期刊
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 16, 期 28, 页码 14408-14419出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c3cp54517b
关键词
-
资金
- International NRW Graduate School of Chemistry
The recently introduced sTDA methodology [S. Grimme, J. Chem. Phys., 2013, 138, 244104] to compute excitation spectra of huge molecular systems is extended to range-separated hybrid (RSH) density functionals. The three empirical parameters of the method which describe a screened two-electron interaction are obtained for some common RSH functionals (omega B97 family, CAM-B3LYP, LC-BLYP) from a fit to theoretical SCS-CC2 reference vertical excitation energies for a set of small to medium-sized chromophores. The method is cross-validated on a set of inter-and intramolecular charge transfer states and a set composed of typical valence transitions. Overall small deviations from reference data of only about 0.2-0.4 eV are found with best performance for CAM-B3LYP and omega B97X-D3. To demonstrate versatility and robustness of the new methodology, applications (the UV/Vis spectrum of the pyridine polymer and the ECD spectrum of (P)-[11]helicene) and frequently used charge transfer examples are discussed. In one case, 11000+ excited electronic states of a system containing 330 atoms were calculated. We show that the asymptotically correct sTDA-RSH combination yields results often superior to those based on global hybrids and that it opens up new possibilities for the computation of excited states in materials science and bio-molecular systems.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据