Six-dimensional quantum dynamics study for the dissociative adsorption of HCl on Au(111) surface

Abstract

The six-dimensional quantum dynamics calculations for the dissociative chemisorption of HCl on Au(111) are carried out using the time-dependent wave-packet approach, based on an accurate PES which was recently developed by neural network fitting to density functional theory energy points. The influence of vibrational excitation and rotational orientation of HCl on the reactivity is investigated by calculating the exact six-dimensional dissociation probabilities, as well as the four-dimensional fixed-site dissociation probabilities. The vibrational excitation of HCl enhances the reactivity and the helicopter orientation yields higher dissociation probability than the cartwheel orientation. A new interesting site-averaged effect is found for the title molecule-surface system that one can essentially reproduce the six-dimensional dissociation probability by averaging the four-dimensional dissociation probabilities over 25 fixed sites. © 2013 AIP Publishing LLC.

Validity of the site-averaging approximation for modeling the dissociative chemisorption of H2 on Cu(111) surface: A quantum dynamics study on two potential energy surfaces

“…33 A new finding for the site-averaging approximation was presented for both reactions for HCl/DCl initially in (v = 0, j = 0) state, 31,32 i.e., the 6D dissociation probability can essentially be reproduced without ZPE corrections by averaging the 4D site-specific dissociation probabilities over impact sites, as long as enough impact points are used in the averaging. If the validity of this new site-averaging approximation generally holds in other molecule-surface reactions, it should be a very promising approach to investigate the moleculesurface reactions at a full-dimensional quantum mechanical level.…”

“…Such full-dimensional quantum dynamics calculations were limited to the diatomic molecules such as H 2 dissociating on metal surfaces, [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] and the recent work of HCl/DCl dissociating on Au(111) surface. [31][32][33] Early in 1995, Gross et al carried out the first full-dimensional quantum dynamics calculation on non-activated dissociation of H 2 on Pd(100) surface. 25, 26 Kroes and co-workers demonstrated that electron-hole pair excitation need not be considered to obtain accurate results for activated dissociation of H 2 on Pt(111) surface by performing full-dimensional quantum dynamics calculations.…”

“…However, large differences were seen between the results using the fourdimensional (4D) site-specific and the full-dimensional (6D) calculations of diatomic dissociative chemisorption. 17,31,32 Early in 1997, Dai and Light found that the dissociation probabilities from the 4D fixed-site quantum dynamics calculations are quite different from those from 6D calculations in the H 2 +Cu(111) system. 17 In addition, they averaged the 4D fixed-site dissociation probabilities for H 2 initially in the ground rovibrational state (v = 0, j = 0) over three impact sites (bridge, center, and top) to obtain the site-averaging dissociation probability, which is similar in shape with the 6D dissociation probability, while the latter is shifted to higher energy by about 0.05 eV.…”

Vibrational energy transfer near a dissociative adsorption transition state: State-to-state study of HCl collisions at Au(111)

“…Similar to H 2 on Cu(111), HCl can dissociate on Au(111) over a reaction barrier (at E i > 1 eV, 17 calculated barrier height: 0.65 eV 18,19 ) and the reaction is strongly enhanced by vibrational excitation, 17 reflecting a possible late transition state. 18,20,21 Vibrational…”

Quantum State–Resolved Studies of Chemisorption Reactions

“…In the studies presented in this review, there is no conclusive evidence that nonadiabatic effects influence the dissociation dynamics. Recent experiments on the dissociation of HCl on Au (111) by Shirhatti et al (145) measured the sticking coefficient to be much lower than predicted theoretically (146). A possible reason might be that the calculations neglect nonadiabatic effects, which have been observed in surface scattering experiments for the same system (14)(15)(16).…”