Here we report a detailed study on spectroscopy, structure and dynamics of water molecules at air/water interface, investigated with Sum Frequency Generation Vibrational Spectroscopy (SFGVS). Quantitative polarization and experimental configuration analysis of the SFG data in different polarizations with four sets of experimental configurations can shed new lights on our present understanding of the air/water interface. Firstly, we concluded that the motion of the interfacial water molecules can only be in a limited angular range, instead rapidly varying over a broad angular range in the vibrational relaxation time suggested previously. Secondly, because different vibrational modes of different molecular species at the interface has different symmetry properties, polarization and symmetry analysis of the SFG-VS spectral features can help assignment of the SFG-VS spectra peaks to different interfacial species. These analysis concluded that the narrow 3693cm−1 and broad 3550cm−1 peaks belong to Cv symmetry, while the broad 3250cm−1 and 3450cm−1 peaks belong to the symmetric stretching modes with C2v symmetry. Thus, the 3693cm−1 peak is assigned to the free OH, the 3550cm−1 peak is assigned to the single hydrogen bonded OH stretching mode, and the 3250cm−1 and 3450cm−1 peaks are assigned to interfacial water molecules as two hydrogen donors for hydrogen bonding (with C2v symmetry), respectively. Thirdly, analysis of the SFG-VS spectra concluded that the singly hydrogen bonded water molecules at the air/water interface have their dipole vector direct almost parallel to the interface, and is with a very narrow orientational distribution. The doubly hydrogen bond donor water molecules have their dipole vector point away from the liquid phase. 表面和頻光譜分析系統(tǒng)(SFG) PL2230系列高能量全固態(tài)鎖模皮秒Nd:YAG激光器 Ekspla CARS 相干反斯托克斯拉曼顯微光譜儀