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首页> 外文期刊>The Journal of Chemical Physics >Electronic energy transfer through non-adiabatic vibrational-electronic resonance. II. 1D spectra for a dimer
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Electronic energy transfer through non-adiabatic vibrational-electronic resonance. II. 1D spectra for a dimer

机译：通过非绝热振动 - 电子共振传递电子能源。 II。 二聚体的1D光谱

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Vibrational-electronic resonance in photosynthetic pigment-protein complexes invalidates Forster's adiabatic framework for interpreting spectra and energy transfer, thus complicating determination of how the surrounding protein affects pigment properties. This paper considers the combined effects of vibrational-electronic resonance and inhomogeneous variations in the electronic excitation energies of pigments at different sites on absorption, emission, circular dichroism, and hole-burning spectra for a non-degenerate homodimer. The non-degenerate homodimer has identical pigments in different sites that generate differences in electronic energies, with parameters loosely based on bacteriochlorophyll a pigments in the Fenna-Matthews-Olson antenna protein. To explain the intensity borrowing, the excited state vibrational-electronic eigenvectors are discussed in terms of the vibrational basis localized on the individual pigments, as well as the correlated/anti-correlated vibrational basis delocalized over both pigments. Compared to those in the isolated pigment, vibrational satellites for the correlated vibration have the same frequency and precisely a factor of 2 intensity reduction through vibrational delocalization in both absorption and emission. Vibrational satellites for anti-correlated vibrations have their relaxed emission intensity reduced by over a factor 2 through vibrational and excitonic delocalization. In absorption, anti-correlated vibrational satellites borrow excitonic intensity but can be broadened away by the combination of vibronic resonance and site inhomogeneity; in parallel, their vibronically resonant excitonic partners are also broadened away. These considerations are consistent with photosynthetic antenna hole-burning spectra, where sharp vibrational and excitonic satellites are absent. Vibrational-excitonic resonance barely alters the inhomogeneously broadened linear absorption, emission, and circular dichroism spectra from those for a purely
机译：光合色素蛋白复合物中的振动电子共振使福尔斯特的绝热框架无效地解释光谱和能量转移，从而使周围蛋白质的测定复杂化色素物质。本文考虑了振动 - 电子共振和不同部位在吸收，发射，圆形二色性和空穴燃烧光谱的不同部位的电子励磁能量中的振动电子激发能量的综合作用。对于非退化同源过二聚体的空穴燃烧光谱。非退化的同源二聚体在不同部位具有相同的颜料，其在不同的位置产生电子能量的差异，参数松散地基于FENNA-MATTHEWS-OLSON天线蛋白中的菌种血糖血糖A颜料。为了解释强度借用，在各种颜料上定位的振动基础上讨论激发态振动 - 电子特征向量，以及在两种颜料上划分的相关/抗相关振动基础。与隔离颜料中的那些相比，相关振动的振动卫星具有相同的频率，并且通过在吸收和发射中通过振动疏水化精确降低2强度降低。用于反相关振动的振动卫星通过振动和激发器的临床化，使其放松的发射强度减少了超过一个因子2。在吸收，反相关的振动卫星借用兴奋强度，但可以通过振动共振和位点的组合扩展;并行地，它们的具有增强谐振的激子合作伙伴也扩大了。这些考虑因素与光合天线空穴燃烧光谱一致，其中不存在尖锐的振动和激发卫星。振动激发性共振几乎没有改变纯粹用于纯粹宽的线性吸收，发射和圆形二色性光谱。

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