report the results of our tests of a recent long-range correction (lc) [A. Humeniuk and R. Mitrić, J. Chem. Phys. 143, 134120 (2015)] for time-dependent (TD) lc-DFTB by carrying out TD-lc-DFTB fewest switches surface hopping calculations of energy and charge transfer times using the relatively new DFTBABY [A. Humeniuk and R. Mitrić, Comput. Phys. Commun. 221, 174 (2017)] program. An advantage of this method is the ability to run enough trajectories to get meaningful ensemble averages. Our interest in the present work is less in determining exact energy and charge transfer rates than in understanding how the results of these calculations vary with the value of the range-separation parameter (R_lc = 1/μ) for a model organic solar cell heterojunction consisting of a gas-phase van der Waals complex P/F made up of a single pentacene (P) molecule together with a single buckminsterfullerene (F) molecule. The default value of R_lc = 3.03 a₀ is found to be much too small as neither energy nor charge transfer is observed until R_lc ≈ 10 a₀. Tests at a single geometry show that the best agreement with high-quality ab initio spectra is obtained in the limit of no lc (i.e., very large R_lc). A plot of energy and charge transfer rates as a function of R_lc is provided, which suggests that a value of R_lc ≈ 15 a₀ yields the typical literature (condensed-phase) charge transfer time of about 100 fs. However, energy and charge transfer times become as high as ∼300 fs for R_lc ≈ 25 a₀. A closer examination of the charge transfer process P^*/F → P⁺/F^- shows that the initial electron transfer is accompanied by a partial delocalization of the P hole onto F, which then relocalizes back onto P, consistent with a polaron-like picture in which the nuclei relax to stabilize the resultant redistribution of charges.