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Photon catalysis of deuterium iodide photodissociation

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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

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Publication details

The article was received on 28 Sep 2018, accepted on 26 Nov 2018 and first published on 26 Nov 2018


Article type: Paper
DOI: 10.1039/C8CP06107F
Citation: Phys. Chem. Chem. Phys., 2019, Advance Article
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    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, Advance Article , DOI: 10.1039/C8CP06107F

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