Issue 26, 2019

Photon catalysis of deuterium iodide photodissociation

Abstract

A catalyst enhances a reaction pathway without itself being consumed or changed. Recently, there has been growing interest in the concept of “photon catalysis” in which nonresonant photons, which are neither absorbed nor scattered, promote reactions. The driving force behind this effect is the interaction between the strong electric field associated with a pulsed, focused laser and the polarizability of the reacting system. In this study, the effect of near-infrared, nonresonant radiation on the photodissociation of deuterium iodide is demonstrated. We use nanosecond pulses rather than time-resolved spectroscopy to investigate the average effect of the electric field on the branching ratio for forming D + I(2P3/2) and D + I(2P1/2). Changes in the measured D-atom speeds between field-free and strong-field conditions confirm substantial differences in dissociation dynamics. Both the magnitude and direction of change in the branching ratios are dependent upon the photodissociation wavelength. Experiments and theoretical calculations confirm that the mechanism for photon catalysis under these conditions is dynamic Stark shifting of potential energy surfaces rather than electric-field-induced alignment of reagent molecules.

Graphical abstract: Photon catalysis of deuterium iodide photodissociation

Supplementary files

Article information

Article type
Paper
Submitted
28 Ndz 2018
Accepted
26 Huk 2018
First published
26 Huk 2018

Phys. Chem. Chem. Phys., 2019,21, 14195-14204

Author version available

Photon catalysis of deuterium iodide photodissociation

K. I. Hilsabeck, J. L. Meiser, M. Sneha, N. Balakrishnan and R. N. Zare, Phys. Chem. Chem. Phys., 2019, 21, 14195 DOI: 10.1039/C8CP06107F

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