Assessing computationally efficient isomerization dynamics: ΔSCF density-functional theory study of azobenzene molecular switching.
Assessing computationally efficient isomerization dynamics: ΔSCF density-functional theory study of azobenzene molecular switching.
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评估计算有效的异构化动力学：偶氮苯分子开关的 ΔSCF 密度泛函理论研究。
DOI：
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发表时间：
2012
影响因子：
4.4
通讯作者：
K. Reuter
中科院分区：
文献类型：
--
作者：
R. Maurer;K. Reuter
用→π∗自洽场密度泛函理论、含时密度泛函理论和近似耦合团簇单双势能面(RI-π→π∗)对典型分子开关偶氮苯的S_0、S_1(nΔ)和S_2(Δ)势能面进行了详细比较。这三种方法在PES的拓扑结构上都是一致的，而且与现有的关于光异构化机理的实验数据完全一致。特别是，当基于相同的基态交换关联(XC)泛函时，求和方法修正的ΔSCF和TD-DFT对S1和S2产生非常相似的结果。虽然这些技术产生了正确的PES拓扑已经在半局部XC泛函的水平上，但与RI-CC2或实验相比，可靠的绝对激发能量需要在远程校正杂交的水平上进行XC处理。然而，特别是Δ自洽势函数关于态交叉的稳健性和它的数值效率表明这种方法是一种很有希望的方法来研究更大的含偶氮苯体系的动力学。
We present a detailed comparison of the S0, S1 (n → π∗) and S2 (π → π∗) potential energy surfaces (PESs) of the prototypical molecular switch azobenzene as obtained by Δ-self-consistent-field (ΔSCF) density-functional theory (DFT), time-dependent DFT (TD-DFT) and approximate coupled cluster singles and doubles (RI-CC2). All three methods unanimously agree in terms of the PES topologies, which are furthermore fully consistent with existing experimental data concerning the photo-isomerization mechanism. In particular, sum-method corrected ΔSCF and TD-DFT yield very similar results for S1 and S2, when based on the same ground-state exchange-correlation (xc) functional. While these techniques yield the correct PES topology already on the level of semi-local xc functionals, reliable absolute excitation energies as compared to RI-CC2 or experiment require an xc treatment on the level of long-range corrected hybrids. Nevertheless, particularly the robustness of ΔSCF with respect to state crossings as well as its numerical efficiency suggest this approach as a promising route to dynamical studies of larger azobenzene-containing systems.
影响因子：
4.4
作者：
Hagen, Sebastian;Kate, Peter;Tegeder, Petra
通讯作者：
Tegeder, Petra