Vibrational spectroscopy and dynamics of the hydrazoic and isothiocyanic acids in water and methanol.
Small anions in polar solvents are benchmark systems for fast vibrational energy relaxation (VER) due to the Coulombic effects that promote solute-solvent interactions. In order to investigate the effects of solute charge and solvent isotope effects on vibrational spectra and dynamics, infrared pump-probe studies have been used to determine VER (T(1)) times for the pseudohalide acids, XNCS and XN(3) (X = H, D), in protic solvents, H(2)O, D(2)O, CH(3)OH, and CD(3)OD. These results are compared with the well-studied azide and thiocyanate anions. Solvent isotope effects of the vibrational frequency shifts of azide and for VER rates of both azide and thiocyanate are similar to those for the hydro- and deutero-protonated species in water. VER times are longer for HN(3)/H(2)O, HN(3)/CH(3)OH, and DN(3)/CD(3)OD (T(1) = 2.3, 5.6, and 3.7 ps, respectively) than for the corresponding anions in solution (0.8, 3.0, and 2.1 ps), which is consistent with the idea that ions relax more quickly than neutrals. But the times measured for DN(3)/D(2)O, HNCS/H(2)O, and DNCS/D(2)O (T(1) = 1.2, 1.5, and 4.4 ps, respectively) are shorter than for the corresponding ions (2.3, 2.7, and 22.0 ps). Fast VER for DN(3) in D(2)O is attributed to strong coupling to nearby solvent bands and/or to Fermi resonances that promote intramolecular vibrational relaxation. For the HNCS and DNCS, the faster rates can be understood by recognizing that the charge displacements are similar to those for the anion.
Houchins
Cassidy
C
Chemistry Division, Code 6111, U.S. Naval Research Laboratory, Washington, DC 20375-5342, USA.
Weidinger
Daniel
D
Owrutsky
Jeffrey C
JC