Why Do TD-DFT Excitation Energies of BODIPY/Aza-BODIPY Families Largely Deviate from Experiment? Answers from Electron Correlated and Multireference Methods

被引:174
作者
Momeni, Mohammad R. [1 ]
Brown, Alex [1 ]
机构
[1] Univ Alberta, Dept Chem, Edmonton, AB T6G 2G2, Canada
基金
加拿大自然科学与工程研究理事会;
关键词
COUPLED-CLUSTER SINGLES; QUADRATIC CONFIGURATION-INTERACTION; GENERALIZED-GRADIENT-APPROXIMATION; POLARIZABLE CONTINUUM MODEL; DENSITY-FUNCTIONAL THEORY; EXCITED-STATES; OPTICAL SIGNATURES; PERTURBATION-THEORY; HIGHLY FLUORESCENT; AZA-BODIPY;
D O I
10.1021/ct500775r
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 vertical excitation energies of 17 boron-dipyrromethene (BODIPY) core structures with a variety of substituents and ring sizes are benchmarked using time-dependent density functional theory (TD-DFT) with nine different functionals combined with the cc-pVTZ basis set. When compared to experimental measurements, all functionals provide mean absolute errors (mean AEs) greater than 0.3 eV, larger than the 0.1-0.3 eV differences typically expected from TD-DFT. Due to the high linear correlation of TD-DFT results with experiment, most functionals can be used to predict excitation energies if corrected empirically. Using the CAM-B3LYP functional, 0-0 transition energies are determined, and while the absolute difference is improved (mean AE = 0.478 eV compared to 0.579 eV), the correlation diminishes substantially (R-2 = 0.961 to 0.862). Two very recently introduced charge transfer (CT) indices, q(CT) and d(CT), and electron density difference (EDD) plots demonstrate that CT does not play a significant role for most of the BODIPYs examined and, thus, cannot be the source of error in TD-DFT. To assess TD-DFT methods, vertical excitation energies are determined utilizing TD-HF, configuration interaction CIS and CIS(D), equation of motion EOM-CCSD, SAC-CI, and Laplace-transform based local coupled-cluster singles and approximate doubles LCC2* methods. Moreover, multireference CASSCF and CASPT2 vertical excitation energies were also obtained for all species (except CASPT2 was not feasible for the four largest systems). The SAC-Cl/cc-pVDZ, LCC2*/cc-pVDZ, and CASPT2/cc-pVDZ approaches are shown to have the smallest mean AEs of 0.154, 0.109, and 0.100 eV, respectively; the utility of the LCC2* approach is demonstrated for eight extended BODIPYs and aza-BODIPYs. We found that the problems with TD-DFT arise from difficulties in dealing with the differential electron correlation (as assessed by comparing CCS, CC2, LR-CCSD, CCSDR(T), and CCSDR(3) vertical excitation energies for five compounds) and from contributions of multireference character and double excitations (from analysis of the CASSCF wave functions).
引用
收藏
页码:2619 / 2632
页数:14
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