Effect of surface motion on the rotational quadrupole alignment parameter of D 2 reacting on Cu(111)

Ab initio molecular dynamics (AIMD) calculations using the specific reaction parameter approach to density functional theory are presented for the reaction of D2 on Cu(111) at high surface temperature (Ts = 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 experimentC. Díaz gratefully acknowledges support under MICINN project FIS2010-15127 and CAM program NANOBIOMAGNET S2009/MAT1726. B. Jackson gratefully acknowledges support from the Division of Chemical Sciences, Office of Basic Energy Sciences, Office of Energy Research, U. S. Department of Energy, under Grant No. DE-FG02-87ER1374