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Citation: ZHANG Shu-Qiang, WANG Ya-Qiong, ZHENG Xu-Ming. Density Functional Theory Investigation of the Photoisomerization Reaction of Nitroalkanes and Nirroaromatic Compounds[J]. Acta Physico-Chimica Sinica, ;2006, 22(12): 1489-1494. doi: 10.3866/PKU.WHXB20061211 shu

Density Functional Theory Investigation of the Photoisomerization Reaction of Nitroalkanes and Nirroaromatic Compounds

1.
(Key Laboratory of Advanced Texile Materials of Ministry of Educations, Department of Applied Chemistry, College of Science, Zhejiang Sci-Tech University, Hangzhou 310018, P. R. China)

Received Date: 6 June 2006
Available Online: 6 December 2006

The geometry structures and the energy barriers for the ground-state isomerization reactions of nitromethane, nitroethylene, nitrobenzene, and trans-β-nitrostyrene were computed using B3LYP/6-31G* level of theory. Their electronic transition energies were obtained using B3LYP-TD/6-31G* calculations. The results indicated that the C—N bond lengths of trans-β-nitrostyrene and nitrobenzen were significantly shorter than that of nitromethane, meanwhile the isomerization energy barriers of trans-β-nitrostyrene and nitrobenzen were somewhat lower than that of nitromethane. The energy difference (ΔE) between the vertical electronic transition energy and the transition state of the ground-state isomerization decreased dramatically with the increase of the molecular unsaturation as the molecule went from trans-β-nitrostyrene to nitrobenzene and to nitromethane. This suggests that as the unsaturation degree of the substituent R increases for R—NO2, the curve crossing between the excited state and the ground isomerization potential energy surface increases and this greatly favors the isomerization exit channel. The calculated first transition-allowed absorption band (also called A-band absorption) was assigned to a π→π* transition for these molecules. While the A-band electronic transition of nitromethane is mainly localized on the NO2 group, those of trans-β-nitrostyrene, nitrobenzene and nitroethylene are largely delocalized over the molecules, which causes the intramolecular charge-transfer processes to take place between the NO2 group and the C6H5—C=C group, the C6H5 group as well as the C=C group. Thus the localization or delocalization of the A-band electronic transition of nitroalkanes or nitroaromatics plays an important role in manipulating its photodissociation channel or photoisomerization channel.
- Photoisomerization;Electronic transition energies;Density functional theory;Nitro-compounds
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