Tian Boxue, Eriksson Emma S E, Eriksson Leif A
School of Chemistry, National University of Ireland - Galway, Galway, Ireland and Örebro Life Science Center, School of Science and Technology, Örebro University, 701 82 Örebro, Sweden.
J Chem Theory Comput. 2010 Jul 13;6(7):2086-94. doi: 10.1021/ct100148h.
The spectral properties of Tookad (Pd-bacteriopheophorbide, Pd-BPheid), an effective photosensitizer that targets mainly prostate tumors, and metal-free BPheid have been studied using time-dependent density functional theory (TD-DFT). The well-established B3LYP functional, which is known to overestimate excitation energies, was included in the study along with recently introduced range-separated and meta hybrid DFT functionals CAM-B3LYP, M06, M06-2X, M06HF, ωB97XD, ωB97X, ωB97, LC-ωPBE, and PBE0 (PBE1PBE). The main focus is the performance of the new functionals in predicting low-lying excitations (>600 nm), to explore their potential roles in drug development for photodynamic therapy. The data suggests that ωB97XD overall performs best for the Qy transition band (the red-most absorption), followed by CAM-B3LYP. LC-ωPBE, ωB97, B3LYP, and PBE1PBE all generated the Qy band far from the experimental position. The error in absorption energy for the Qy band was found to be at most 0.05 eV for ωB97XD, compared to 0.15-0.19 eV for B3LYP. The use of different basis sets used in excited-state calculations was shown to be of less importance as was the use of either B3LYP or M06 in geometry optimizations.
已使用含时密度泛函理论（TD-DFT）研究了主要靶向前列腺肿瘤的有效光敏剂Tookad（钯-细菌脱镁叶绿酸，Pd-BPheid）和无金属BPheid的光谱性质。研究中纳入了已得到广泛应用但已知会高估激发能的B3LYP泛函，以及最近引入的范围分离和杂化元密度泛函CAM-B3LYP、M06、M06-2X、M06HF、ωB97XD、ωB97、ωB97、LC-ωPBE和PBE0（PBE1PBE）。主要重点是这些新泛函在预测低能激发（>600 nm）方面的性能，以探索它们在光动力疗法药物开发中的潜在作用。数据表明，ωB97XD在Qy跃迁带（最红吸收）方面总体表现最佳，其次是CAM-B3LYP。LC-ωPBE、ωB97、B3LYP和PBE1PBE生成的Qy带均远离实验位置。发现ωB97XD的Qy带吸收能量误差至多为0.05 eV，而B3LYP的误差为0.15 - 0.19 eV。结果表明，激发态计算中使用不同基组的重要性较低，几何优化中使用B3LYP或M06的重要性也较低。
