Journal of the American Chemical Society, Vol.117, No.33, 8618-8626, 1995
Solvent Effects on Molecular and Ionic Spectra .6. Hydrogen-Bonding and the Delocalized Nature of the First (1)(N,Pi-Asterisk) Excited-State of Pyrazine
Our method (Parts 1-5(1-6)) for estimating solvent shifts of species which have strong specific interactions (e.g., hydrogen bonding) with the solvent is applied to calculate the absorption and fluorescence solvatochromic (solvent) shifts of dilute pyrazine in water. On the basis of interpretation of solvent shift data, pyrazine in its S-1 (1)(n,pi*) excited state has been thought to display reduced nuclear symmetry, with the excitation localized on just one of the two nitrogen atoms; this view has also been supported by electronic structure calculations. Such localization could occur, despite the presence of significant through-bond interactions between the nitrogen lone pairs, if the reorganization energy associated with symmetry breaking were sufficiently large. Here, the alternate description is developed for the electronic structure of this excited state of pyrazine based on studies of the free molecule, of pyrazine-water clusters, and of pyrazine in dilute aqueous solution. For the free molecule, extensive ab initio Davidson-corrected CASSCF with MRCI calculations strongly suggest a high-symmetry geometry, and verify that this is the correct interpretation of the available experiment data. For pyrazine-water clusters, only a high-symmetry model is shown capable of describing the observed high-resolution spectra, and for pyrazine in solution, only a high-symmetry model is shown to be capable of interpreting the observed fluorescence solvent shift.
Keywords:MONTE-CARLO SIMULATIONS;N-PI TRANSITIONS;ELECTRONIC-SPECTRA;AZABENZENE MOLECULES;POTENTIAL FUNCTIONS;ABSORPTION-SPECTRA;TRIPLET ABSORPTION;DILUTE PYRIMIDINE;REACTION FIELD;NUCLEIC-ACIDS