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Title: Sum frequency generation vibrational spectroscopy (SFG-VS) for complex molecular surfaces and interfaces: Spectral lineshape measurement and analysis plus some controversial issues

Abstract

Sum-frequency generation vibrational spectroscopy (SFG-VS) was first developed in the 1980s and it has been proven a uniquely sensitive and surface/interface selective spectroscopic probe for characterization of the structure, conformation and dynamics of molecular surfaces and interfaces. In recent years, there has been significant progress in the development of methodology and instrumentation in the SFG-VS toolbox that has significantly broadened the application to complex molecular surfaces and interfaces. In this review, after presenting a unified view on the theory and methodology focusing on the SFG-VS spectral lineshape, as well as the new opportunities in SFG-VS applications with such developments, some of the controversial issues that have been puzzling the community are to be discussed. The aim of this review is to present to the researchers and students interested in molecular surfaces and interfacial sciences up-to-date perspectives complementary to the existing textbooks and reviews on SFG-VS.

Authors:
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1339877
Report Number(s):
PNNL-SA-121029
Journal ID: ISSN 0079-6816; 48274
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Progress in Surface Science; Journal Volume: 91; Journal Issue: 4
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Sum-frequency generation vibrational spectroscopy; Surface selectivity; Surface nonlinear spectroscopy; Surfaces and interfaces; Molecular orientation; Dipole contribution; Phase-resolved SFG-VS; Chiral SFG-VS; Environmental Molecular Sciences Laboratory

Citation Formats

Wang, Hong-Fei. Sum frequency generation vibrational spectroscopy (SFG-VS) for complex molecular surfaces and interfaces: Spectral lineshape measurement and analysis plus some controversial issues. United States: N. p., 2016. Web. doi:10.1016/j.progsurf.2016.10.001.
Wang, Hong-Fei. Sum frequency generation vibrational spectroscopy (SFG-VS) for complex molecular surfaces and interfaces: Spectral lineshape measurement and analysis plus some controversial issues. United States. doi:10.1016/j.progsurf.2016.10.001.
Wang, Hong-Fei. 2016. "Sum frequency generation vibrational spectroscopy (SFG-VS) for complex molecular surfaces and interfaces: Spectral lineshape measurement and analysis plus some controversial issues". United States. doi:10.1016/j.progsurf.2016.10.001.
@article{osti_1339877,
title = {Sum frequency generation vibrational spectroscopy (SFG-VS) for complex molecular surfaces and interfaces: Spectral lineshape measurement and analysis plus some controversial issues},
author = {Wang, Hong-Fei},
abstractNote = {Sum-frequency generation vibrational spectroscopy (SFG-VS) was first developed in the 1980s and it has been proven a uniquely sensitive and surface/interface selective spectroscopic probe for characterization of the structure, conformation and dynamics of molecular surfaces and interfaces. In recent years, there has been significant progress in the development of methodology and instrumentation in the SFG-VS toolbox that has significantly broadened the application to complex molecular surfaces and interfaces. In this review, after presenting a unified view on the theory and methodology focusing on the SFG-VS spectral lineshape, as well as the new opportunities in SFG-VS applications with such developments, some of the controversial issues that have been puzzling the community are to be discussed. The aim of this review is to present to the researchers and students interested in molecular surfaces and interfacial sciences up-to-date perspectives complementary to the existing textbooks and reviews on SFG-VS.},
doi = {10.1016/j.progsurf.2016.10.001},
journal = {Progress in Surface Science},
number = 4,
volume = 91,
place = {United States},
year = 2016,
month =
}
  • Sum-frequency generation vibrational spectroscopy (SFG) can provide detailed information and understanding of molecular vibrational spectroscopy, orientational and conformational structure, and interactions of molecular surfaces and interfaces, through quantitative measurement and analysis. In this review, we present the current status and discuss the main developments on the measurement of intrinsic SFG spectral lineshape, formulations for polarization measurement and orientation analysis of the SFG-VS spectra. The main focus is to present a coherent formulation and discuss the main concepts or issues that can help to make SFG-VS a quantitative analytical and research tool in revealing the chemistry and physics of complex molecularmore » surface and interface.« less
  • We report in this work detailed measurements on the chiral and achiral sum-frequency vibrational spectra in the C-H stretching vibration region (2800-3050cm-1) of the air/liquid interfaces of R-limonene and S-limonene, using the recently developed high-resolution broadband sum-frequency generation vibrational spectroscopy (HR-BB-SFG-VS). The achiral SFG spectra of R-limonene and S-limonene, as well as the equal amount (50/50) racemic mixture show that the enantiomers are with the same interfacial orientations. The interference chiral SFG spectra of the limonene enantiomers exhibit spectral signature from chiral response of the Cα-H stretching mode, and spectral signature from prochiral response of the CH2 asymmetric stretching mode,more » respectively. The chiral spectral feature of the Cα-H stretching mode changes sign from R-limonene to S-limonene, and disappears for the 50/50 racemic mixture. While the prochiral spectral feature of the CH2 asymmetric stretching mode is the same for R-limonene and S-limonene, and also surprisingly remains the same for the 50/50 racemic mixture. These results provided detail information in understanding the structure and chirality of molecular interfaces, and demonstrated the sensitivity and potential of SFG-VS as unique spectroscopic tool for chirality characterization and chiral recognition at the molecular interface.« less
  • No abstract prepared.
  • The emergence of sub-wavenumber high-resolution broadband sum-frequency generation vibrational spectroscopy (HR-BBSFG-VS) [Velarde et al., J. Chem. Phys., 2011, 135, 241102] has offered new opportunities in obtaining and understanding the spectral lineshape and temporal effects on the surface vibrational spectroscopy. Particularly, the high accuracy in the HR-BBSFG-VS spectral lineshape measurement provides detailed information on the complex coherent vibrational dynamics through spectral measurement. Here we present a unified formalism of the theoretical and experimental approaches for obtaining the accurate lineshape of the SFG response, and then present a analysis on the higher and lower spectral resolution SFG spectra as well as theirmore » temporal effects of the cholesterol molecules at the air/water interface. With the high spectral resolution and accurate lineshape, it is shown that the parameters from the sub-wavenumber resolution SFG spectra can be used not only to understand but also to quantitatively reproduce the temporal effects in the lower resolution SFG measurement. These not only provide a unified picture in understanding both the frequency-domain and the time-domain SFG response of the complex molecular interface, but also provide novel experimental approaches that can directly measure them.« less