论文标题

胶体量子点分子中电子转移的绝热与绝热过渡

Nonadiabatic to Adiabatic Transition of Electron Transfer in Colloidal Quantum Dot Molecules

论文作者

Hou, Bokang, Thoss, Michael, Banin, Uri, Rabani, Eran

论文摘要

电子转移是化学,生物学和物理学的重要且基本的过程,并且近年来受到了极大的关注。也许是涉及电子转移的非绝热和绝热状态之间过渡的最有趣的问题之一,因为捐赠者和受体之间的耦合(杂交)能量($ j $)是多样化的。在这里,使用胶体量子点分子,一类新的耦合量子点二聚体,我们在计算上说明了如何通过简单地更改颈部尺寸和/或量子点大小来调整供体和受体量子点之间的杂交能量。这提供了一个手柄,可以调整电子从非绝热过度抑制的MARCUS制度转移到单个系统中连贯的绝热状态,而无需更改重组能量,$λ$或典型的声子频率,$ω_c$。我们开发了一个原子模型来说明几种捐赠者和受体状态以及它们如何将其与晶格振动相结合,并利用Ehrenfest平均场混合量子 - 经典方法将电荷传递动力学描述为非耐绝热参数,$γ$。我们发现,随着系统被驱动到连贯的绝热极限,即使在升高的温度下,电荷传输速率也增加了几个数量级,并描绘了最强烈地与电荷传递反应坐标相对的点间和扭转声模式。

Electron transfer is an important and fundamental process in chemistry, biology and physics, and has received significant attention in recent years. Perhaps one of the most intriguing questions concerns with the realization of the transitions between nonadiabatic and adiabatic regimes of electron transfer, as the coupling (hybridization) energy, $J$, between the donor and acceptor is varied. Here, using colloidal quantum dot molecules, a new class of coupled quantum dot dimers, we computationally demonstrate how the hybridization energy between the donor and acceptor quantum dots can be tuned by simply changing the neck dimensions and/or the quantum dot size. This provides a handle to tune the electron transfer from the nonadiabatic over-damped Marcus regime to the coherent adiabatic regime in a single system, without changing the reorganization energy, $λ$, or the typical phonon frequency, $ω_c$. We develop an atomistic model to account for several donor and acceptor states and how they couple to the lattice vibrations, and utilize the Ehrenfest mean-field mixed quantum-classical method to describe the charge transfer dynamics as the nonadiabatic parameter, $γ$, is varied. We find that charge transfer rates increase by several orders of magnitude as the system is driven to the coherent, adiabatic limit, even at elevated temperatures, and delineate the inter-dot and torsional acoustic modes that couple most strongly to the charge transfer reaction coordinate.

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