文献类型：期刊文献

英文题名：Assessment of Range-Separated Exchange Functionals and Nonempirical Functional Tuning for Calculating the Static Second Hyperpolarizabilities of Streptocyanines

作者：Wang, Chao[1];Yuan, Yizhong[2,3];Tian, Xiaohui[2,3]

机构：[1]Zhejiang Univ, Dept Polymer Sci & Engn, MOE Key Lab Macromol Synth & Functionalizat, Hangzhou 310027, Peoples R China;[2]East China Univ Sci & Technol, Minist Educ, Key Lab Ultrafine Mat, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, Sch Mat Sci & Engn, Dept Mat Sci & Engn, Shanghai Key Lab Adv Polymer Mat, Shanghai 200237, Peoples R China

年份：2017

卷号：38

期号：9

起止页码：594

外文期刊名：JOURNAL OF COMPUTATIONAL CHEMISTRY

收录：;EI(收录号：20170503312179);WOS:【SCI-EXPANDED(收录号:WOS:000394874800004)】；

基金：Contract grant sponsor: Fundamental Research Funds for the Central Universities; Contract grant number: 22A201514002

语种：英文

外文关键词：RSE functionals; optimal IP-tuning; second hyperpolarizabilities; cyanines

摘要：DFT method can severely overestimate the response properties for p-conjugation systems. The range-separated exchange and recently developed optimal IP-tuning process are evaluated on the prediction of static second hyperpolarizabilities of streptocyanines of increasing molecular length. The finite field results have shown that the exact exchange at midium and long distance can relieve only a part of the overshooting but still beyond satisfaction. The exact exchange at short distance has the oppsite effects showing the failure of converntional hGGA. The optimal tuned range-separated exchange functionals show little improvements performing worse than the default ones. Importantly, the electronic structure-property relationship, bond order alternation-c, is not well established with DFT method. (C) 2017 Wiley Periodicals, Inc.