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Organic compounds with conjugated double bonds show strong absorption features in the UV–visible region of the electromagnetic spectrum attributed to π → π* electronic excitations. Generally, a UV–vis absorption spectrum is recorded as a plot of absorbance vs wavelength. The wavelength of maximum absorbance, which manifests as a peak in the absorption spectrum, is denoted as λmax.
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Conformer-Selective Photoelectron Circular Dichroism.

Etienne Rouquet1,2, Jennifer Dupont1, Valeria Lepere1

  • 1Institut des Sciences Moléculaires d'Orsay (ISMO), CNRS, Université Paris-Saclay, F-91405, Orsay, France.

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|March 5, 2024
PubMed
Summary
This summary is machine-generated.

Photoelectron circular dichroism (PECD) now distinguishes molecular conformers. This new method reveals distinct PECD signals for axial and equatorial forms of chiral 1-indanol, advancing molecular recognition studies.

Keywords:
ChiralityConformer-specific spectroscopyPhotoelectron Circular DichroismPhotoionizationVelocity Map Imaging

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Area of Science:

  • Physical Chemistry
  • Spectroscopy
  • Chiroptical Methods

Background:

  • Molecular recognition relies on conformational flexibility and chirality.
  • Photoelectron circular dichroism (PECD) is theoretically sensitive to conformational isomerism.
  • Experimental validation of PECD for conformer-selectivity has been limited.

Purpose of the Study:

  • Develop a novel PECD scheme for simultaneous probing of molecular conformation and chirality.
  • Demonstrate conformer-selective PECD using resonance-enhanced two-photon ionization (RE2PI).
  • Investigate the PECD of chiral 1-indanol conformers.

Main Methods:

  • Implemented a new PECD scheme utilizing UV/Vis nanosecond laser excitations.
  • Employed resonance-enhanced two-photon ionization (RE2PI) for conformer-specific ππ* S1←S0 transitions.
  • Studied chiral 1-indanol, analyzing axial and equatorial conformers.

Main Results:

  • Achieved high spectral resolution for conformer-selective PECD.
  • Observed significant differences in PECD sign, magnitude, and shape between 1-indanol conformers.
  • Analyzed the impact of ionization energy and laser polarization on PECD.

Conclusions:

  • The developed RE2PI-based PECD method successfully distinguishes between axial and equatorial conformers of 1-indanol.
  • Conformer-specificity in PECD opens new avenues for analytical chemistry, particularly for flexible molecules.
  • This technique enhances the application of PECD in studying complex molecular systems.