ESIPT和TICT荧光发射的电子结构特征及发射能计算

采用含时密度泛函理论(TDDFT)与单激发组态相互作用(CIS)相结合的计算方案对八种结构相似的水杨酰苯胺衍生物及其类似物第一激发单重态(S1)进行考察, 证实它们的荧光发射分属分子内质子转移(ESIPT)和分子扭转-电荷转移(TICT)两种不同机制且结论与已知实验事实相符. ESIPT发光的化合物在电子跃迁前后无明显的电荷转移发生, 发射能计算的适用泛函是OLYP和BLYP等无Hartree-Fock(HF)交换成分的纯泛函; TICT发光的化合物在电子跃迁前后发生明显的电荷转移, 其适用泛函为含约37% HF交换成分的混合型泛函(例如mPW1B95和MPW1K). 按上述原则来选择适用泛函, 即可在TDDFT/6-31G(d)//CIS/3-21G(d)理论水平上正确预测水杨酰苯胺衍生物和类似物的发射能, 平均精度可达0.2 eV. 兼具质子转移与电荷转移双反应通道的化合物, 两者的竞争遵从能量最小原理, 结果使荧光发射仅选择其中一个通道进行. 泛函的选择只与实际发生的反应有关, 与并未实际发生的反应通道无关. 附加的八个算例进一步表明, 此成功的计算方案可望推广应用于其它类型的ESIPT和TICT荧光有机物.

Electronic Structure Characteristics of ESIPT and TICT Fluorescence Emissions and Calculations of Emitting Energies

A scheme of time-dependent density functional theory (TDDFT) combined with the single-excitation configuration interaction (CIS) approach was employed to investigate the first excited singlet state (S1) for eight salicylanilide derivatives and analogues, which have similar structural formulas. The results showed that fluorescence-emitting mechanisms of these compounds were in two distinct manners (excited-state intramolecular proton transfer (ESIPT) and twisted intramolecular charge transfer (TICT)), which agreed with the well-known experiments. For ESIPT compounds with inconspicuous charge transfer (CT) during electron transition, pure functionals without Hartree-Fock (HF) exchange energy, such as OLYP and BLYP, were suitable to calculate emitting energies. For TICT compounds with large CT during electron transition, hybrid functionals with about 37% HF exchange energy, such as mPW1B95 and MPW1K, performed well. On condition that the exchange-correlation (XC ) functionals were chosen properly according to the rules above, reliable emitting energies for salicylanilide derivatives and analogues could be obtained at the TDDFT/6-31G (d)//CIS/3-21G (d) level. The average accuracy reached about 0.2 eV. For the salicylanilides with both of proton transfer (PT) and CTreaction channels, only one channel occurred actually according to the principle of energy minimum. This actual reaction decided proper XC functionals, whereas the reaction that did not occur actually was trivial. Eight appendent compounds were calculated to prove that this successful scheme is expected to be suitable for other ESIPT and TICT compounds.