Can Short- and Middle-Range Hybrids Describe the Hyperpolarizabilities of Long-Range Charge-Transfer Compounds?

被引:57
作者
Garza, Alejandro J. [1 ]
Wazzan, Nuha A. [3 ]
Asiri, Abdullah M. [3 ,4 ]
Scuseria, Gustavo E. [1 ,2 ,3 ]
机构
[1] Rice Univ, Dept Chem, Houston, TX 77251 USA
[2] Rice Univ, Dept Phys & Astron, Houston, TX 77251 USA
[3] King Abdulaziz Univ, Fac Sci, Dept Chem, Jeddah 21589, Saudi Arabia
[4] King Abdulaziz Univ, CEAMR, Jeddah 21589, Saudi Arabia
基金
美国国家科学基金会;
关键词
NONLINEAR-OPTICAL PROPERTIES; DENSITY-FUNCTIONAL THEORY; DELOCALIZATION ERROR; TRANSFER EXCITATIONS; POLARIZABILITIES; EXCHANGE; (HYPER)POLARIZABILITIES; DIARYLETHENES; APPLICABILITY; CHROMOPHORES;
D O I
10.1021/jp510062b
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The hyperpolarizabilities of five prototypical and four recently synthesized long-range charge-transfer (CT) organic compounds are calculated using short- and middle-range (SR and MR) hybrid functionals. These results are compared with data from MP2 and other DFT methods including GGAs, global hybrids, long-range corrected functionals (LC-DFT), and optimally tuned LC-DFT. Although it is commonly believed that the overestimation of hyperpolarizabilities associated with CT excitations by GGA and global hybrid functionals is the result of their wrong asymptotic exchange potential, and that LC-DFT heals this issue, we show here that SR and MR functionals yield results similar to those from LC-DFT. Hence, the long-range correction per se does not appear to be the key element in the well-known improved description of hyperpolarizabilities by LC-DFT. Rather, we argue that the inclusion of substantial amounts of Hartree-Fock exchange, which reduces the many-electron self-interaction error, is responsible for the relatively good results afforded by range separated hybrids. Additionally, we evaluate the effects of solvent and frequency on hyperpolarizabilities computed by SR and MR hybrids and compare these predictions with other DFT methods and available experimental data.
引用
收藏
页码:11787 / 11796
页数:10
相关论文
共 90 条
[1]  
[Anonymous], ACS S SERIES
[2]  
[Anonymous], ORGANIC MAT NONLINEA
[3]  
Asiri A. M., 2012, ACTA CRYSTALLOGR E, VE68, po915
[4]   (2E)-2-[(2H-1,3-Benzodioxol-5-yl) methylidene]-2,3-dihydro-1H-inden-1-one [J].
Asiri, Abdullah M. ;
Faidallah, Hassan M. ;
Al-Nemari, Khulud F. ;
Ng, Seik Weng ;
Tiekink, Edward R. T. .
ACTA CRYSTALLOGRAPHICA SECTION E-CRYSTALLOGRAPHIC COMMUNICATIONS, 2012, 68 :O1015-+
[5]   (2E)-2-(Furan-2-ylmethylidene)-2,3dihydro-1H-inden-1-one [J].
Asiri, Abdullah M. ;
Faidallah, Hassan M. ;
Al-Nemari, Khulud F. ;
Ng, Seik Weng ;
Tiekink, Edward R. T. .
ACTA CRYSTALLOGRAPHICA SECTION E-CRYSTALLOGRAPHIC COMMUNICATIONS, 2012, 68 :O1065-+
[6]   (2E)-2-(4-Bromobenzylidene)-2,3-dihydro-1H-inden-1-one [J].
Asiri, Abdullah M. ;
Faidallah, Hassan M. ;
Al-Nemari, Khulud F. ;
Ng, Seik Weng ;
Tiekink, Edward R. T. .
ACTA CRYSTALLOGRAPHICA SECTION E-CRYSTALLOGRAPHIC COMMUNICATIONS, 2012, 68 :O755-U2406
[7]   Hybrid density functional theory meets quasiparticle calculations: A consistent electronic structure approach [J].
Atalla, Viktor ;
Yoon, Mina ;
Caruso, Fabio ;
Rinke, Patrick ;
Scheffler, Matthias .
PHYSICAL REVIEW B, 2013, 88 (16)
[8]   Delocalization Error and "Functional Tuning" in Kohn-Sham Calculations of Molecular Properties [J].
Autschbach, Jochen ;
Srebro, Monika .
ACCOUNTS OF CHEMICAL RESEARCH, 2014, 47 (08) :2592-2602
[9]   Charge-Transfer Excitations and Time-Dependent Density Functional Theory: Problems and Some Proposed Solutions [J].
Autschbach, Jochen .
CHEMPHYSCHEM, 2009, 10 (11) :1757-1760
[10]   Exact-exchange density functional theory for hyperpolarizabilities [J].
Bokhan, Denis ;
Bartlett, Rodney J. .
JOURNAL OF CHEMICAL PHYSICS, 2007, 127 (17)