论文标题

光合激子之间的谐振振动 - 电气耦合不充分用减少的基础组来描述

Resonant Vibrational-Electronic Coupling between Photosynthetic Excitons is Inadequately Described by Reduced Basis Sets

论文作者

Sahu, Amitav, Kurian, Jo Sony, Tiwari, Vivek

论文摘要

在几种光合蛋白中,已经在实验和理论上研究了振动 - 电(振动)共振及其在能量和电荷转移中的作用。使用在典型的光合蛋白上建模的二聚体,我们将精确集合描述提供的激发子描述与振动尺寸降低的基集相反。我们使用对全哈密顿量的分析描述降低,我们表明,在存在电子激发和未开发位点的振动激发的情况下,这种基础状态之间的建设性干扰会导致激发量之间的振动耦合在增加的量子振动量的增加,从而逐渐强大。这种效果会导致振动子的三个显着特征,结合通过振动降低的振动振动尺寸 - 1。振动共振标准本身,2。振动辅助的完美分散定位,即使站点之间的纯粹电子混合在越来越多的核能越来越多的核能中,也会越来越多地振动,但振动的完美分离率越来越多。共振振动耦合涉及较高的振动量子。从光谱上可观察到的减少基础振动共振描述的局限性方面,在吸收和发射光谱中看到了几种差异,但由于压倒性的线扩展,可能会掩盖。但是,我们表明,在减少基于振动环共振的基础描述下,在基本上未描述几种与电子激发相关的振动激子界定和与电子激发相关的振动畸变。

Vibrational-electronic (vibronic) resonance and its role in energy and charge transfer has been experimentally and theoretically investigated in several photosynthetic proteins. Using a dimer modeled on a typical photosynthetic protein, we contrast the description of such excitons provided by an exact basis set description, as opposed to a basis set with reduced vibrational dimensionality. Using a reduced analytical description of the full Hamiltonian, we show that in the presence of vibrational excitation both on electronically excited as well as unexcited sites, constructive interference between such basis states causes vibronic coupling between excitons to become progressively stronger with increasing quanta of vibrational excitation. This effect leads to three distinguishing features of excitons coupled through a vibronic resonance which are not captured in basis sets with reduced vibrational dimensionality - 1. the vibronic resonance criterion itself, 2. vibronically assisted perfect delocalization between sites even though purely electronic mixing between the sites is imperfect due to energetic disorder, 3. the nuclear distortion accompanying vibronic excitons becoming increasingly larger for resonant vibronic coupling involving higher vibrational quanta. In terms of spectroscopically observable limitations of reduced basis set descriptions of vibronic resonance, several differences are seen in absorption and emission spectra, but may be obscured on account of overwhelming line broadening. However, we show that several features such as vibronic exciton delocalization and vibrational distortions associated with electronic excitations, which ultimately dictate the excited state wavepacket motions and relaxation processes, are fundamentally not described under reduced basis set descriptions of vibronic resonance.

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