A New Method To Evaluate Excited States Lifetimes Based on Green's Function: Application to Dye-Sensitized Solar Cells

作者：Sulzer David; Iuchi Satoru; Yasuda Koji^*

来源：Journal of Chemical Theory and Computation, 2016, 12(7): 3074-3086.

DOI：10.1021/acs.jctc.6b00181

Dye-sensitized solar cell (DSSCs) are the promising device for electricity generation. However, the initial stage in which an electron is injected from a dye to the semiconductor has not been precisely understood. Standard quantum chemistry methods cannot handle infinite number of orbitals coming from the band structure of the semiconductor, whereas solid state calculations cannot handle many excited states at a reasonable computational cost. In this regard, we propose a new method to evaluate lifetimes of many excited states of a molecule on a semi-infinite surface. On the basis of the theory of resonance state, the effect of the semi-infinite semiconductor is encoded into the complex self-energy from surface Greens function. The lifetimes of excited states are evaluated through the imaginary part of the self-energy, and the self-energy correction is included into excitation energies obtained from time-dependent density functional theory calculations. This new method is applied to a DSSC system composed of black dye attached to the TiO2 semiconductor, and the computed lifetimes are linked to the natures of excited states and to the surface properties. The present method provides the firm ground for analysis of interplay between many excited states of the dye and band structure of the semiconductor.

• 出版日期2016-7