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A theoretical study of electronic spectra of radical cations of some dihydroxynaphthalenes
Author(s) -
Khan Zahid H.
Publication year - 1992
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560420610
Subject(s) - chemistry , ionization energy , atomic electron transition , open shell , electronic structure , ionization , molecular electronic transition , x ray photoelectron spectroscopy , spectral line , spectroscopy , diagram , computational chemistry , configuration interaction , electron configuration , atomic physics , ion , molecule , physics , organic chemistry , nuclear magnetic resonance , statistics , mathematics , quantum mechanics , astronomy
Electronic transition energies of radical cations of 1.2‐, 1.3‐, 1.6‐, and 1.7−dihydroxynaphthalenes are calculated using an open‐shell SCF method with configuration interaction. The results are critically analyzed and a correlation diagram is given that shows the energy‐shift and intensity variation in the electronic transitions when moving from one system to another, thus revealing the characteristic behavior of the transitions depending on the positions of the hydroxyl substituents. An interesting relation connecting the electronic spectroscopy with the UV photoelectron spectroscopy is suggested on the basis of which the first ionization potentials ( IPS ) of the substituted aromatic systems can be inferred from the calculated energy of the A ‐type ( HOMO → LUMO ) transitions for their radical cations. Furthermore, the predictability of the IP s is found to be considerably increased with the incorporation of “molecular size” in the regression.