Finding the optimal exchange-correlation functional to describe the excited state properties of push-pull organic dyes designed for thermally activated delayed fluorescence

被引：25

作者：

Cardeynaels, Tom ^{[1
,2
,3
]}

Paredis, Simon ^{[2
,3
]}

Deckers, Jasper ^{[2
,3
]}

Brebels, Sonny ^{[2
,3
]}

Vanderzande, Dirk ^{[2
,3
]}

Maes, Wouter ^{[2
,3
]}

Champagne, Benoit ^{[1
]}

机构：

[1] Univ Namur, Namur Inst Struct Matter, Theoret & Struct Phys Chem Unit, Lab Theoret Chem, Rue Bruxelles 61, B-5000 Namur, Belgium

[2] Hasselt Univ, Inst Mat Res IMO IMOMEC, Design & Synth Organ Semicond DSOs, Agoralaan 1, B-3590 Diepenbeek, Belgium

[3] IMEC, IMOMEC Div, Wetenschapspk 1, B-3590 Diepenbeek, Belgium

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2020年 / 22卷 / 28期

基金：

比利时弗兰德研究基金会;

关键词：

LIGHT-EMITTING-DIODES; SINGLET-TRIPLET GAP; CHARGE-TRANSFER; DENSITY FUNCTIONALS; TADF MATERIALS; CC2; ELECTROLUMINESCENCE; PREDICTION; MECHANISM; ENERGIES;

D O I：

10.1039/d0cp02409k

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：

To gauge the suitability of an organic dye for thermally activated delayed fluorescence (TADF), its excited state properties are often calculated using density functional theory. For this purpose, the choice of the exchange-correlation (XC) functional is crucial as it heavily influences the quality of the obtained results. In this work, 19 different XC functionals with various amounts of Hartree-Fock (HF) exchange and/or long-range correction parameters are benchmarkedversusresolution-of-the-identity second-order coupled cluster (riCC2) calculations for a set of 10 prototype intramolecular donor-acceptor compounds. For the time-dependent density functional theory (TD-DFT) calculations, LC-BLYP(omega= 0.20) and M06-2X are the better performing XC functionals when looking at singlet and triplet excitation energies, respectively. For the singlet-triplet energy gap, LC-BLYP(omega= 0.17), LC-omega PBE(omega= 0.17) and a hybrid LC-BLYP(omega= 0.20)/M06-2X method give the smallest mean average errors (MAEs). Using the Tamm-Dancoff approximation (TD-DFT/TDA), the MAEs are further reduced for the triplet vertical excitation energies and the singlet-triplet energy gaps.

引用

页码：16387 / 16399

页数：13