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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Calculation of Electronic Circular Dichroism Spectra with Time-Dependent Double-Hybrid Density Functional Theory
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Calculation of Electronic Circular Dichroism Spectra with Time-Dependent Double-Hybrid Density Functional Theory

机译：时变双混合密度泛函理论计算电子圆二色性光谱

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Time-dependent double-hybrid density functional theory is applied to the calculation of the electronic circular dichroism (CD) spectra of molecules. The TD-B2PLYP method is based on vertical excitation energies obtained from its hybrid-GGA part B2LYP in a conventional TD-DFT linear response treatment and a CIS(D) type perturbation correction for these excited states. A new benchmark set of six representative organic molecules with a wide variety of different electronic character is introduced for this investigation. The simulated TD-B2PLYP spectra are compared to experiment and those computed with the TD-B2LYP (i.e., no CIS(D) correction) and TD-B3LYP methods. Vertical excitation energies at the perturbatively corrected level are, in the majority of cases, more accurate than, e.g., with TD-B3LYP. Relative band positions are also reproduced better. In one example, the high-energy CD bands are not computed with sufficient accuracy, which is attributed to an instability of the perturbation correction. Due to the inclusion of a large portion of "exact" exchange (53%) in B2PLYP, the spectra feature less artificially created excited states and CD bands than with TD-B3LYP. In all six examined cases, TD-B2PLYP gives qualitatively correct spectra, whereas the hybrid functionals sometimes show a more erratic behavior. Therefore, we can recommend the use of the new double-hybrid approach for the computation of CD and the prediction of absolute configurations of chiral molecules.
机译：基于时间的双杂化密度泛函理论被应用于分子的电子圆二色性（CD）光谱的计算。 TD-B2PLYP方法基于在常规TD-DFT线性响应处理中从其混合GGA部分B2LYP获得的垂直激发能量，以及针对这些激发态的CIS（D）型扰动校正。本研究引入了一个新的基准测试组，该基准组包含六个具有各种不同电子特性的代表性有机分子。将模拟的TD-B2PLYP光谱与实验进行比较，并使用TD-B2LYP（即未进行CIS（D）校正）和TD-B3LYP方法进行计算。在大多数情况下，经过扰动校正的水平的垂直激发能比例如TD-B3LYP更为准确。相对乐队的位置也更好地再现。在一个示例中，没有以足够的精度来计算高能CD带，这归因于扰动校正的不稳定性。由于在B2PLYP中包含了很大一部分“精确”交换（53％），因此与TD-B3LYP相比，该光谱具有较少的人工创建的激发态和CD谱带。在所有六个被检查的情况下，TD-B2PLYP给出了定性正确的光谱，而混合功能有时表现出更不稳定的行为。因此，我们可以推荐使用新的双杂交方法来计算CD和预测手性分子的绝对构型。

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