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Hydrogen bonding and solvatochromatic shift of the lowest 1 (n, π*) excitation of s‐tetrazine in its hydrated clusters and dilute solutions
Author(s) -
Xie Daiqian,
Zeng Jun
Publication year - 2004
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.20074
Subject(s) - tetrazine , chemistry , hydrogen bond , excited state , aqueous solution , solvent , ab initio , cluster (spacecraft) , computational chemistry , molecule , crystallography , atomic physics , organic chemistry , physics , computer science , programming language
Abstract Hydrogen bonding involving azine and its derivatives such as nucleic bases is very important for understanding the structure and function of biological systems. In this work, we have investigated the hydrogen bonding structures of the hydrated cluster and dilute aqueous solution of s‐tetrazine using computer simulation techniques, and evaluated the absorption and fluorescence shifts of the lowest 1 (n, π*) excitation of s‐tetrazine solution using our solvent shift method. For the s‐tetrazine–water cluster, a linear orthodox hydrogen bond arrangement is predicted in both ground and excited states with small structural and energetic differences, and a bifurcated hydrogen bond isomerization is anticipated. Further, ab initio calculations have verified these conformations. For the s‐tetrazine–water solution, a mixture of two hydrogen bonding arrangements is found to be in both ground and excited states, resulting in small magnitudes of absorption and fluorescence solvent shifts. This finalizes our series investigation of hydrogen bonding and solvent shifts of dilute azines in water. © 2004 Wiley Periodicals, Inc. J Comput Chem 25: 1487–1494, 2004