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Charge-Transfer Properties of Dye-Sensitized Solar Cells via Long-Range-Corrected Density Functional Theory

Published online by Cambridge University Press:  01 February 2011

Bryan Matthew Wong
Bryan Matthew Wong*
Affiliation:
bmwong@sandia.gov, Sandia National Laboratories, Materials Chemistry Department, Livermore, California, United States
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Abstract

The excited-state properties in a series of solar cell dyes are investigated with a long-range-corrected (LC) functional which provides a more accurate description of charge-transfer states. Using time-dependent density functional theory (TDDFT), the LC formalism correctly predicts a large increase in the excited-state electric dipole moment of the dyes with respect to that of the ground state, indicating a sizable charge separation associated with the S1 ← S0 excitation. The performance of the LC-TDDFT formalism, illustrated by computing excitation energies, oscillator strengths, and excited-state dipole moments, demonstrates that the LC technique provides a consistent picture of charge-transfer excitations as a function of molecular size. In contrast, the widely-used B3LYP functional severely overestimates excited-state dipole moments and underestimates the experimentally observed excitations, especially for larger dye molecules. The results of the present study emphasize the importance of long-range exchange corrections in TDDFT for investigating the charge-transfer dynamics in solar cell dyes.

Keywords

electronic structuresimulationoptoelectronic
Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 1120: Symposium M – Energy Harvesting–Molecules and Materials , 2008 , 1120-M01-03
Copyright
Copyright © Materials Research Society 2009

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