Quantum State-Resolved Energy Transfer Dynamics at Gas-Liquid Interfaces: IR Laser Studies of CO^d2 Scattering from Perfluorinated Liquids

Published

September 1, 2005

Author(s)

B G. Perkins, David Nesbitt

Abstract

An apparatus for detailed study of quantum state resolved inelastic energy transfer dynamics at the gas-liquied interface is described. The approach relies on supersonic jet cooled molecular beams impinging on a continually renewable liquid surface in vacuum, exploiting sub-Doppler high resolution laser absorption methods to probe rotation, vibration and translational, distributions in the scattered flux. First results are presented for skimmed beams of jet cooled CO_2(Tdbeam^15 K) colliding at normal incidence witha liquid perfluoropolyether (PFPE) surface at E_{inc = 11 kvsl/mol, with tunable Pb-salt diode laser direct absorption on the CO}d2 _{3 asymmetric stretch. Measured rotational distributions in both 00}00 and 01^10 vibrational manifolds indicate CO_{2 inelastically scatters from the liquid surface into a clearly non-Boltzmann distribution, indicating non-equilibrium dynamics with average rotational energies in excess of the liquid (T}ds=300 K). Furthermore, high resolution analysis of the absorption profiles reveals Doppler widths correspond to temperatures significantly warmer than T_{s and increase systematically with J rotational state. These rotational and translational distributions can be reconciled with the presence of two distinct collision pathways, (i) a T 300 K component due to trapping-desorption (TD) events, and (ii) a much hotter distribution (T 750 K) due to prompt direct impulsive scattering (IS) from the gas-liquid interface. In constant vibrational populations in the CO}d2 bending mode are inefficiently excited by scattering from the liquid, which is consistent with much slower T-V collisional energy transfer.

Citation

Journal of Physical Chemistry

Volume

109

Pub Type

Journals

Keywords

CO^d2, gas-liquid interface, gas-surface, impulsive scattering, infrared absorption, PFPE, trapping-desorption

Citation

Perkins, B. and Nesbitt, D. (2005), Quantum State-Resolved Energy Transfer Dynamics at Gas-Liquid Interfaces: IR Laser Studies of CO^d2 Scattering from Perfluorinated Liquids, Journal of Physical Chemistry (Accessed October 21, 2025)