Albert Sieghard, Bekhtereva Elena, Bolotova Irina, Chen Ziqiu, Fábri Csaba, Hollenstein Hans, Quack Martin, Ulenikov Oleg
Physical Chemistry, ETH-Zürich, CH-8093, Zürich, Switzerland.
Phys Chem Chem Phys. 2017 Oct 11;19(39):26527-26534. doi: 10.1039/c7cp04762b.
We report a comparison of the analysis of the low energy spectrum of CHF and CHF from the THz (FIR) range to the ν fundamental at high resolution (δ[small nu, Greek, tilde] < 0.001 cm or otherwise Doppler limited) on the basis of FTIR spectra taken both with ordinary light sources and with the synchrotron radiation from the Swiss Light Source. Several vibrational levels are accurately determined including, in particular, the 2ν CH-bending overtone and the ν CH-stretching fundamental of CHF. Comparison of experimental results with those from accurate full dimensional vibrational calculations allows for a study of the time-dependent quantum dynamics of intramolecular vibrational redistribution (IVR) in the CH chromophore both on short time scales (fs) and longer time scales (ps) when coupling to the lower frequency modes becomes important and where the C/C isotope effects are very large.
我们报告了基于使用普通光源和瑞士光源同步辐射所获取的傅里叶变换红外光谱（FTIR），对太赫兹（远红外）波段的CHF和CHF低能谱与高分辨率（δ[小写希腊字母ν，波浪线] < 0.001 cm或其他多普勒极限）下的ν基频进行分析的比较。精确测定了几个振动能级，特别是包括CHF的2ν CH弯曲泛音和ν CH伸缩基频。将实验结果与精确的全维振动计算结果进行比较，能够研究当与低频模式耦合变得重要且C/C同位素效应非常大时，发色团CH中分子内振动再分布（IVR）在短时间尺度（飞秒）和较长时间尺度（皮秒）上的时间相关量子动力学。
