Organic Electronic Materials: Recent Advances in the DFT Description of the Ground and Excited States Using Tuned Range-Separated Hybrid Functionals

被引:321
作者
Koerzdoerfer, Thomas [1 ]
Bredas, Jean-Luc [2 ,3 ]
机构
[1] Univ Potsdam, Inst Chem, D-14476 Golm, Germany
[2] Georgia Inst Technol, Sch Chem & Biochem, Atlanta, GA 30332 USA
[3] Georgia Inst Technol, Ctr Organ Photon & Elect, Atlanta, GA 30332 USA
基金
美国国家科学基金会;
关键词
MAIN-GROUP THERMOCHEMISTRY; SELF-INTERACTION ERROR; DENSITY FUNCTIONALS; CHARGE; SPECTRA; POLYACETYLENE; EXCITATIONS; ABSORPTION; KINETICS;
D O I
10.1021/ar500021t
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
CONSPECTUS: Density functional theory (DFT) and its time-dependent extension (TD-DFT) are powerful tools enabling the theoretical prediction of the ground- and excited-state properties of organic electronic materials with reasonable accuracy at affordable computational costs. Due to their excellent accuracy-to-numerical-costs ratio, semilocal and global hybrid functionals such as B3LYP have become the workhorse for geometry optimizations and the prediction of vibrational spectra in modern theoretical organic chemistry. Despite the overwhelming success of these out-of-the-box functionals for such applications, the computational treatment of electronic and structural properties that are of particular interest in organic electronic materials sometimes reveals severe and qualitative failures of such functionals. Important examples include the overestimation of conjugation, torsional barriers, and electronic coupling as well as the underestimation of bond-length alternations or excited-state energies in low-band-gap polymers. In this Account, we highlight how these failures can be traced back to the delocalization error inherent to semilocal and global hybrid functionals, which leads to the spurious delocalization of electron densities and an overestimation of conjugation. The delocalization error for systems and functionals of interest can be quantified by allowing for fractional occupation of the highest occupied molecular orbital. It can be minimized by using long-range corrected hybrid functionals and a nonempirical tuning procedure for the range-separation parameter. We then review the benefits and drawbacks of using tuned long-range corrected hybrid functionals for the description of the ground and excited states of pi-conjugated systems. In particular, we show that this approach provides for robust and efficient means of characterizing the electronic couplings in organic mixed-valence systems, for the calculation of accurate torsional barriers at the polymer limit, and for the reliable prediction of the optical absorption spectrum of low-band-gap polymers. We also explain why the use of standard, out-of-the-box range-separation parameters is not recommended for the DFT and/or TD-DFT description of the ground and excited states of extended, pi-conjugated systems. Finally, we highlight a severe drawback of tuned range-separated hybrid functionals by discussing the example of the calculation of bond-length alternation in polyacetylene, which leads us to point out the challenges for future developments in this field.
引用
收藏
页码:3284 / 3291
页数:8
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