title: The lowest singlet (n,pi*) and (pi,pi*) excited states of the hydrogen-bonded complex between water and pyrazine.
abstract: The hydrogen bonding between water and pyrazine in its ground, lowest (n,pi*), and lowest (pi,pi*) states is investigated using density-functional theory (DFT), time-dependent density function theory (TD-DFT), coupled-cluster singles and doubles (CCSD) theory and equation-of-motion coupled cluster (EOM-CCSD) theory. For all states, the minimum-energy configuration is found to be an orthodox linear hydrogen-bonded species, with the bond strength increasing by 0.4 kcal mol-1 upon formation of the (pi,pi*) state and decreasing by 1.0 kcal mol-1 upon formation of the (n,pi*) state. The calculated solvent shifts for the complexes match experimental data and provide a basis for the understanding of the aqueous solvation of pyrazine, and the excited-state complexes are predicted to be only short-lived, explaining the failure of molecular beam experiments to observe them. Quite a different scenario for hydrogen bonding to the (n,pi*) excited state is found compared to those of H2O:pyridine and H2O:pyrimidine: for pyridine linear hydrogen bonds are unstable and hydrogen bonds to the electron-enriched pi cloud are strong, whereas for pyrimidine the excitation localizes on the nonbonded nitrogen leaving the hydrogen-bonding unaffected. For H2O:pyrazine, the (n,pi*) excitation remains largely delocalized, providing a distinct intermediary scenario.
authors.affiliation: School of Chemistry, The University of Sydney, NSW 2006, Australia.
authors.forename: Zheng-Li
authors.initials: ZL
authors.lastname: Cai
authors.forename: Jeffrey R
authors.initials: JR
authors.lastname: Reimers
mesh_terms: D006860:Hydrogen Bonding; D008956:Models, Chemical; D011719:Pyrazines / Q000737:chemistry*; D011789:Quantum Theory; D014867:Water / Q000737:chemistry*
chemical_list: D011719:Pyrazines; D014867:Water