Quantum dynamical simulation of electron-transfer reactions in an anharmonic environment.
Quantum dynamical simulation of electron-transfer reactions in an anharmonic environment.
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DOI：
10.1021/jp072367x
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发表时间：
2007-07
期刊：
影响因子：
--
通讯作者：
Haobin Wang;M. Thoss
中科院分区：
文献类型：
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作者：
Haobin Wang;M. Thoss
应用多层多组态含时Hartree理论研究了凝聚相环境中具有非简谐势函数的超快电子转移反应的量子动力学。研究了非谐性对环境原子核自由度和分子内振动自由度的影响。而前者原则上可以映射到一个虚构的谐波浴，后者不能以这种方式表示，因此，超出了常用的线性响应近似。数值例子来说明这些发现。
The multilayer multiconfiguration time-dependent Hartree theory is applied to study the quantum dynamics of ultrafast electron-transfer reactions in a condensed-phase environment with anharmonic potential functions. Effects of anharmonicity for both the nuclear degrees of freedom of the environment and the intramolecular vibrational degrees of freedom are investigated. Whereas the former can in principle be mapped to a fictitious harmonic bath, the latter cannot be represented in this way and, thus, go beyond the commonly employed linear response approximation. Numerical examples are presented to illustrate these findings.