期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 108, 期 42, 页码 9054-9063出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp048545t
关键词
-
Ultrafast nonlinear vibrational spectroscopy with mid-IR pumping and incoherent anti-Stokes Raman probing is used to study v = 1 excitations of OH stretching (v(OH)) of water and of HOD in D2O solvent (HOD/D2O). The parent v(OH) decay and the appearance of daughter stretching and bending excitations are simultaneously monitored, which allows for characterization of the stretch decay pathways. At all times and with all pump frequencies within the v(OH) band, the excited-state spectrum can be fit by two overlapping subbands, a broader red-shifted band v(OH)(R) and a narrower blue-shifted band v(OH)(B) We show these subbands are dynamically distinguishable. They decay with different lifetimes and evidence characteristically different decay pathways. Excitations of the v(OH)(R) subband generate bending vibrations that v(OH)(B) does not. The shorter lifetime (similar to0.5 ps) of the v(OH)(R) subband compared to the v(OH)(B) subband (0.8-0.9 ps) results primarily from enhanced stretch-to-bend anharmonic coupling. The subbands represent persistent structures in the excited state, in that interconversion between subbands (2-10 ps) is slower than excited-state decay. A tentative structural interpretation is proposed. The v(OH)(R) subband, on the basis of simulations, its red shift and its shorter lifetime, is proposed to result from strongly hydrogen-bonded ice-like water. The v(OH)(R) subband has a smaller amplitude in HOD/D2O than in water, possibly because HOD has a single localized OH-stretching vibration whereas water has two delocalized stretching vibrations.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据