Role of weakly bound complexes in temperature-dependence and relative rates of MxOy– + H2O (M = Mo, W) reactions

Kafader, Jared O.; Ray, Manisha; Raghavachari, Krishnan; Jarrold, Caroline Chick

doi:10.1063/1.4941829

Role of weakly bound complexes in temperature-dependence and relative rates of M_xO_y^– + H₂O (M = Mo, W) reactions

Journal Article · Thu Feb 18 00:00:00 EST 2016 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4941829· OSTI ID:1469677

Kafader, Jared O. ^[1]; ^[2]; Raghavachari, Krishnan ^[2]; Jarrold, Caroline Chick ^[2]

Indiana Univ., Bloomington, IN (United States); Indiana Univ., Bloomington, IN (United States)
Indiana Univ., Bloomington, IN (United States)

Results of a systematic comparison of the Mo_xO_y^– + H₂O and W_xO_y^– + H₂O reaction rate coefficients are reported and compared to previous experimental and computational studies on these reactions. W_xO_y^– clusters undergo more direct oxidation by water to yield W_xO_y+1^– + H₂, while for Mo_xO_y^– clusters, production of Mo_xO_yH₂^– (trapped intermediates in the oxidation reaction) is comparatively more prevalent. However, Mo_xO_y^– clusters generally have higher rate coefficients than analogous W_xO_y^– clusters if Mo_xO_y+1H₂^– formation is included. Results of calculations on the M₂O_y^– + H₂O (M = Mo, W; y = 4, 5) reaction entrance channel are reported. They include charge-dipole complexes formed from long-range interactions, and the requisite conversion to a Lewis acid-base complex that leads to M_xO_y+1H₂^– formation. The results predict that the Lewis acid-base complex is more strongly bound for Mo_xO_y^– clusters than for W_xO_y^– clusters. The calculated free energies along this portion of the reaction path are also consistent with the modest anti-Arrhenius temperature dependence measured for most Mo_xO_y^– + H₂O reactions, and the W_xO_y^– + H₂O reaction rate coefficients generally being constant over the temperature range sampled in this study. For clusters that exhibit evidence of both water addition and oxidation reactions, increasing the temperature increases the branching ratio toward oxidation for both species. In conclusion, a more direct reaction path to H₂ production may therefore become accessible at modest temperatures for certain cluster stoichiometries and structures.

View Accepted Manuscript (DOE)

Research Organization:: Indiana Univ., Bloomington, IN (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: FG02-07ER15889

OSTI ID:: 1469677

Alternate ID(s):: OSTI ID: 1238389

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 7 Vol. 144; ISSN JCPSA6; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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