Gaussian, Inc., 340 Quinnipiac St., Bldg. 40, Wallingford, Connecticut 06492, United States, and Department of Chemistry, Yale University, 225 Prospect St., New Haven, Connecticut 06511, United States.
J Chem Theory Comput. 2011 Feb 8;7(2):456-66. doi: 10.1021/ct100662n. Epub 2010 Dec 22.
In this work, we compare a large variety of density functionals against the equation of motion coupled cluster singles and doubles (EOM-CCSD) method for the calculation of oscillator strengths. Valence and Rydberg states are considered for a test set composed of 11 small organic molecules. In our previous work, the same systems and methods were tested against experimental results for the excitation energies. The results from this investigation confirm our previous findings, i.e., that there is a large difference between the functionals. For the oscillator strength, the average best agreement with EOM-CCSD is provided by CAM-B3LYP followed by LC-ωPBE and, to a lesser extent, B3P86 and LC-BLYP.
在这项工作中，我们将对比大量的密度泛函理论（DFT）方法与含时微扰耦合簇 singles and doubles（EOM-CCSD）方法，来计算振子强度。对于由 11 个小分子组成的测试集，我们考虑了价态和里德堡态。在我们之前的工作中，相同的体系和方法与激发能的实验结果进行了对比。这项研究的结果证实了我们之前的发现，即不同泛函之间存在很大差异。对于振子强度，与 EOM-CCSD 吻合最好的是 CAM-B3LYP，其次是 LC-ωPBE，在较小程度上，还有 B3P86 和 LC-BLYP。
