{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,12,8]],"date-time":"2025-12-08T22:12:42Z","timestamp":1765231962049,"version":"3.41.2"},"reference-count":45,"publisher":"AIP Publishing","issue":"13","content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2011,10,7]]},"abstract":"<jats:p>Reaction probabilities as a function of total angular momentum (opacity functions) and the resulting reaction cross sections for the collision of open shell S(1D) atoms with para-hydrogen have been calculated in the kinetic energy range 0.09\u201310 meV (1\u2013120 K). The quantum mechanical hyperspherical reactive scattering method and quasi-classical trajectory and statistical quasi-classical trajectory approaches were used. Two different ab initio potential energy surfaces (PESs) have been considered. The widely used reproducing kernel Hilbert space (RKHS) PES by Ho et al. [T.-S. Ho, T. Hollebeek, H. Rabitz, S. D. Chao, R. T. Skodje, A. S. Zyubin, and A. M. Mebel, J. Chem. Phys\u2008116, 4124 (2002)]10.1063\/1.1431280 and the recently published accurate double many-body expansion (DMBE)\/complete basis set (CBS) PES by Song and Varandas [Y. Z. Song and A. J. C. Varandas, J. Chem. Phys.\u2008130, 134317 (2009)]10.1063\/1.3103268. The calculations at low collision energies reveal very different dynamical behaviors on the two PESs. The reactivity on the RKHS PES is found to be considerably larger than that on the DMBE\/CBS PES as a result of larger reaction probabilities at low total (here also orbital) angular momentum values and to opacity functions which extend to significantly larger total angular momentum values. The observed differences have their origin in two major distinct topographic features. Although both PESs are essentially barrierless for equilibrium H\u2013H distances, when the H\u2013H bond is compressed the DMBE\/CBS PES gives rise to a dynamical barrier which limits the reactivity of the system. This barrier is completely absent in the RHKS PES. In addition, the latter PES exhibits a van der Walls well in the entrance channel which reduces the height of the centrifugal barrier and is able to support resonances. As a result, a significant larger cross section is found on this PES, with marked oscillations attributable to shape resonances and\/or to the opening of partial wave contributions. The comparison of the results on both PESs is illustrative of the wealth of the dynamics at low collision energy. It is also illuminating about the difficulties encountered in modeling an all-purpose global potential energy surface.<\/jats:p>","DOI":"10.1063\/1.3644337","type":"journal-article","created":{"date-parts":[[2011,10,6]],"date-time":"2011-10-06T15:57:48Z","timestamp":1317916668000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":30,"title":["On the role of dynamical barriers in barrierless reactions at low energies: S(1<i>D<\/i>) + H2"],"prefix":"10.1063","volume":"135","author":[{"given":"Manuel","family":"Lara","sequence":"first","affiliation":[{"name":"Universidad Complutense 1 Departamento de Qu\u00edmica F\u00edsica, Facultad de Qu\u00edmica, , 28040 Madrid, Spain"},{"name":"Universit\u00e9 de Rennes I 2 Institut de Physique de Rennes, UMR CNRS 6251, , F-35042 Rennes, France"}]},{"given":"P. G.","family":"Jambrina","sequence":"additional","affiliation":[{"name":"Universidad Complutense 1 Departamento de Qu\u00edmica F\u00edsica, Facultad de Qu\u00edmica, , 28040 Madrid, Spain"},{"name":"Universidad de Salamanca 3 Grupo de Din\u00e1mica Molecular Departamento de Qu\u00edmica F\u00edsica, , 37008 Salamanca, Spain"}]},{"given":"A. J. C.","family":"Varandas","sequence":"additional","affiliation":[{"name":"Universidade de Coimbra 4 Departamento de Qu\u00edmica, , 3004-535 Coimbra, Portugal"}]},{"given":"J.-M.","family":"Launay","sequence":"additional","affiliation":[{"name":"Universit\u00e9 de Rennes I 2 Institut de Physique de Rennes, UMR CNRS 6251, , F-35042 Rennes, France"}]},{"given":"F. J.","family":"Aoiz","sequence":"additional","affiliation":[{"name":"Universidad Complutense 1 Departamento de Qu\u00edmica F\u00edsica, Facultad de Qu\u00edmica, , 28040 Madrid, Spain"}]}],"member":"317","published-online":{"date-parts":[[2011,10,6]]},"reference":[{"volume-title":"Low Temperatures and Cold Molecules","year":"2008","key":"2023062606104573400_c1"},{"key":"2023062606104573400_c2","doi-asserted-by":"publisher","first-page":"203201","DOI":"10.1103\/PhysRevLett.105.203201","volume":"105","year":"2010","journal-title":"Phys. Rev. Lett."},{"key":"2023062606104573400_c3","doi-asserted-by":"publisher","first-page":"8127","DOI":"10.1039\/c0cp02705g","volume":"13","year":"2011","journal-title":"Phys. Chem. Chem. Phys."},{"key":"2023062606104573400_c4"},{"key":"2023062606104573400_c5","doi-asserted-by":"publisher","first-page":"255","DOI":"10.1002\/SERIES2007","volume":"74","year":"1988","journal-title":"Adv. Chem. 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