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

Xing Chen, Christopher M. Lee, Hong Fei Wang, Lasse Jensen, Seong H. Kim

Research output: Contribution to journalArticle

8 Citations (Scopus)

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, Xijk(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. This study 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 Xijk(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 observe because of the inhomogeneous distribution of crystallites in the bulk sample.

Original languageEnglish (US)
Pages (from-to)18876-18886
Number of pages11
JournalJournal of Physical Chemistry C
Volume121
Issue number34
DOIs
StatePublished - Aug 31 2017

Fingerprint

Crystallites
cellulose
azimuth
Cellulose
Polarization
Crystals
polarization
crystallites
crystals
Phase matching
Quantum theory
Vibrational spectra
Dimers
Density functional theory
Glucose
Molecules
phase matching
glucose
light beams
quantum mechanics

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

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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, Xijk(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. This study 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 Xijk(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 observe because of the inhomogeneous distribution of crystallites in the bulk sample.",
author = "Xing Chen and Lee, {Christopher M.} and Wang, {Hong Fei} and Lasse Jensen and Kim, {Seong H.}",
year = "2017",
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T1 - Experimental and Theoretical Study of Azimuth Angle and Polarization Dependences of Sum-Frequency-Generation Vibrational Spectral Features of Uniaxially Aligned Cellulose Crystals

AU - Chen, Xing

AU - Lee, Christopher M.

AU - Wang, Hong Fei

AU - Jensen, Lasse

AU - Kim, Seong H.

PY - 2017/8/31

Y1 - 2017/8/31

N2 - Comprehensive interpretation of vibrational sum-frequency-generation (SFG) spectroscopic features of SFG-active nanodomains interspersed in amorphous bulk requires the knowledge of nonlinear susceptibility, Xijk(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. This study 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 Xijk(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 observe because of the inhomogeneous distribution of crystallites in the bulk sample.

AB - Comprehensive interpretation of vibrational sum-frequency-generation (SFG) spectroscopic features of SFG-active nanodomains interspersed in amorphous bulk requires the knowledge of nonlinear susceptibility, Xijk(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. This study 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 Xijk(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 observe because of the inhomogeneous distribution of crystallites in the bulk sample.

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