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Updated: Aug 3, 2026

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
Published on: August 6, 2018
Collision relaxation cross section of highly vibrationally excited molecules
1Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, USA.
Abstract:
Through quantum-beat spectroscopy collision relaxation of a high vibrational level of SO2 at 44 877.52 cm(-1) is characterized. This is a first measurement of collision relaxation for a single, highly excited vibrational level. The deduced relaxation cross section of this excited level by Ar is 216 A(2), 5 times the area of the hard sphere, and by an ambient temperature SO2 molecule is 969 A(2), almost 20 times the hard sphere. These cross sections indicate that relaxation collisions of highly vibrationally excited molecules have effective distances much longer than van der Waals radii and involve mechanisms qualitatively different from lower excitations.
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