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Title: Experimental and Theoretical Study of Azimuth Angle and Polarization Dependences of Sum-Frequency-Generation Vibrational Spectral Features of Uniaxially Aligned Cellulose Crystals

Abstract

Comprehensive interpretation of vibrational sum-frequency-generation (SFG) spectroscopic features of SFG-active nanodomains interspersed in amorphous bulk requires the knowledge of nonlinear susceptibility, χijk(2), of the SFG-active phase as a function of its spatial arrangement in the bulk as well as the polarizations of the probe lights. Our work reports the full analysis of the azimuth angle and polarization dependence of SFG signals from a control sample consisting of uniaxially aligned cellulose Iβ crystals. The χijk(2) terms of cellulose were estimated from quantum mechanics calculations using time-dependent density functional theory (TD-DFT), and a simple structural model was built with truncated glucose dimers. The theoretical azimuth angle and polarization dependences of characteristic CH/CH2 and OH stretch modes of cellulose were compared with the experimentally observed trends. These comparisons revealed that the relative polarity of crystallites within the SFG coherence length, the random quasi phase-matching of polycrystalline domains, and the preferential packing of crystallites in the bulk play important roles governing the spectral features. Compared to that of small molecules, the difference between chiral and achiral responses in SFG spectra is more difficult to confirm because of the inhomogeneous distribution of crystallites in the bulk sample.

Authors:
 [1];  [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Pennsylvania State Univ., University Park, PA (United States)
  2. Fudan Univ., Shanghai (China)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Lignocellulose Structure and Formation (CLSF)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1469823
Grant/Contract Number:  
SC0001090
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 34; Related Information: CLSF partners with Pennsylvania State University (lead); North Carolina State University; University of Rhode Island; Virginia Tech University; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 59 BASIC BIOLOGICAL SCIENCES

Citation Formats

Chen, Xing, Lee, Christopher M., Wang, Hong-Fei, Jensen, Lasse, and Kim, Seong H. Experimental and Theoretical Study of Azimuth Angle and Polarization Dependences of Sum-Frequency-Generation Vibrational Spectral Features of Uniaxially Aligned Cellulose Crystals. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b03037.
Chen, Xing, Lee, Christopher M., Wang, Hong-Fei, Jensen, Lasse, & Kim, Seong H. Experimental and Theoretical Study of Azimuth Angle and Polarization Dependences of Sum-Frequency-Generation Vibrational Spectral Features of Uniaxially Aligned Cellulose Crystals. United States. https://doi.org/10.1021/acs.jpcc.7b03037
Chen, Xing, Lee, Christopher M., Wang, Hong-Fei, Jensen, Lasse, and Kim, Seong H. 2017. "Experimental and Theoretical Study of Azimuth Angle and Polarization Dependences of Sum-Frequency-Generation Vibrational Spectral Features of Uniaxially Aligned Cellulose Crystals". United States. https://doi.org/10.1021/acs.jpcc.7b03037. https://www.osti.gov/servlets/purl/1469823.
@article{osti_1469823,
title = {Experimental and Theoretical Study of Azimuth Angle and Polarization Dependences of Sum-Frequency-Generation Vibrational Spectral Features of Uniaxially Aligned Cellulose Crystals},
author = {Chen, Xing and Lee, Christopher M. and Wang, Hong-Fei and Jensen, Lasse and Kim, Seong H.},
abstractNote = {Comprehensive interpretation of vibrational sum-frequency-generation (SFG) spectroscopic features of SFG-active nanodomains interspersed in amorphous bulk requires the knowledge of nonlinear susceptibility, χijk(2), of the SFG-active phase as a function of its spatial arrangement in the bulk as well as the polarizations of the probe lights. Our work reports the full analysis of the azimuth angle and polarization dependence of SFG signals from a control sample consisting of uniaxially aligned cellulose Iβ crystals. The χijk(2) terms of cellulose were estimated from quantum mechanics calculations using time-dependent density functional theory (TD-DFT), and a simple structural model was built with truncated glucose dimers. The theoretical azimuth angle and polarization dependences of characteristic CH/CH2 and OH stretch modes of cellulose were compared with the experimentally observed trends. These comparisons revealed that the relative polarity of crystallites within the SFG coherence length, the random quasi phase-matching of polycrystalline domains, and the preferential packing of crystallites in the bulk play important roles governing the spectral features. Compared to that of small molecules, the difference between chiral and achiral responses in SFG spectra is more difficult to confirm because of the inhomogeneous distribution of crystallites in the bulk sample.},
doi = {10.1021/acs.jpcc.7b03037},
url = {https://www.osti.gov/biblio/1469823}, journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 34,
volume = 121,
place = {United States},
year = {Fri Aug 04 00:00:00 EDT 2017},
month = {Fri Aug 04 00:00:00 EDT 2017}
}

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Cited by: 15 works
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Works referencing / citing this record:

Probing cellulose structures with vibrational spectroscopy
journal, January 2019