关键词: 荧光发射能, 含时密度泛函理论, Hartree-Fock交换成分, 水杨酰苯胺, 质子转移, 电荷转移

Abstract: 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.

Key words: Fluorescence-emitting energy, Time-dependent density functional theory, Proportion of Hartree-Fock exchange energy, Salicylanilide, Proton transfer, Charge transfer