TY - JOUR
T1 - Optical Absorption by Charge-Transfer Molecules
AU - Matyushov, Dmitry V.
AU - Newton, Marshall D.
N1 - Funding Information:
This research was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award DE-SC0015641.
Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/8/1
Y1 - 2019/8/1
N2 - An analytical formalism is developed for the calculation of absorption of radiation by charge-transfer molecules with electronic density delocalized between the donor and acceptor parts. The theory consistently incorporates both the vibronic coupling to quantum intramolecular vibrations and electrostatic interactions with a classical polarizable medium. The formulation operates in terms of basis-invariant parameters and can be used for calculations based on both the localized diabatic states and delocalized adiabatic wave function produced by standard quantum-chemistry algorithms. The basis-invariant reorganization energy is particularly important, since it determines observable spectroscopic parameters, in contrast to the adiabatic reorganization energy based on the molecular charge distributions in the adiabatic vacuum states. Analytical formulas are derived for the charge-transfer absorption band and first two spectral moments connecting spectroscopy to properties of charge-transfer molecules. Electronic delocalization requires a new definition of the Huang-Rhys factor traditionally used to construct vibronic band shapes. Theory's performance is illustrated by application to experimental data for self-exchange charge-transfer optical absorption and for metal-to-ligand emission transitions.
AB - An analytical formalism is developed for the calculation of absorption of radiation by charge-transfer molecules with electronic density delocalized between the donor and acceptor parts. The theory consistently incorporates both the vibronic coupling to quantum intramolecular vibrations and electrostatic interactions with a classical polarizable medium. The formulation operates in terms of basis-invariant parameters and can be used for calculations based on both the localized diabatic states and delocalized adiabatic wave function produced by standard quantum-chemistry algorithms. The basis-invariant reorganization energy is particularly important, since it determines observable spectroscopic parameters, in contrast to the adiabatic reorganization energy based on the molecular charge distributions in the adiabatic vacuum states. Analytical formulas are derived for the charge-transfer absorption band and first two spectral moments connecting spectroscopy to properties of charge-transfer molecules. Electronic delocalization requires a new definition of the Huang-Rhys factor traditionally used to construct vibronic band shapes. Theory's performance is illustrated by application to experimental data for self-exchange charge-transfer optical absorption and for metal-to-ligand emission transitions.
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U2 - 10.1021/acs.jpcb.9b04085
DO - 10.1021/acs.jpcb.9b04085
M3 - Article
C2 - 31287312
AN - SCOPUS:85070537453
SN - 1520-6106
VL - 123
SP - 6564
EP - 6578
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 30
ER -