Reactivity of the 4d transition metals toward N hydrogenation and NH dissociation: a DFT-based HSAB analysis

The Journal of Physical Chemistry. B
Paul Crawford, P Hu

Abstract

The density functional theory (DFT) based hard-soft acid-base (HSAB) reactivity indices, including the electrophilicity index, have been successfully applied to many areas of molecular chemistry. In this work we test the applicability of such an approach to fundamental surface chemistry. We have considered, as prototypical surface reactions, both the hydrogenation of atomic nitrogen and the dissociative adsorption of the NH molecular radical. By use of a DFT methodology, the minimum energy reaction pathways, and corresponding reaction barriers, of the above reactions over Zr(001), Nb(110), Mo(110), Tc(001), Ru(001), Rh(111), and Pd(111) have been determined. By consideration of the chemical potential and chemical hardness of the surface metal atoms, and the principle of electronegativity equalization, it is found that the charge transferred to the NH radical during the process of dissociative adsorption correlates very well with that determined by Mulliken population analysis. Furthermore, it is found that the stability of the NH/surface transition state complex relates directly to this charge transfer and that the trend in transition state stability predicted by a HSAB treatment correlates very strongly with that determined by...Continue Reading

References

Sep 30, 1998·Proceedings of the National Academy of Sciences of the United States of America·A T MaynardD G Covell
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Jul 30, 2002·Physical Review Letters·B L M Hendriksen, J W M Frenken
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Jan 11, 2005·The Journal of Chemical Physics·Xue-Qing GongP Hu
Jul 13, 2006·The Journal of Physical Chemistry. a·Julianna OláhPaul Geerlings

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Citations

Mar 28, 2013·Journal of Molecular Modeling·Leonardo Moreira da CostaJosé Walkimar de M Carneiro
Nov 15, 2011·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Anton KokaljIngrid Milošev
May 5, 2011·Chemistry : a European Journal·Tomoya IshizukaTakahiko Kojima
Mar 16, 2011·Physical Chemistry Chemical Physics : PCCP·Emmet J O'ReillyRobert J Forster

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