%0 Journal Article %1 moore2006kinetic %A Moore, Nelly A %A Mitric, Roland %A Justes, Dina R %A Bonacic-Koutecky, Vlasta %A Castleman Jr., A W %D 2006 %I American Chemical Society %J Journal of Physical Chemistry B %K cation cluster ethylene kinetics mechanism vanadia %N 7 %P 3015--3022 %R 10.1021/jp055652u %T Kinetic Analysis of the Reaction between (V2O5)n=1,2+ and Ethylene. %V 110 %X A systematic exptl. and theor. investigation of the influence of reactant energy on the reactivity of (V2O5)n=1,2+ clusters with ethylene (Justes, D. R.; Mitric, R.; Moore, N. A.; Bonacic-Koutecky, V.; Castleman, A. W. Jr. J. Am. Chem. Soc., 2003, 125, 6289)1 provided evidence of the rate controlling steps in the reaction. Herein, we present further exptl. and theor. evidence for our recently proposed radical cation mechanism for oxygen atom transfer from (V2O5)n=1,2+ clusters to ethylene. In particular the results of ab initio mol. dynamics simulations are found to further support the radical cation mechanism. Exptl. reaction cross sections at the zero pressure limit and rate coeffs. show that the energy dependence of the reaction cross section is in accord with the Langevin formula. Evidence is presented that ion-mol. assocn. is the rate detg. step, whereas subsequent hydrogen transfer and formation of acetaldehyde proceed without significant barriers. We propose a kinetic model for the reaction cross section that fully accounts for the exptl. findings. The model offers the prospect of elucidating the details of the general reaction mechanisms through a study of the energy dependence of the reaction cross sections. on SciFinder(R)

@article{moore2006kinetic, abstract = {A systematic exptl. and theor. investigation of the influence of reactant energy on the reactivity of (V2O5)n=1,2+ clusters with ethylene (Justes, D. R.; Mitric, R.; Moore, N. A.; Bonacic-Koutecky, V.; Castleman, A. W. Jr. J. Am. Chem. Soc., 2003, 125, 6289)1 provided evidence of the rate controlling steps in the reaction. Herein, we present further exptl. and theor. evidence for our recently proposed radical cation mechanism for oxygen atom transfer from (V2O5)n=1,2+ clusters to ethylene. In particular the results of ab initio mol. dynamics simulations are found to further support the radical cation mechanism. Exptl. reaction cross sections at the zero pressure limit and rate coeffs. show that the energy dependence of the reaction cross section is in accord with the Langevin formula. Evidence is presented that ion-mol. assocn. is the rate detg. step, whereas subsequent hydrogen transfer and formation of acetaldehyde proceed without significant barriers. We propose a kinetic model for the reaction cross section that fully accounts for the exptl. findings. The model offers the prospect of elucidating the details of the general reaction mechanisms through a study of the energy dependence of the reaction cross sections. [on SciFinder(R)]}, added-at = {2018-04-13T09:37:37.000+0200}, author = {Moore, Nelly A and Mitric, Roland and Justes, Dina R and Bonacic-Koutecky, Vlasta and {Castleman Jr.}, A W}, biburl = {https://www.bibsonomy.org/bibtex/260f0055ed2b8a9c2f3e2c75a98c24efd/jhoche}, doi = {10.1021/jp055652u}, interhash = {587b15e2eb444ff7edd72095ca144462}, intrahash = {60f0055ed2b8a9c2f3e2c75a98c24efd}, issn = {1520-6106}, journal = {Journal of Physical Chemistry B}, keywords = {cation cluster ethylene kinetics mechanism vanadia}, number = 7, pages = {3015--3022}, publisher = {American Chemical Society}, pubstate = {published}, timestamp = {2019-03-25T17:38:38.000+0100}, title = {Kinetic Analysis of the Reaction between (V2O5)n=1,2+ and Ethylene.}, tppubtype = {article}, volume = 110, year = 2006 }