Charge-transfer bands in crystal spectra of molecular complexes
Charge-transfer bands in crystal spectra of molecular complexes
复制标题
分子复合物晶体光谱中的电荷转移带
DOI：
10.1016/0022-2852(67)90148-8
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发表时间：
1967
影响因子：
1.4
通讯作者：
H. Akamatu
中科院分区：
文献类型：
--
作者：
H. Kuroda;T. Kunii;Shoji Hiroma;H. Akamatu
用显微分光光度计测得6种分子络合物晶体在240-1300mμ波段的偏振吸收光谱，这些分子络合物分别以四氰基乙烯、对氟苯胺和1，3，5-三硝基苯为电子受主，在结晶态观察到与溶液中形成的1：1络合物的相应带的波数相近的电荷转移带.第一和第二电荷转移带的分裂分别为13.6∼14.5kK和7.0scf 7.3kK，大致相当于施主和受主分子占据的最高轨道和次要轨道之间的能量差。第一电荷转移带和第二电荷转移带之间的分裂分别为13.6∼14.5kK和7.0scf 7.3kK。在结晶态的电荷转移带上经常出现振动结构，而在溶液中形成的1：1络合物的电荷转移带上从未观察到这种振动结构。
The polarized absorption spectra in the 240–1300 mμ region were measured by means of a microspectrophotometer on crystals of six molecular complexes which involve pyrene and perylene as the electron donor and tetracyanoethylene,p-fluoranil, and 1,3,5-trinitrobenzene as the electron acceptor.The charge-transfer band in the crystalline state is observed at a wave number approximately equal to that of the corresponding band of the 1:1 complex formed in solution. The first charge-transfer band is exclusively polarized in the direction of the crystal axis along which donor and acceptor molecules are alternately stacked on each other if it is well separated from any local-excitation band.The splitting between the first and second charge-transfer bands is 13.6 ∼ 14.5 kK for the perylene complexes and 7.0 ∼ 7.3 kK for the pyrene complexes, which roughly corresponds to the energy difference between the highest and next occupied SCF molecular orbitals of the donor. It is also confirmed that a vibrational structure does often appear on the charge-transfer band in the crystalline state, while it has never been observed on the charge-transfer band of the 1:1 complex formed in solution.