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We present a novel {em ab initio} approach for computing intramolecular charge and energy transfer rates based upon a projection operator scheme that parses out specific internal nuclear motions that accompany the electronic transition. Our approach concentrates the coupling between the electronic and nuclear degrees of freedom into a small number of reduced harmonic modes that can be written as linear combinations of the vibrational normal modes of the molecular system about a given electronic minima. Using a time-convolutionless master-equation approach, parameterized by accurate quantum-chemical methods, we benchmark the approach against experimental results and predictions from Marcus theory for triplet energy transfer for a series of donor-bridge-acceptor systems. We find that using only a single reduced mode--termed the primary mode, one obtains an accurate evaluation of the golden-rule rate constant and insight into the nuclear motions responsible for coupling the initial and final electronic states. We demonstrate the utility of the approach by computing the inelastic electronic transition rates in a model donor-bridge-acceptor complex that has been experimentally shown that its exciton transfer pathway can be radically modified by mode-specific infrared excitation of its vibrational mode.
Electronic and optical properties of doped organic semiconductors are dominated by local interactions between donor and acceptor molecules. However, when such systems are in crystalline form, long-range order competes against short-range couplings. I
An interesting interplay between two different modifiers and the surface of titanium dioxide leads to a significant change in photoelectrochemical properties of the designed hybrid materials. The semiconductor is photosensitized by one of the counter
We investigate the electronic dynamics of a model organic photovoltaic (OPV) system consisting of polyphenylene vinylene (PPV) oligomers and a [6,6]-phenyl C61-butyric acid methylester (PCBM) blend using a mixed molecular mechanics/quantum mechanics
For electron-phonon Hamiltonians with the couplings linear in the phonon operators we construct a class of unitary transformations that separate the normal modes into two groups. The modes in the first group interact with the electronic degrees of fr
Carbene-metal-amides (CMAs) are a promising family of donor-bridge-acceptor molecular charge-transfer emitters for organic light-emitting diodes (OLEDs). Here a universal approach is introduced to tune the energy of their charge-transfer emission. A