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Updated: Jul 31, 2026

Spatial Separation of Molecular Conformers and Clusters
Published on: January 9, 2014
Orientational dynamics of hydrogen-bonded phenol
Y L A Rezus1, D Madsen, H J Bakker
1FOM-institute for Atomic and Molecular Physics, Kruislaan 407, 1098 SJ Amsterdam, The Netherlands. rezus@amolf.nl
Hydrogen bonding significantly alters molecular reorientation dynamics. Femtosecond spectroscopy reveals that acetone-bound phenol-d exhibits frequency-dependent orientational changes, unlike free phenol-d.
Area of Science:
- Physical Chemistry
- Spectroscopy
- Molecular Dynamics
Background:
- Hydrogen bonding plays a crucial role in chemical and biological processes.
- Understanding molecular reorientation dynamics is key to elucidating reaction mechanisms and material properties.
Purpose of the Study:
- To investigate the influence of hydrogen bonding on the orientational dynamics of the OD-stretch vibration in phenol-d.
- To compare the reorientation dynamics of phenol-d in chloroform with phenol-d hydrogen-bonded to acetone.
Main Methods:
- Femtosecond mid-infrared pump-probe spectroscopy was employed.
- Two distinct sample systems were analyzed: phenol-d in chloroform and phenol-d with excess acetone in chloroform.
Main Results:
- Phenol-d in chloroform showed rotational diffusion of the OD group around the CO bond with a correlation time of 3.7 ps.
- Phenol-d hydrogen-bonded to acetone exhibited frequency-dependent reorientation times, ranging from 3 ps (blue side) to over 30 ps (red side).
Conclusions:
- Hydrogen bonding to acetone dramatically slows and frequency-modulates the orientational dynamics of the OD-stretch vibration in phenol-d.
- The observed spectral dependence highlights the complex interactions and energy landscape changes induced by hydrogen bonding.
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