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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Optical rotation calculated with time-dependent density functional theory: The OR45 Benchmark
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Optical rotation calculated with time-dependent density functional theory: The OR45 Benchmark

机译：随时间变化的密度泛函理论计算的旋光度：OR45基准

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摘要

Time-dependent density functional theory (TDDFT) computations are performed for 42 organic molecules and three transition metal complexes, with experimental molar optical rotations ranging from 2 to 2 × 10~4 deg cm~2 dmol~(-1). The performances of the global hybrid functionals B3LYP, PBE0, and BHLYP, and of the range-separated functionals CAM-B3LYP and LC-PBE0 (the latter being fully long-range corrected), are investigated. The performance of different basis sets is studied. When compared to liquid-phase experimental data, the range-separated functionals do, on average, not perform better than B3LYP and PBE0. Median relative deviations between calculations and experiment range from 25 to 29%. A basis set recently proposed for optical rotation calculations (LPol-ds) on average does not give improved results compared to aug-cc-pVDZ in TDDFT calculations with B3LYP. Individual cases are discussed in some detail, among them norbornenone for which the LC-PBE0 functional produced an optical rotation that is close to available data from coupled-cluster calculations, but significantly smaller in magnitude than the liquid-phase experimental value. Range-separated functionals and BHLYP perform well for helicenes and helicene derivatives. Metal complexes pose a challenge to first-principles calculations of optical rotation.
机译：对42种有机分子和3种过渡金属配合物进行了时变密度泛函理论（TDDFT）计算，实验摩尔旋光度范围为2至2×10〜4 deg cm〜2 dmol〜（-1）。研究了全局混合功能B3LYP，PBE0和BHLYP以及范围分隔的功能CAM-B3LYP和LC-PBE0（后者经过完全远程校正）的性能。研究了不同基集的性能。与液相实验数据相比，平均而言，范围分隔的功能确实比B3LYP和PBE0更好。计算和实验之间的相对偏差中位数为25％至29％。与使用B3LYP的TDDFT计算中的aug-cc-pVDZ相比，最近提出的用于旋光度计算（LPol-ds）的平均基数集不能提供更好的结果。对个别情况进行了详细讨论，其中降冰片烯酮的LC-PBE0功能产生的旋光度接近耦合簇计算的可用数据，但幅度明显小于液相实验值。范围分离的官能团和BHLYP对于螺旋烯和螺旋烯衍生物表现良好。金属配合物对光学旋转的第一性原理提出了挑战。

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