Performance assessment of density‐functional methods for study of charge‐transfer complexes
Performance assessment of density‐functional methods for study of charge‐transfer complexes
复制标题
用于研究电荷转移复合物的密度泛函方法的性能评估
DOI：
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发表时间：
2003
影响因子：
3
通讯作者：
S. Scheiner
中科院分区：
文献类型：
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作者：
M. Liao;Yun Lu;S. Scheiner
不同的密度泛函应用于一些弱结合的分子间π -π电荷转移（CT）配合物。大多数功能，包括最近开发的mPWPW91和mPW1PW91，严重低估了实验激发能；只有半和半杂化BH&HLYP泛函才有很好的一致性。PW91PW91与晶体中测量的分子间距离最吻合，而BH&HLYP值约为0.1 Å过长。具有非局部交换校正的各种杂化泛函提供了与溶液中测量的实验生成热相比较有利的结合能。©2003 Wiley期刊公司[J] .计算机工程学报，2009,31 (4):623-631
Various density functionals are applied to a number of weakly bound intermolecular π–π charge‐transfer (CT) complexes. Most functionals, including the recently developed mPWPW91 and mPW1PW91, grossly underestimate experimental excitation energies; good agreement is obtained only with the half‐and‐half hybrid BH&HLYP functional. PW91PW91 provides the best agreement with intermolecular distances measured in crystal, while the BH&HLYP values are about 0.1 Å too long. Various hybrid functionals with nonlocal exchange correction provide binding energies that compare favorably with the experimental heats of formation measured in solution. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 623–631, 2003