TY - JOUR
T1 - Comparison of molecular dynamics and variational transition-state-theory calculations of the rate constant for H-atom association with the diamond {111} surface
AU - Song, Kihyung
AU - De Sainte Claire, Pascal
AU - Hase, William L.
AU - Hass, Kenneth C.
PY - 1995
Y1 - 1995
N2 - The quasiclassical trajectory method was used to study the dynamics and kinetics of H-atom association with a C-atom radical site on the diamond {111} surface. The calculations employed an analytic potential-energy surface derived previously [P. de Sainte Claire, P. Barbarat, and W. L. Hase, J. Chem. Phys. 101, 2476 (1994)] from high-level ab initio calculations. The trajectory rate constant calculated here of 1.70.3×1013 cm3 mol-1 s-1 for temperatures of 1000 and 2000 K is in excellent agreement with the one calculated previously on the same analytic potential-energy surface using canonical variational transition-state theory. For H atoms impinging perpendicularly and directly onto the C-atom radical site, the association probability is sensitive to the frequencies of the diamond lattice and the treatment of the lattices zero-point energy. However, trajectories with this orientation make a negligible contribution to the thermal rate constant, which is found to be nearly insensitive to the lattice frequencies and zero-point energy. Trajectories, for which H atoms move toward the surface with a small angle relative to the surface plane and pass above the C-atom radical site before associating, make an important contribution to the association rate constant.
AB - The quasiclassical trajectory method was used to study the dynamics and kinetics of H-atom association with a C-atom radical site on the diamond {111} surface. The calculations employed an analytic potential-energy surface derived previously [P. de Sainte Claire, P. Barbarat, and W. L. Hase, J. Chem. Phys. 101, 2476 (1994)] from high-level ab initio calculations. The trajectory rate constant calculated here of 1.70.3×1013 cm3 mol-1 s-1 for temperatures of 1000 and 2000 K is in excellent agreement with the one calculated previously on the same analytic potential-energy surface using canonical variational transition-state theory. For H atoms impinging perpendicularly and directly onto the C-atom radical site, the association probability is sensitive to the frequencies of the diamond lattice and the treatment of the lattices zero-point energy. However, trajectories with this orientation make a negligible contribution to the thermal rate constant, which is found to be nearly insensitive to the lattice frequencies and zero-point energy. Trajectories, for which H atoms move toward the surface with a small angle relative to the surface plane and pass above the C-atom radical site before associating, make an important contribution to the association rate constant.
UR - http://www.scopus.com/inward/record.url?scp=0000140258&partnerID=8YFLogxK
U2 - 10.1103/PhysRevB.52.2949
DO - 10.1103/PhysRevB.52.2949
M3 - Review article
AN - SCOPUS:0000140258
VL - 52
SP - 2949
EP - 2958
JO - Physical Review B
JF - Physical Review B
SN - 0163-1829
IS - 4
ER -