<i>In Situ</i>Measurement of Chirality of Molecules and Molecular Assemblies with Surface Nonlinear Spectroscopy

Wang, Hong‐Fei

doi:10.1002/9781118120187.ch14

Cited by 5 publications

(20 citation statements)

References 158 publications

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“…Similar (p + mp)‐(p‐mp) SFG‐VS spectral measurements on R ‐(+)‐ and S ‐(–)‐limonene liquid surfaces were reported previously . In that study, chiral spectral features around ~2880 cm ‐1 and ~2835 cm ‐1 was reported, while a 2920 cm ‐1 chiral spectral feature was barely identifiable.…”

Section: Discussionsupporting

confidence: 87%

“…It is also important to see the differences between the interference chiral spectra in this work and the bulk chiral SFG spectra on the R ‐(+)‐limonene and the S ‐(–)‐limonene bulk liquids by Shen and coworkers . It is clear that the bulk chiral SFG can only observe the isotropic chiral signals . In the isotropic bulk limonene liquid, the bulk chiral and achiral signals were only observed in the transmission geometry, and no bulk chiral signal was observed in the reflection geometry .…”

Section: Discussionmentioning

confidence: 80%

“…However, this chiral CH vibration with the C 1 symmetry still retains much of the C ∞ characteristics since the dipole transition is still closely (even though not completely) direct to the CH axis. Therefore, the β ccc term should still be the dominant achiral term together with smaller β aac and β bbc terms, and other achiral terms of the CH group are expected to be significantly small . Even though β ccc is the dominant achiral term among the chiral CH hyperpolarizability tensors, it is itself achiral and it has no contribution to the macroscopic chiral susceptibility term .…”

Section: Discussionmentioning

confidence: 99%

“…There are seven polarization combinations for the effective susceptibility

χ_{eff}^{(2)}

, among them

{italicχ}_{italicssp}^{()(, 2)}, {italicχ}_{italicsps}^{()(, 2)}, {italicχ}_{italicpss}^{()(, 2)}, and {italicχ}_{italicppp}^{()(, 2)}

terms are achiral terms, while

{italicχ}_{italicpsp}^{()(, 2)}, {italicχ}_{italicspp}^{()(, 2)}, and {italicχ}_{italicpps}^{()(, 2)}

are chiral terms with the tensor elements

χ_{IJK}^{(2)}

( I ≠ J ≠ K) . Thus, the achiral structure of surfaces can be probed by using ssp, sps, pss, and ppp polarization combinations, while surface chirality can be probed by using the psp , spp , and pps polarizations.…”

Section: Methodsmentioning

confidence: 99%

“…Thus, the achiral structure of surfaces can be probed by using ssp, sps, pss, and ppp polarization combinations, while surface chirality can be probed by using the psp , spp , and pps polarizations. Since in many cases the chiral terms are often much smaller than the achiral terms, direct measurement of the chiral term can be experimentally challenging or impossible, not only because the chiral signal can be at or be lower than the experimental noise level, but also because imperfect polarization control may often lead to the leaking of the much larger achiral signal into the chiral polarization measurement and cause false chiral signal . Thus, the following heterodyne, or interference, technique is usually employed to make the chiral SFG measurement …”

Section: Methodsmentioning

confidence: 99%

See 4 more Smart Citations

Intrinsic Chirality and Prochirality at Air/R‐(+)‐ and S‐(–)‐Limonene Interfaces: Spectral Signatures With Interference Chiral Sum‐Frequency Generation Vibrational Spectroscopy

Zhang

Wei

et al. 2014

Chirality

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We report in this work detailed measurements of the chiral and achiral sum-frequency vibrational spectra in the C-H stretching vibration region (2800-3050 cm(-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 RS racemic mixture (50/50 equal amount mixture), show that the corresponding molecular groups of the R and S enantiomers are with the same interfacial orientations. The interference chiral SFG spectra of the limonene enantiomers exhibit a spectral signature from the chiral response of the Cα-H stretching mode, and a spectral signature from the prochiral response of the CH(2) asymmetric stretching mode, respectively. The chiral spectral feature of the Cα-H stretching mode changes sign from R-(+)-limonene to S-(-)-limonene surfaces, and disappears for the RS racemic mixture surface. While the prochiral spectral feature of the CH(2) asymmetric stretching mode is the same for R-(+)-limonene and S-(-)-limonene surfaces, and also surprisingly remains the same for the RS racemic mixture surface. Therefore, the structures of the R-(+)-limonene and the S-(-)-limonene at the liquid interfaces are nevertheless not mirror images to each other, even though the corresponding groups have the same tilt angle from the interfacial normal, i.e., the R-(+)-limonene and the S-(-)-limonene at the surface are diastereomeric instead of enantiomeric. These results provide detailed information in understanding the structure and chirality of molecular interfaces and demonstrate the sensitivity and potential of SFG-VS as a unique spectroscopic tool for chirality characterization and chiral recognition at the molecular interface.

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Section: Discussionsupporting

confidence: 87%

Section: Discussionmentioning

confidence: 80%

Section: Discussionmentioning

confidence: 99%

“…There are seven polarization combinations for the effective susceptibility

χ_{eff}^{(2)}

, among them

{italicχ}_{italicssp}^{()(, 2)}, {italicχ}_{italicsps}^{()(, 2)}, {italicχ}_{italicpss}^{()(, 2)}, and {italicχ}_{italicppp}^{()(, 2)}

terms are achiral terms, while

{italicχ}_{italicpsp}^{()(, 2)}, {italicχ}_{italicspp}^{()(, 2)}, and {italicχ}_{italicpps}^{()(, 2)}

are chiral terms with the tensor elements

χ_{IJK}^{(2)}

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 3 more Smart Citations

Intrinsic Chirality and Prochirality at Air/R‐(+)‐ and S‐(–)‐Limonene Interfaces: Spectral Signatures With Interference Chiral Sum‐Frequency Generation Vibrational Spectroscopy

Zhang

Wei

et al. 2014

Chirality

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

Wang

2016

Progress in Surface Science

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113

127

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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 have been many progresses 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 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.

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Robust Self-Referencing Method for Chiral Sum Frequency Generation Spectroscopy

McDermott

Petersen

2015

J. Phys. Chem. B

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Chiral sum frequency generation spectroscopy (SFG) is of great interest for studying biological systems, among others. Whereas the chiral response in circular dichroism is about 0.1% of the achiral response, the chiral SFG response can be the same order of magnitude as the achiral SFG signal. However, chiral SFG is limited by the attainable signal-to-noise of the weak nonlinear signals and therefore extremely sensitive to proper alignment. We present a robust method for chiral SFG and demonstrate the use on solid-air surfaces with achiral and chiral molecules. We simultaneously measure two orthogonal polarizations-either the interference chiral SFG (±45° polarized) or the pure chiral and achiral SFG-using a waveplate and beam displacer. Both optics are placed in the detection arm and can be easily incorporated into any SFG setup. Furthermore, we employ self-referencing to calibrate alignment for each sample individually using a polarizer in the detection arm. These methods greatly increase the reliability and quality of chiral SFG measurements.

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In SituMeasurement of Chirality of Molecules and Molecular Assemblies with Surface Nonlinear Spectroscopy

Cited by 5 publications

References 158 publications

Intrinsic Chirality and Prochirality at Air/R‐(+)‐ and S‐(–)‐Limonene Interfaces: Spectral Signatures With Interference Chiral Sum‐Frequency Generation Vibrational Spectroscopy

Intrinsic Chirality and Prochirality at Air/R‐(+)‐ and S‐(–)‐Limonene Interfaces: Spectral Signatures With Interference Chiral Sum‐Frequency Generation Vibrational Spectroscopy

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

Robust Self-Referencing Method for Chiral Sum Frequency Generation Spectroscopy

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