用傅立叶变换激光腔内吸收光谱方法研究分子高振动态

A novel high-resolution and high-sensitive Fourier-transform intra-cavity laser absorption spectroscopy technique was introduced. For some molecules like deuterated water, which is of both fundamental and applied interests, many infrared absorption bands were recorded and analyzed. Most of these spectroscopy data are obtained for the first time. The intra-molecule interactions and the characters of local mode vibrations were investigated, what can be important references to realize bond-selective chemistry utilizing local-mode vibrations. By the means of ab initio calculations, the dipole moment surfaces (DMS) of some molecules were calculated and the DMS models were developed. Together with the result from the potential energy surfaces analysis, the prediction of IR band intensities was obtained which interpreted some 'abnormal' experimental results. We pointed out that the nonlinearity and cross interactions of the bond dipoles are important for the first time, and those terms what have been neglected in literatures are really the key to such 'abnormal' results.

发展和完善高分辨高灵敏度的傅立叶变换激光腔内吸收光谱技术，并用于观测卤代甲烷和卤代乙炔类型分子高振动态光谱的能级和强度，以便研究这类分子中M—H键的局域模振动及其与相邻的近共振能级的耦合，从而为下一步对这类分子实现“选键化学”作好准备。