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Issue 9, 2017
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Rotational and steric effects in water dissociative chemisorption on Ni(111)

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Abstract

Powerful laser techniques have recently enabled quantum-state resolved molecular beam experiments for investigating gas-surface reactions, which have unveiled intriguing vibrational, rotational, and also steric effects. For reactions involving polyatomic molecules, e.g., the dissociative chemisorption of methane and water, the rotational and related steric effects are far less understood despite a large body of theoretical work having been able to reproduce the observed vibrational mode specificity and related bond selectivity semi-quantitatively or even within chemical accuracy. Herein, we report a high dimensional quantum dynamics study of water dissociation on Ni(111) on a first-principles potential energy surface, focusing on the reactivities of D2O in various rotational quantum states with different spatial orientations. Through an accurate quantum mechanical description of this asymmetric top, remarkable dependence of the reactivity on the orientation is observed. This dependence is site specific and rotational state specific. These single site rotational and steric effects are partially justified by a sudden model on the basis of the overlap between the rotational wavefunctions and the angular potential near the transition state, but rotational steering also plays a significant role which complicates the dynamics. Although site averaging weakens the influence of initial rotational excitations and leads to minor effects to the reactivity, steric effects are predicted to be observable if the water molecule is selectively excited and aligned by a linearly polarized laser.

Graphical abstract: Rotational and steric effects in water dissociative chemisorption on Ni(111)

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Publication details

The article was received on 14 Jun 2017, accepted on 26 Jul 2017 and first published on 26 Jul 2017


Article type: Edge Article
DOI: 10.1039/C7SC02659E
Citation: Chem. Sci., 2017,8, 6662-6669
  • Open access: Creative Commons BY license
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    Rotational and steric effects in water dissociative chemisorption on Ni(111)

    B. Jiang, Chem. Sci., 2017, 8, 6662
    DOI: 10.1039/C7SC02659E

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