A theoretical forecast of the hydrogen bond changes in the electronic excited state for BN and its derivatives

Central European Journal of Physics - Tập 10 - Trang 116-123 - 2011
Dandan Wang1, Ce Hao1, Se Wang1, Hong Dong1, Jieshan Qiu1
1State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian, Liaoning, China

Tóm tắt

The relationship between electronic spectral shifts and hydrogen-bonding dynamics in electronically excited states of the hydrogen-bonded complex is put forward. Hydrogen bond strengthening will induce a redshift of the corresponding electronic spectra, while hydrogen bond weakening will cause a blueshift. Time-dependent density function theory (TDDFT) was used to study the excitation energies in both singlet and triplet electronically excited states of Benzonitrile (BN), 4-aminobenzonitrile (ABN), and 4-dimethylaminobenzonitrile (DMABN) in methanol solvents. Only the intermolecular hydrogen bond C≡N...H-O was involved in our system. A fairly accurate forecast of the hydrogen bond changes in lowlying electronically excited states were presented in light of a very thorough consideration of their related electronic spectra. The deduction we used to depict the trend of the hydrogen bond changes in excited states could help others understand hydrogen-bonding dynamics more effectively.

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