光化学与光功能材料.pptVIP

上次课的内容 光子和分子之间的相互作用（光的吸收过程) 跃迁发生的条件：对称性；轨道重叠；自选反转 激发态 单线态和三线态 激发态和基态性质之间的区别 3.4 激发态的失活过程 3.4 激发态的失活过程- 单分子(分子内）反应 Fluorescence Fluorescence intensity (F) Quantum yield (?f) Fluorescence rate constant and lifetime (kf and ??) Fluorescence spectra and Stoke’s Shift Phosphorescence Intensity Quantum yield Long lifetime; low quantum yield; 3.4 激发态的失活过程 - 双分子或多分子的过程 发生的条件: Donor的发射光谱和Acceptor的吸收光谱有重叠, 而且两个分子靠的距离足够近. 检测的手段: 荧光 (???) 3.4 激发态的失活过程 - 双分子或多分子的过程 3.4.2. 能量传递 (energy transfer) D* + A = D + A* Donor; Acceptor 3.4.2. 能量传递 (Energy transfer)的机理 重叠积分——Overlap integral (J) where fD is the normalized donor emission spectrum, and εA is the acceptor molar extinction coefficient 3.4.2. 能量传递 (energy transfer) The energy transfer efficiency (?) The distance between the donor and the acceptor The spectral overlap of the donor emission spectrum and the acceptor absorption spectrum. The relative orientation of the donor emission dipole moment and the acceptor absorption dipole moment. The energy transfer efficiency (?Ent) where kEnt is the rate of energy transfer, kf the radiative decay rate and the ki are the rate constants of any other de-excitation pathway. where ?0 is the fluorescence quantum yield of the donor in the absence of the acceptor, κ2 is the dipole orientation factor, n is the refractive index of the medium, NA is Avogadro‘s number, and J is the spectral overlap integral. Calculation of Energy transfer efficiency(?) and Rate constant (k) Where ? is the fluorescence lifetime of donor in the presence of acceptor; ?0 is the fluorescence lifetime of donor without acceptor; ?f is the fluorescence quantum yield of donor in the presence of acceptor and ?f0 is the fluorescence quantum yield of donor without of acceptor Marcus 电子转移理论----解释 3.5 激发态的寿命 ? 激发态的寿命: 激发态分子失活到原来的1/e时所需要的时间; e为自然对数的底 (2.718) 数学定义: ? = 1/kf + 1/kic + 1/knr+ 1/ket + 1/kent…… 各种失活过程的速率常数的倒数的和 激发态的寿命不仅和分子的结构有关, 同时和分子所处的环境很大的关系, 譬如: 溶剂的极性; 温度和压力等.人们在这个领域已经积累了丰富的理论和实际