Effect of Surface Motion on the Rotational Quadrupole Alignment Parameter of ${\mathbf{D}}_{2}$ Reacting on Cu(111)

Effect of Surface Motion on the Rotational Quadrupole Alignment Parameter of $D_{2}$ Reacting on Cu(111)

Francesco Nattino, Cristina Díaz, Bret Jackson, and Geert-Jan Kroes

Phys. Rev. Lett. 108, 236104 – Published 8 June 2012

Abstract

Ab initio molecular dynamics (AIMD) calculations using the specific reaction parameter approach to density functional theory are presented for the reaction of $D_{2}$ on Cu(111) at high surface temperature ( $T_{s} = 925 K$ ). The focus is on the dependence of reaction on the alignment of the molecule’s angular momentum relative to the surface. For the two rovibrational states for which measured energy resolved rotational quadrupole alignment parameters are available, and for the energies for which statistically accurate rotational quadrupole alignment parameters could be computed, statistically significant results of our AIMD calculations are that, on average, (i) including the effect of the experimental surface temperature (925 K) in the AIMD simulations leads to decreased rotational quadrupole alignment parameters, and (ii) including this effect leads to increased agreement with experiment.

Received 2 February 2012

DOI:https://doi.org/10.1103/PhysRevLett.108.236104

Authors & Affiliations

Francesco Nattino¹, Cristina Díaz², Bret Jackson³, and Geert-Jan Kroes¹

¹Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands
²Departamento de Química Módulo 13, Universidad Autónoma de Madrid, 28049 Madrid, Spain
³Department of Chemistry, University of Massachusetts, Amherst, Massachusetts 01003, USA