64 Zhi-Jun Sui et al.

to study the DHP reaction by our group (Yang et al., 2010, 2011, 2012) and
the results are summarized here. The mechanism for DHP is illustrated by
using these results and the results from other experimental and theoretical
studies.

2.1. Computational details

DFT calculations were carried out with the VASP package (Kresse and
Furthmüller, 1996a,b; Kresse and Hafner, 1993), using a plane wave basis
set, where Kohn–Sham equations were solved self-consistently with the
generalized gradient approximation functional proposed by Perdew et al.
(1996). A plane wave energy cutoff of 400 eV was used, and the geometries
were relaxed using a force-based conjugate gradient algorithm until the
forces on all the unconstrained atoms were less than 0.03 eV/Å. A four-layer
slab with a p(3  3) supercell was used to represent the Pt(111) surface,
achieving a coverage of adsorbates of 1/9 ML. When studying the reactions
at the stepped Pt(211), a (1  4) unit cell with nine layers was used and the
bottom four layers were fixed to their crystal positions. Five Pt-Sn alloyed
surfaces, namely, Pt3Sn/Pt(111) and Pt2Sn/Pt(111) (surface alloys) and
Pt3Sn(111), Pt2Sn(111), and PtSn2(111) (bulk alloys) were constructed to
study the effect of Sn addition. For more details, such as the k-point grids
of these surfaces and the segregation energy calculations on the alloyed sur-
faces, the readers are referred to Ciobica and van Santen (2002) and Yang
et al. (2010, 2011, 2012). The geometries of gas-phase species were relaxed
by putting a molecule into a box with dimensions of 20 Å  20.5 Å  21 Å
and carrying out a spin-polarized gamma-point calculation.
The transitional states (TS) were located with the dimer method
(Henkelman and Jonsson, 1999, 2001; Olsen et al., 2004). The most stable
configurations of the reactant on the surface were determined by the stan-
dard DFT minimization. These configurations were used as the initial state,
from which the dimer method was used to find the lowest curvature mode
and to climb up the potential energy surface from minima to saddle points.
A force tolerance of 0.03 eV/Å was used in all the transition state searches.

2.2. Adsorption of carbonaceous species

Adsorption is the first step of heterogeneous catalytic reactions and is the
basis of our work. The most favorable adsorption sites and calculated adsorp-
tion energies over the flat Pt(111) and stepped Pt(211) are summarized in
Table 2.1, and the adsorption sites are represented schematically in Fig. 2.1.