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题名: C-H stretching vibrations of methyl, methylene and methine groups at the vapor/alcohol (n=1-8) interfaces
作者: Lu, R;  Gan, W;  Wu, BH;  Zhang, Z;  Guo, Y;  Wang, HF
刊名: JOURNAL OF PHYSICAL CHEMISTRY B
发表日期: 2005-07-28
DOI: 10.1021/jp051565q
卷: 109, 期:29, 页:14118-14129
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Physical
研究领域[WOS]: Chemistry
英文摘要: In IR and Raman spectral studies, the congestion of the vibrational modes in the C-H stretching region between 2800 and 3000 cm(-1) has complicated spectral assignment, conformational analysis, and structural and dynamics studies, even with quite a few of the simplest molecules. To resolve these issues, polarized spectra measurement on a well aligned sample is generally required. Because the liquid interface is generally ordered and molecularly thin, and sum frequency generation vibrational spectroscopy (SFG-VS) is an intrinsically coherent polarization spectroscopy, SFG-VS can be used for discerning details in vibrational spectra of the interfacial molecules. Here we show that, from systematic molecular symmetry and SFG-VS polarization analysis, a set of polarization selection rules could be developed for explicit assignment of the SFG vibrational spectra of the C-H stretching modes. These polarization selection rules helped assignment of the SFG-VS spectra of vapor/alcohol (n = 1-8) interfaces with unprecedented details. Previous approach on assignment of these spectra relied on IR and Raman spectral assignment, and they were not able to give such detailed assignment of the SFG vibrational spectra. Sometimes inappropriate assignment was made, and consequently misleading conclusions on interfacial structure, conformation and even dynamics were reached. With these polarization rules in addition to knowledge from IR and Raman studies, new structural information and understanding of the molecular interactions at these interfaces were obtained, and some new spectral features for the C-H stretching modes were also identified. Generally speaking, these new features can be applied to IR and Raman spectroscopic studies in the condensed phase. Therefore, the advancement on vibrational spectra assignment may find broad applications in the related fields using IR and Raman as vibrational spectroscopic tools.
关键词[WOS]: SUM-FREQUENCY GENERATION ;  AIR-WATER-INTERFACE ;  POLYSTYRENE/POLY(METHYL METHACRYLATE) BLENDS ;  LIQUID-VAPOR INTERFACE ;  NORMAL-ALKYL CHAINS ;  MOLECULAR-ORIENTATION ;  POLY(METHYL METHACRYLATE) ;  SURFACE-STRUCTURES ;  RAMAN-SPECTRUM ;  2ND-HARMONIC GENERATION
语种: 英语
WOS记录号: WOS:000230698100039
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/139850
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Chinese Acad Sci, Inst Chem, State Key Lab Mol React Dynam, Beijing 100080, Peoples R China
2.Chinese Acad Sci, Grad Sch, Beijing 100864, Peoples R China

Recommended Citation:
Lu, R,Gan, W,Wu, BH,et al. C-H stretching vibrations of methyl, methylene and methine groups at the vapor/alcohol (n=1-8) interfaces[J]. JOURNAL OF PHYSICAL CHEMISTRY B,2005,109(29):14118-14129.
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