s-tetrazine in aqueous solution: A density functional study of hydrogen bonding and electronic excitations

被引:33
作者
Odelius, M [1 ]
Kirchner, B [1 ]
Hutter, J [1 ]
机构
[1] Univ Zurich, Inst Phys Chem, CH-8057 Zurich, Switzerland
关键词
D O I
10.1021/jp0368381
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Using density functional theory based methods we studied vertical and adiabatic excitations of the s-tetrazine molecule, small clusters with water molecules and a single s-tetrazine molecule within 60 water molecules using periodic boundary conditions. We therefore achieve a consistent description of s-tetrazine from the isolated molecule to full solvation in water. The explicit treatment of solvent molecules allows for an accurate treatment of solute-solvent interactions. For the isolated s-tetrazine molecule a comparison with earlier high level ab initio calculations and other density functional calculations is made. In accordance with experiment the most favorable two-water-adduct displays a homodromic feature, i.e., a chain of hydrogen bonding from the nitrogen of the s-tetrazine to its methenyl (CH) group. Radial distribution functions calculated from a Car-Parrinello molecular dynamics simulation of the aqueous solution clearly show an unexpected preference of water for hydrogen bonding to the C-H group over the nitrogen lone pairs. Only infrequent and short-lived hydrogen bonds from water molecules to the nitrogen atoms are found. Calculations of vertical excitations using time-dependent density functional theory showed that the solvent shifts can be explained from the polarization of the Kohn-Sham orbitals of the solute. Hydrogen bonding has only a minor effect on the solvent shifts of low lying states of s-tetrazine.
引用
收藏
页码:2044 / 2052
页数:9
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