Physical properties and chemical reactivity of alternant hydrocarbons and related compounds. XVI. Electronic absorption and phosphorescence spectra of aryl phenyl ketones
Physical properties and chemical reactivity of alternant hydrocarbons and related compounds. XVI. Electronic absorption and phosphorescence spectra of aryl phenyl ketones
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交替碳氢化合物和相关化合物的物理性质和化学反应性。
DOI：
10.1021/j100724a063
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发表时间：
1969
期刊：
影响因子：
--
通讯作者：
J. Pitts
中科院分区：
文献类型：
--
作者：
C. Párkányi;E. Baum;J. R. Wyatt;J. Pitts
通过 Pariser-Parr-Pople 型 LCI-SCF-MO 计算研究了八种芳基苯基酮的光谱性质。计算的 (So→Si) 激发能和酮的吸收带最大值的波长之间存在合理的一致性。获得了六种酮的磷光发射光谱，并且对于那些具有最低 (x, x*) 三重态的化合物，计算的 (So→T) 激发能和 0-0 发射带的波长之间存在合理的一致性。如果可能，通过磷光激发方法确认 0-0 带的位置。在所有情况下，预测的跃迁能量被发现都太低。发现计算值与单重态和三重态跃迁的观测值的偏差相同，从而准确预测最低 (x, x*) 激发态的 ST 分裂。造成这种误差的主要因素是酮基计算参数的选择、所研究化合物平面性的偏差以及光谱带位置的溶剂依赖性。
Spectral properties of eight aryl phenyl ketones were investigated by Pariser-Parr-Pople type LCI-SCF-MO calculations. Reasonable agreement is found between calculated (So—» Si) excitation energies and wavelengths of absorption band maxima of the ketones. Phosphorescence emission spectra for six of the ketones were obtained, and reasonable agreement is found between calculated (So—> T) excitation energy and wavelength of the 0-0 emission band for those compounds assigned to have a lowest-lying (x, x*) triplet state. The position of the 0-0 band was confirmed by phosphorescence excitation methods where possible. In all cases, the pre-dicted transition energy was found to be too low. Calculated values were found to deviate equally from observed values for both singletand triplet transitions resulting in accurate predictions of ST splittings for the lowest (x, x*) excited states. Major contributions to this error would be made by choice of calculation parameters for the keto group, deviations from planarity of the compounds studied, and solvent dependence of the spectral band positions.