Belosludov Rodion V, Nevonen Dustin, Rhoda Hannah M, Sabin Jared R, Nemykin Victor N
Institute for Materials Research , Tohoku University , Katahira 2-1-1 , Aoba-ku Sendai 980-8577 , Japan.
Department of Chemistry , University of Manitoba , Winnipeg , Manitoba R3T 2N2 , Canada.
J Phys Chem A. 2019 Jan 10;123(1):132-152. doi: 10.1021/acs.jpca.8b07647. Epub 2018 Dec 18.
An insight into the electronic structure of the metal-free, unsubstituted, and nonperipherally substituted with electron-donating groups tetraazaporphyrin (HTAP), phthalocyanine (HPc), naphthalocyanine (HNc), anthracocyanine (HAc) platforms has been gained and discussed on the basis of experimental UV-vis and MCD spectra as well as density functional theory (DFT), time-dependent DFT (TDDFT), and semiempirical ZINDO/S calculations. Experimental data are suggestive of potential crossover behavior between the 1 B and 1 B excited states (in traditional D notation) around 800 nm. A large array of exchange-correlation functionals were tested to predict the vertical excitation energies in HTAPs, HPcs, HNcs, and HAcs both in gas phase and solution. In general, TDDFT-predicted energies of the Q and Q bands and the splitting between them correlate well with the amount of Hartree-Fock exchange present in a specific exchange-correlation functional with the long-range corrected LC-BP86 and LC-wPBE functionals providing the best agreement between theory and experiment. The pure GGA (BP86) exchange-correlation functional significantly underestimated, while long-range corrected LC-BP86 and LC-wPBE exchange-correlation functionals and semiempirical ZINDO/S method strongly overestimated the intramolecular charge-transfer (ICT) transitions experimentally observed for -OR, -SR, and -NR substituted at nonperipheral position phthalocyanines and their analogues in the 450-650 nm region. The hybrid CAM-B3LYP, PBE1PBE, and B3LYP exchange-correlation functionals were found to be much better in predicting energies of such ICT transitions. Overall, we did not find a single exchange-correlation functional that can accurately (MAD < 0.05 eV) and simultaneously predict the energies and the splittings of the Q and Q bands as well as energies of the ICT transitions in a large array of substituted and unsubstituted metal-free phthalocyanines and their benzoannulated analogues.
基于实验紫外可见光谱和磁圆二色光谱以及密度泛函理论（DFT）、含时密度泛函理论（TDDFT）和半经验ZINDO/S计算，对无金属、未取代以及非周边被供电子基团取代的四氮杂卟啉（HTAP）、酞菁（HPc）、萘酞菁（HNc）、蒽菁（HAc）平台的电子结构进行了深入研究和讨论。实验数据表明，在800 nm左右，1B和1B激发态（传统D符号表示）之间可能存在交叉行为。测试了大量的交换相关泛函，以预测气相和溶液中HTAP、HPc、HNc和HAc的垂直激发能。一般来说，TDDFT预测的Q带和Q带能量以及它们之间的分裂与特定交换相关泛函中存在的哈特里 - 福克交换量有很好的相关性，其中长程校正的LC - BP86和LC - wPBE泛函在理论和实验之间提供了最佳一致性。纯广义梯度近似（GGA，BP86）交换相关泛函显著低估了能量，而长程校正的LC - BP86和LC - wPBE交换相关泛函以及半经验ZINDO/S方法则强烈高估了在450 - 650 nm区域非周边位置被 - OR、 - SR和 - NR取代的酞菁及其类似物实验观察到的分子内电荷转移（ICT）跃迁。发现杂化的CAM - B3LYP、PBE1PBE和B3LYP交换相关泛函在预测此类ICT跃迁能量方面要好得多。总体而言，我们没有找到一个能准确（平均绝对偏差 < 0.05 eV）且同时预测大量取代和未取代的无金属酞菁及其苯并稠合类似物中Q带和Q带的能量及分裂以及ICT跃迁能量的单一交换相关泛函。
