We present a comparative study on the C-H stretching vibrations at air/DMSO （dimethyl sulfoxide） interface with both the free-induction decay （FID） coherent vibrational dynamics and the sub-wavenumber high resolut...We present a comparative study on the C-H stretching vibrations at air/DMSO （dimethyl sulfoxide） interface with both the free-induction decay （FID） coherent vibrational dynamics and the sub-wavenumber high resolution sum-frequency generation vibrational spectroscopy measurements. In principle the frequency-domain and time-domain spectroscopic measurements should generate identical information for a given molecular system. However, when the molecular systems are with several coupled or overlapping vibrational modes, obtain- ing detailed spectroscopic and coherent dynamics information is not as straightforward and rather difficult from either the time-domain or the frequency domain measurements. For the case of air/DMSO interface that is with moderately complex vibrational spectra, we show that the frequency-domain measurement with sub-wavenumber high-resolution sum-frequency generation vibrational spectroscopy is probably more advantageous than the time- domain measurement in obtaining quantitative understanding of the structure and coherent dynamics of the molecular interface.展开更多
The effect of pH on the conformation of surface alkyl groups and the structure of interfacial water molecules on poly[2-(dime-thylamino)ethyl methacrylate](PDEM) at the air/water interface were investigated with sum f...The effect of pH on the conformation of surface alkyl groups and the structure of interfacial water molecules on poly[2-(dime-thylamino)ethyl methacrylate](PDEM) at the air/water interface were investigated with sum frequency generation vibrational spectroscopy(SFG-VS).At pH 4.1,the hydrogen bonding SFG spectra were similar to that of the air/pure water interface.As the pH increased from 5.4 to 9.6,the SFG intensities of both highly ordered hydrogen bonding(3200 cm-1 band) and less-ordered hydrogen bonding(3400 cm-1 band) were enhanced because of the charge-induced effect of deprotonated PDEM.The free OH peak disappeared completely because it was replaced by interfacial PDEM molecules.At pH 11.5,a new spectral band appeared at about 3580 cm-1 in the ppp and sps spectra,and this could be assigned to the C2v asymmetric stretching mode of the water molecules through molecular symmetry simulation.These hydrogen bonding structures are fully consistent with the conformational change of PDEM alkyl groups,and PDEM molecules act as a Hofmeister solvent.PDEM molecules are kosmotropic when they are charged and become more chaotropic as the pH increases.展开更多
文摘We present a comparative study on the C-H stretching vibrations at air/DMSO （dimethyl sulfoxide） interface with both the free-induction decay （FID） coherent vibrational dynamics and the sub-wavenumber high resolution sum-frequency generation vibrational spectroscopy measurements. In principle the frequency-domain and time-domain spectroscopic measurements should generate identical information for a given molecular system. However, when the molecular systems are with several coupled or overlapping vibrational modes, obtain- ing detailed spectroscopic and coherent dynamics information is not as straightforward and rather difficult from either the time-domain or the frequency domain measurements. For the case of air/DMSO interface that is with moderately complex vibrational spectra, we show that the frequency-domain measurement with sub-wavenumber high-resolution sum-frequency generation vibrational spectroscopy is probably more advantageous than the time- domain measurement in obtaining quantitative understanding of the structure and coherent dynamics of the molecular interface.
基金supported by the Main Direction Program of Knowledge Innovation of Chinese Academy of Sciences (KJCX-EW-W09)the National Natural Science Foundation of China (91027042,21073199)
文摘The effect of pH on the conformation of surface alkyl groups and the structure of interfacial water molecules on poly[2-(dime-thylamino)ethyl methacrylate](PDEM) at the air/water interface were investigated with sum frequency generation vibrational spectroscopy(SFG-VS).At pH 4.1,the hydrogen bonding SFG spectra were similar to that of the air/pure water interface.As the pH increased from 5.4 to 9.6,the SFG intensities of both highly ordered hydrogen bonding(3200 cm-1 band) and less-ordered hydrogen bonding(3400 cm-1 band) were enhanced because of the charge-induced effect of deprotonated PDEM.The free OH peak disappeared completely because it was replaced by interfacial PDEM molecules.At pH 11.5,a new spectral band appeared at about 3580 cm-1 in the ppp and sps spectra,and this could be assigned to the C2v asymmetric stretching mode of the water molecules through molecular symmetry simulation.These hydrogen bonding structures are fully consistent with the conformational change of PDEM alkyl groups,and PDEM molecules act as a Hofmeister solvent.PDEM molecules are kosmotropic when they are charged and become more chaotropic as the pH increases.
