Quantum chemistry calculations for molecules coupled to reservoirs: Formalism, implementation, and application to benzenedithiol
Quantum chemistry calculations for molecules coupled to reservoirs: Formalism, implementation, and application to benzenedithiol
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DOI：
10.1063/1.2716664
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发表时间：
2007-05-07
影响因子：
4.4
通讯作者：
Evers, F.
中科院分区：
文献类型：
--
作者：
Arnold, A.;Weigend, F.;Evers, F.
现代量子化学计算通常是针对孤立的大分子或原子团簇，总能量和粒子数是固定的。然而，在许多情况下，如量子输运计算或电化学环境中的分子，分子可以与储存器交换粒子（和能量）。这种情况下的计算需要从正则描述切换到巨正则描述，其中固定化学势而不是粒子数。为了实现这一目标，作者提出了一个标准量子化学包的实现。将介绍通过1，4-苯二硫醇的非线性电荷输运的应用。他们解释了领先的有限偏置效应的传输作为一个非平衡斯塔克效应的后果，并讨论了与早期工作的关系。(C)2007年，美国物理学会。
Modern quantum chemistry calculations are usually implemented for isolated systems-big molecules or atom clusters; total energy and particle number are fixed. However, in many situations, like quantum transport calculations or molecules in a electrochemical environment, the molecule can exchange particles (and energy) with a reservoir. Calculations for such cases require to switch from the canonical to a grand canonical description, where one fixes the chemical potential rather than particle number. To achieve this goal, the authors propose an implementation in standard quantum chemistry packages. An application to the nonlinear charge transport through 1,4-benzenedithiol will be presented. They explain the leading finite bias effect on the transmission as a consequence of a nonequilibrium Stark effect and discuss the relation to earlier work. (C) 2007 American Institute of Physics.