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Kramers problem for nonequilibrium current-induced chemical reactions

机译:非平衡电流诱导化学反应的Kramers问题

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We discuss the use of tunneling electron current to control and catalyze chemical reactions. Assuming the separation of time scales for electronic and nuclear dynamics we employ Langevin equation for a reaction coordinate. The Langevin equation contains nonconservative current-induced forces and gives nonequilibrium, effective potential energy surface for current-carrying molecular systems. The current-induced forces are computed via Keldysh nonequilibrium Greens functions. Once a nonequilibrium, current-depended potential energy surface is defined, the chemical reaction is modeled as an escape of a Brownian particle from the potential well. We demonstrate that the barrier between the reactant and the product states can be controlled by the bias voltage. When the molecule is asymmetrically coupled to the electrodes, the reaction can be catalyzed or stopped depending on the polarity of the tunneling current.
机译:我们讨论了使用隧道电子流控制和催化化学反应的方法。假设电子和核动力学的时间尺度是分开的,我们将Langevin方程用作反应坐标。 Langevin方程包含非保守的电流感应力,并为载流分子系统提供了非平衡的有效势能面。通过Keldysh非平衡格林函数计算电流感应力。一旦定义了不平衡的,取决于电流的势能面,就将化学反应建模为布朗粒子从势阱中逸出。我们证明了反应物和产物状态之间的势垒可以通过偏置电压来控制。当分子与电极不对称偶联时,取决于隧穿电流的极性,反应可以被催化或终止。

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