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Updated: Jul 4, 2025

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
Published on: August 6, 2018
Continuous-wave cavity ringdown for high-sensitivity polarimetry and magnetometry measurements.
Dang-Bao-An Tran1, Evan G P Edwards1, David P Tew1
1Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QZ, United Kingdom.
We developed a new cavity ringdown polarimetry technique for precise chiral molecule measurements. This method accurately determines optical rotations in gases and solutions, advancing chiroptical activity analysis.
Area of Science:
- Physical Chemistry
- Spectroscopy
- Analytical Chemistry
Background:
- Chiroptical activity measurements are crucial for understanding molecular structure and interactions.
- Cavity ringdown polarimetry offers high sensitivity but requires advanced methodologies for precise measurements.
- Existing techniques may face limitations in sensitivity or applicability to various phases.
Purpose of the Study:
- To develop a novel continuous-wave laser-based cavity ringdown polarimetry variant.
- To achieve highly precise chiroptical activity and magnetometry measurements.
- To demonstrate the method's capability in evaluating Verdet constants and optical rotations of chiral molecules in different phases.
Main Methods:
- Utilized a continuous-wave laser at 532 nm for cavity ringdown polarimetry.
- Employed external modulation of laser frequency to probe non-degenerate left- and right-circularly polarized cavity modes.
- Applied the technique to measure Verdet constants of CeF3 and fused silica, and optical rotations of gas- and solution-phase chiral molecules.
Main Results:
- Successfully evaluated Verdet constants for crystalline CeF3 and fused silica.
- Determined optical rotations for gas-phase α-pinene and R-(+)-limonene vapors.
- Quantified optical rotations for solution-phase D-glucose and L-histidine, achieving high detection sensitivities.
Conclusions:
- The novel cavity ringdown polarimetry variant enables precise chiroptical activity measurements across different molecular phases.
- The method's sensitivity is suitable for detecting subtle optical rotations in both gaseous and liquid samples.
- Experimental results for R-(+)-limonene optical rotation were rationalized through quantum chemistry computations, validating the technique's accuracy.
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