Hydrogen transfer in hydrocarbon conversions over

transition metal surfaces

Andrew V. Zeigarnik
a,
*
, Ra ul E. Valdes-Perez
b,
*
, Natalia I. Egorova
c
a
Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117334, Russia
b
Computer Science Department, Carnegie Mellon University, Pittsburgh, PA 15213, USA
c
Laboratory of Chemical Kinetics and Catalysis, Lomonosov Academy of Fine Chemical Technology, Moscow 117571, Russia
Received 29 September 2000; accepted for publication 11 April 2001
Abstract
Hydrogen-transfer steps are a poorly studied and rarely proposed class of elementary reactions in heterogeneous
catalysis over metal surfaces. In these steps, a hydrogen atom that is attached to the carbon in one surface species
transfers to a carbon atom of another species. Unity bond indexquadratic exponential potential (UBIQEP) calcu-
lations of the activation energies for three model surfaces representing substrates with strong, weak, and intermediate
chemisorption abilities, combined with UBIQEP/DFT data for the Pt(1 1 1) surface, suggest that there is no great
energetic impediment to these steps. Therefore, they should not be arbitrarily ignored when building mechanisms of
hydrocarbon conversions over metal surfaces. Moreover, kinetics simulations show that conditions are possible under
which one-step hydrogen transfer is faster than the two-step process with the formation of adsorbed hydrogen. 2001
Elsevier Science B.V. All rights reserved.
Keywords: Models of surface chemical reactions; Semi-empirical models and model calculations; Catalysis; Models of surface kinetics
1. Introduction
This article treats a type of elementary step that
has received little attention in studies of hydro-
carbon conversions over transition metal catalyst
surfaces: a hydrogen atom attached to the carbon
in one surface species transfers to a carbon atom of
another species. An example is in which ethylidene
provides an a-H atom to the adsorbed ethylene,
forming ethylidyne and ethyl. We were motivated
to focus on such steps because of our experience in
exploring mechanisms of ethane hydrogenolysis
[1,2] with the computer programs MECHEM MECHEM [35]
and CHEMNET CHEMNET [5,6].
These programs help advance hypotheses on
the mechanisms of catalytic reactions; details on
these programs can be found via the citations.
Here we just note that the programs are based on
combinatorial searches and help to generate vari-
ous plausible mechanisms. Of course, the number
of mechanisms generated by the programs depends
Surface Science 487 (2001) 146158
www.elsevier.nl/locate/susc
*
Corresponding authors. Tel.: +1-412-268-7127; fax: +1-
412-268-3608/5575.
E-mail addresses: azeigarn@cs.cmu.edu (A.V. Zeigarnik),
valdes@cs.cmu.edu (R.E. Valdes-Perez).
0039-6028/01/$ - see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S0039- 6028( 01) 01086- X
on how a reaction problem is formulated. In the
case of ethane hydrogenolysis, we found that the
number of hypothetical mechanisms generated by
the programs is in the tens of thousands. Such a
combinatorial richness is mainly due to the ability
to conjecture hydrogen-transfer steps, which we
allowed in the absence of any good reason not to
(the programs explicated the consequences either
way). This richness recurs when we explore other
reactions such as ethylene hydrogenation, Fischer
Tropsch synthesis, and others [7].
The relevant published data on hydrogen-
transfer steps are very scarce; they are sketched in
Section 2. We have found no convincing evidence
that justies either excluding or including hydro-
gen-transfer steps as building blocks for hypo-
thetical pathways of hydrocarbon conversions.
Therefore, it is of interest to nd evidence bearing
on the plausibility of hydrogen-transfer steps. If
they are insignicant, then the problem of mech-
anism elucidation is much simplied by excluding
a large set of combinatorial possibilities (whether
generated by computer programs or proposed
humanly). If these steps are plausible, it behooves
researchers to reconsider the mechanisms of reac-
tions where these steps might be operative. This
article will argue that the steps are plausible.
This paper estimates the energetics (activa-
tion energies) of these steps using the unity bond
index-quadratic exponential potential (UBIQEP)
method developed by Shustorovich and Sellers
[8,9]. The method makes use of data on simple
atomic adsorbate binding energies to estimate the
adsorption heats of more complex adsorbates, as
well as the enthalpies and activation energies of the
elementary surface reactions in which they partici-
pate. Recent work along this line [10] estimated
the binding energy of atomic carbon using experi-
mental data on the binding energies of various
carbon-centered adsorbates. Then we calculated
the binding energies of other species. These new
data are the basis for the calculations in this paper.
2. Preliminary data on hydrogen-transfer steps
Ethane hydrogenolysis is an ideal reaction in
which to consider hydrogen-transfer steps. The
mechanism of this reaction, which most research-
ers seem to agree on, includes ethane dehydroge-
nation steps to form adsorbed C
2
H
x
species, the
cleavage of CC bond, and the hydrogenation
of adsorbed CH
y
. This is the so-called Sinfelt
Taylor mechanism [11]. In our computational ex-
periments, the MECHEM MECHEM program cited above
minimizes the numbers of species and steps in a
mechanism, and hence its reasonable suggestion
was to combine hydrogenation steps together with
dehydrogenation. The combination of these two
types of steps gives one hydrogen-transfer step.
This raises the important issue of whether the
surface accommodates a hydrogen atom before it
attaches to the carbon atom of the second species.
Thomson and Webb [12] were the rst authors
known to us who directly pointed to the possibil-
ity of hydrogen-transfer steps. They studied the
hydrogenation of olens and concluded that hy-
drogen-transfer steps form the basis for the mech-
anism of these reactions. According to Thompson
and Webb, the general features of olen hydro-
genation reactions are as follows: (a) the apparent
activation energies of olen hydrogenation vary
only slightly from one metal surface to another; (b)
olen hydrogenation is structure insensitive; (c)
olens are able to self-hydrogenate when hydro-
gen is absent from the gas phase, and this process
yields various carbonaceous hydrogen-decient
species on the surface; etc. These and other (less
important) circumstances are suggestive of the
idea that the surface does not provide hydrogen
for hydrogenation; rather, some species act as hy-
drogenating agents [12].
Further studies revealed that, upon heating
ethylene to room temperature, various single crys-
tal surfaces such as Pt(1 1 1), Pt(1 0 0), Rh(1 1 1),
Rh(1 0 0), Pd(1 1 1), Ru(0 0 0 1), and Ir(1 1 1), as
well as various supported metals, readily form
ethylidyne (see, for example Ref. [13] and refer-
ences therein) which is a very stable species. Zaera
and French studied in detail the mechanism of
ethylidyne formation and concluded with a two-
step mechanism with a 1,2-H shift to form ethy-
lidene, and a-hydrogen abstraction from the latter
[13]. Note that in this mechanism, hydrogen is not
abstracted by the surface. The 1,2-shift is com-
pletely analogous to a hydrogen transfer (in the
A.V. Zeigarnik et al. / Surface Science 487 (2001) 146158 147
sense adopted in this paper) except that hydrogen
jumps from one carbon to another in the same
species.
Ethylidyne and other species cover the surface
and block most of the active sites, but ethylene
hydrogenation still occurs. So one of the early
Zaera and Somorjai hypotheses for the ethylene
hydrogenation mechanism was based on the idea
that ethylidyne acts as a hydrogen-transfer agent
on Pt(1 1 1) [14]:
H
2
(gas) 2H(ads)
CCH
3
(ads) H(ads) CHCH
3
(ads)
2CHCH
3
(ads) C
2
H
4
(ads) 2CCH
3
C
2
H
6
Of course, the last step is not elementary, but
the idea is that ethylidyne is a source of hydrogen
which may transfer to ethylene via a surface-
adsorbed state or directly.
However, further studies of ethylene hydro-
genation showed that ethylidyne is more of a
spectator than an intermediate in this reaction [15
17].
In the microkinetic modeling of ethylene hy-
drogenation [18], it was found that the com-
monly accepted HoriutiPolanyi mechanism fails
to describe adequately the pattern of deuterated
product distribution. To eliminate this limitation,
Dumesic and co-workers [18] considered add-in
steps to account for H/D exchange, including
C
2
H
5
(ads) C
2
H
5
(ads) C
2
H
6
C
2
H
4
(ads)
although they found that adding this step does not
improve the description of experimental data, but
rather makes it worse. So this mechanistic pro-
posal was rejected.
Hoek and Sachtler [19] studied the enantio-
selective hydrogenation of methylacetoacetate to
chiral methylhydroxybutyrate on nickel catalysts
modied with tartaric acid and nickel tartrate
complexes. They suggested that oxygen atoms of
tartrate ligands are hydrogen-transfer agents. These
ligands deliver adsorbed hydrogen atoms, formed
by the dissociative adsorption of H
2
, to the sub-
strate.
Huang and Sachtler recently reported a hydro-
gen transfer on silica-supported Pt and Ru cata-
lysts in the co-hydrogenation of CD
3
CN and
C
3
H
7
CN [20]. For the ruthenium surface, they
assumed the following steps without considering in
detail whether they are elementary:
In these reactions, hydrogen transfers from a car-
bon atom to nitrogen.
Based on the data on hydrogenation reac-
tions of ethylene [12] methylacetoacetate [19], and
acetonitrile [20,21], Huang and Sachtler proposed
a general concept of overlayer catalysis that as-
sumes the possibility of hydrogen transfer from the
surface to the hydrogenation substrate through an
overlayer, specically through oxygen, nitrogen, or
carbon atoms of adsorbed species [22].
We know several examples of similar steps from
homogeneous catalysis. For example, Grigoryan
and co-workers studied (r-bond metathesis reac-
tions in solutions in the presence of ZieglerNatta
catalysts based on TiCl
4
, vanadium and iron
acetylacetonates, and organolithium compounds
[23]. Specically, the organoiron fragments con-
taining a FeC
2
H
5
bond and methane produced
ethane [24]:
FeC
2
H
5
CH
4
C
2
H
6
FeCH
3
According to Grigoryan [23], many organo-
metal complexes are known to participate in r-
bond metathesis reactions leading to methane
activation and functionalization. Among these,
there are lutetium, scandium, thorium, and other
metal complexes. Hotcamp et al. [25] reported a
reaction from organopalladium chemistry in a
solution:
PdCH
3

13
CH
4
Pd
13
CH
3
CH
4
Silica-supported hydrides of tantalum, chro-
mium, and tungsten were found to catalyze the
metathesis of linear and branched alkanes [26].
The mechanism includes several steps of r-bond
metathesis type:
148 A.V. Zeigarnik et al. / Surface Science 487 (2001) 146158
One of the r-bond metathesis reactions that
completes the cycle is essentially a hydrogen-
transfer step.
Generally, hydrogen-transfer reactions are
rarely proposed as building blocks for the mecha-
nisms of hydrocarbon conversions. Moreover, their
elementariness is doubtful. All examples known to
us from heterogeneous and homogeneous catalysis
include the participation of closed-shell molecules
(like methane and ethane). On the other hand, the
only argument against hydrogen-transfer steps is
that they have little precedent in the literature.
Therefore, we began to seek physical and chemical
arguments, since these steps could be important
for various types of hydrocarbon transformations
on surfaces (hydrogenation, dehydrogenation, hy-
drogenolysis, H/D exchange, isomerization, etc.),
as well as in other reactions (FischerTropsch
synthesis, methane reforming, etc.).
If the activation energies of these steps are high,
then these steps should not occur. If they are low,
then we should consider these steps in candidate
pathways unless other contrary evidence can be
found.
3. UBIQEP calculation scheme and prior data
An advantage of the UBIQEP method is that
it requires no special software and computational
resources, while it provides reasonably accurate
estimates of the activation energies if the binding
energies used as input are accurate. Thus, Blowers
and Masel examined the accuracy of the bond-
order conservation assumption in the case of some
gas-phase hydrogenolysis and dehydrogenation
reactions [27]. We also compared various UBI
QEP data reported in the literature with experi-
mental data and found fairly good agreement [28].
In our previous work, we considered the zero-
coverage limit on various metal surfaces: Ni(1 1 1),
Pd(1 1 1), Pt(1 1 1), Rh(1 1 1), Ru(0 0 0 1), Ir(1 1 1),
Cu(1 1 1), and Au(1 1 1). For these metals, we
employed the binding energies of various adsor-
bates on these surfaces to calculate the binding
energies of atomic carbon and then the missing
binding energies for other adsorbates [10,29].
Many binding energies (calculated by dierent
methods) for specic adsorbates coincided or were
close, although some specic trends were dierent.
Specically, the DFT and UBIQEP binding en-
ergies for CH
x
followed radically dierent trends.
In both cases, the curves of binding energies vs.
number of hydrogen atoms in CH
x
can be ap-
proximated by third- or fourth-order polynomials
with alternating positive and negative coecients.
However, the signs of coecients alternate ``in
dierent phases''. Whenever a coecient is posi-
tive for DFT, it is negative for UBIQEP and vice
versa. The DFT binding energies increase roughly
in proportion to the number of bonds formed
between an adsorbate and the surface. The UBI
QEP binding energies increase roughly in propor-
tion to the number of bonds that might be formed
if the contact atom(s) of an adsorbate employed all
its co-ordination vacancies. Therefore, the best
agreement between DFT and UBIQEP is reached
when the contact atoms use all of their valencies. It
is dicult to choose a priori between the two
schemes because no clear reference points are
available: the scatters of experimental data are too
broad.
We found excellent qualitative agreement be-
tween our data and the data obtained using the
model of polar covalence bond (PCB) developed
by Sanderson and modied for chemisorption
bond calculations by Frese [30]. The UBIQEP
binding energies of atomic carbon increased in the
series
A.V. Zeigarnik et al. / Surface Science 487 (2001) 146158 149
Pd < Ru ~ Pt < Ni < Ir < Fe [10; 29[:
The PCB binding energies increased in the series
Pd < Pt ~ Ru < Ni ~ Ir < Fe [30[:
The metals examined in our previous calcula-
tions can conventionally be subdivided into three
groups in terms of the chemisorption strength: (i)
weak surfaces, including Group IB metals Cu and
Au; (ii) moderate, including Group VIII metals
except Fe; and (iii) strong, consisting of Fe alone
(and probably W, which was not considered).
Therefore, to probe hydrogen-transfer reactions,
we chose one representative from each of these
three groups, namely Cu, Pt and Fe. The binding
energies borrowed from our previous paper are
listed in Table 1. Our ongoing research seeks to
rene these values.
To calculate the activation energies of a hy-
drogen-transfer step
X(ads) YH(ads) XH(ads) Y(ads)
we use the formula
E
a
= 0:5[DH Q
XH
Q
Y
=(Q
XH
Q
Y
)[ (1)
Q
X
, Q
Y
, Q
YH
, and Q
XH
are the chemisorption
heats of X, Y, YH and XH, respectively. DH is
the enthalpy of the reaction on the surface calcu-
lated from the thermodynamic cycle desorption
gas-phase reaction adsorption
DH = Q
X
Q
YH
D Q
XH
Q
Y
: (2)
D is the enthalpy of the gas-phase reaction calcu-
lated from the bond energies
D = D
X
D
YH
D
XH
D
Y
: (3)
The activation energy of the reverse reaction
E
reverse
is calculated from the activation energy of
the forward reaction E
forward
and the enthalpy DH:
E
reverse
= DH E
forward
(4)
If the activation energy is lower than zero, we used
a thermodynamic correction: this activation en-
ergy is set to zero, and the corresponding activa-
tion energy of the reverse reaction is set to the
reaction enthalpy with an appropriate sign. When
calculating the forward activation energies for el-
ementary steps, we chose a direction that fullled
the condition that D > 0.
The activation energies of dissociation steps
Table 1
Binding energies (in kcal/mol) for CH
x
and C
2
H
x
calculated using the UBIQEP method and the corrected values of carbon binding
energies
Adsorbate (co-ordination) D
a
Cu(1 1 1) Pt(1 1 1) Fe(1 1 0) Equation
b
C 122.1 176.2 192.5
CH (g
1
l
3
) 81 73.4 120.7 135.5 4.2.2.4
CH
2
(g
1
l
2
) 183 48.9 86.4 98.7 4.2.2.4
CH
3
(g
1
l
1
) 293 26.4 50.1 56.5 4.2.3.1
CH
3
CH
3
674 6.2
c
7.6
d
8.7
e

CH
3
CH
2
(g
1
l
1
) 576 27.1 51.4 57.9 4.2.3.1
CH
3
CH (g
1
l
2
) 466 50.5 88.9 101.4 4.2.2.4
CH
2
CH
2
(g
2
l
2
) 538 7.9 15.9 17.2 4.2.1.10
CH
3
C (g
1
l
3
) 376 72.7 119.8 134.5 4.2.3.1
CH
2
CH (g
2
l
2
) 421 11.1 18.4 19.5 4.2.1.7
CH
2
C (g
2
l
2
) 348 50.9 62.5 69.9 4.2.1.7
CH@CH (g
2
l
2
) 392 8.9 17.9 19.3 4.2.1.10
CH@C (g
2
l
2
) 259 34.9 43.0 36.5 4.2.1.7
CH
4
4.5
c
6.0
d
7.0
e

a
D is the sum of bond energies for the corresponding species in the gas phase.
b
The numbers of equations are taken from Ref. [9].
c
The value obtained by extrapolating the plot of physisorption energies for n-alkanes on Cu(1 0 0) vs. chain length to ethane [31].
d
The experimental value [32].
e
A value which is 1 kcal/mol higher than for Ni(1 1 1).
150 A.V. Zeigarnik et al. / Surface Science 487 (2001) 146158
YH(ads) Y(ads) H(ads)
are calculated by the analogous formulas
E
a
= 0:5[DH Q
H
Q
Y
=(Q
H
Q
Y
)[; (5)
DH = Q
YH
D Q
H
Q
Y
; (6)
D = D
YH
D
Y
: (7)
The UBIQEP method can also be combined
with other methods or with experiment by using
binding energies from these external sources and
calculating the activation energies of steps by Eq.
(1).
4. Results and discussion
4.1. UBIQEP predictions
Table 2 shows the calculated activation energies
in kcal/mol for the hydrogen-transfer steps. All
species in the table are adsorbed on the surface.
Closed-shell molecules, like methane and ethane,
are also trapped intermediates. Table 2 contains
the complete set of hydrogen-transfer reactions for
species that contain one or two carbon atoms. This
complete set was generated with the CHEMNET CHEMNET
program [6]. Our rst conclusion is that, based on
the UBIQEP calculations of energetics, there is
no reason to exclude all hydrogen-transfer steps
when building mechanisms of hydrocarbon con-
versions over metal surfaces.
Of course, the reaction rates do not depend only
on the activation energies; the pre-exponential
factors and species concentrations are important.
However, some inferences are possible. For in-
stance, reactions 5, 10, 113, 119, 130, 140 from
Table 2 occur on none of the metal surfaces and so
can be safely excluded from the mechanism of any
reaction, because their activation energies are too
high and the rates are too low even at high species
concentrations. Some reactions occur readily on
the weakly chemisorbing surface of Cu(1 1 1) but
do not occur on the strongly chemisorbing surface
of Fe(1 1 0). For instance, the activation energy of
reaction 84 is 71.7 kcal/mol for Fe(1 1 0), whereas
it is only 9.2 kcal/mol for Cu(1 1 1). Other such
examples are reactions 107, 172, and 176. Con-
verse examples are also seen, although they are
rarer. For instance, reactions 131 and 167 have an
activation energy of zero for strong surfaces, but
are relatively slow on weak surfaces.
A number of reactions should occur on any of
the surfaces unless there are reasons other than
energetics. Such instances are reactions 27, 28, 33,
3841 and many others with activation energies of
zero or nearly zero. We failed to nd (by hand)
any simple heuristic rule that predicts the ener-
getics of these reactions.
The activation energies of some reactions tend
to increase with the chemisorbing strength of the
surface. Others are insensitive to the chemisorp-
tion strength. For the remainder, the activation
energies decrease with an increase in the strength
of surface chemisorption.
Let us consider the reactions' sensitivity to the
strength of the surface. The sensitivity can be ex-
pressed as a ratio of the dierence between the
activation energies on weak (e.g., Cu) and strong
(e.g., Fe) surfaces to the dierences between the
respective binding energies of carbon (or any other
adsorbate taken as a reference).
S =
DE
a
DQ
C

:
In our case, DQ
C
= 192:5 122:1 = 70:4 kcal/mol.
Then, all the reactions from Table 2 can conven-
tionally be subdivided into three classes: (i) poorly
sensitive (S 60:2), (ii) highly sensitive (S P0:6),
and (iii) moderately sensitive (intermediate values
of S).
Most of the reactions (126 out of 204) are
poorly sensitive to the chemisorbing strength of a
surface. That is, if a reaction occurs on one sur-
face, then it may also occur on other surfaces with
a high probability. Only 17 are highly sensitive:
reactions 4, 12, 21, 62, 69, 84, 100, 102, 107, 112,
122, 139, 144, 172, 176, 193 and 195. The others
are moderately sensitive.
Some reactions from Table 2 belong to a special
class of reactions that contain a same species on
both the left-hand and right-hand sides of the
equation. We call these pseudoisomerizations. Such
steps are rarely proposed, but they are possible
A.V. Zeigarnik et al. / Surface Science 487 (2001) 146158 151
Table 2
Activation energies (in kcal/mol) of hydrogen-transfer reactions on Fe(1 1 0), Pt(1 1 1), and Cu(1 1 1) and the sensitivities of these
reactions to the chemisorption strength of the surface (see text for explanation)
No. H-transfer reaction Cu(1 1 1)
a
Pt(1 1 1)
a
Pt(1 1 1)
b
Fe(1 1 0)
a
Sensitivity
1 CCH
2
CHCH 45.2 51.4 13.7 54.5 0.13
2 CCH
3
CH
2
CH 55.2 49.4 14.0 51.4 0.06
3 CCH
4
CH
3
CH 50.8 35.4 1.1 35.2 0.22
4 CCH
3
CCHCH
2
C 31.5 66.0 34.5 76.0 0.63
5 CCHCHCHCHC 74.7 82.5 41.0 84.2 0.14
6 CCH
2
CCHCHC 72.6 83.1 27.8 84.7 0.17
7 CCH
3
CH
3
CHCH
3
CH
2
44.8 32.4 0.2 32.2 0.18
8 CCH
3
CH
2
CHCH
2
CH
2
24.9 48.2 0.0 54.9 0.43
9 CCH
3
CH
2
CHCH
3
CH 54.3 49.2 11.6 51.2 0.04
10 CCH
2
CH
2
CHCH
2
CH 81.4 89.1 11.6 90.9 0.13
11 CCH
3
CHCHCH
3
C 36.0 47.0 8.5 50.2 0.20
12 CCH
3
CHCHCH
2
CH 52.1 90.5 6.3 101.4 0.70
13 CCH
2
CHCHCHCH 4.6 10.4 3.8 11.9 0.10
14 CCH
2
CHCHCH
2
C 5.6 10.1 16.9 11.6 0.09
15 CHCHCH
2
C 0.0 9.2 69.6 13.3 0.19
16 CHCH
2
CH
3
C 0.0 1.3 50.1 5.7 0.08
17 CHCH
3
CCH
4
0.0 0.3 39.5 5.5 0.08
18 CHCH
3
CH
2
CH
2
17.3 24.7 36.0 26.9 0.14
19 CHCH
4
CH
3
CH
2
11.4 12.4 26.5 12.6 0.02
20 CHCH
3
CCCH
3
CH 0.5 13.4 72.1 17.3 0.24
21 CHCH
3
CCH
2
CH
2
C 4.4 39.3 64.2 49.6 0.64
22 CHCHCHCCH
2
CH 5.6 6.4 54.6 7.1 0.02
23 CHCHCHCH
2
CHC 29.5 40.3 77.6 43.0 0.19
24 CHCH
2
CCCH
3
C 14.0 5.6 42.5 3.2 0.15
25 CHCH
2
CCCH
2
CH 4.6 6.6 41.4 7.3 0.04
26 CHCH
2
CCH
2
CHC 28.8 41.1 56.2 43.9 0.21
27 CHCHCCCHCH 0.0 0.0 19.3 0.0 0.00
28 CHCHCCCH
2
C 0.0 0.0 32.4 0.0 0.00
29 CHCH
3
CH
3
CH
2
CH
3
CH
2
2.7 0.0 20.8 0.0 0.04
30 CHCH
3
CH
2
CCH
3
CH
3
0.0 3.9 35.3 9.2 0.13
31 CHCH
3
CH
2
CH
2
CH
2
CH
2
0.0 21.2 21.4 27.6 0.39
32 CHCH
3
CH
2
CH
2
CH
3
CH 17.0 24.4 33.9 26.6 0.14
33 CHCH
2
CH
2
CCH
3
CH
2
0.0 0.0 48.6 0.0 0.00
34 CHCH
2
CH
2
CH
2
CH
2
CH 36.3 46.9 34.2 49.6 0.19
35 CHCH
3
CHCCH
3
CH
2
0.0 2.3 50.2 6.8 0.10
36 CHCH
3
CHCH
2
CH
3
C 10.1 21.5 27.0 24.8 0.21
37 CHCH
3
CHCH
2
CH
2
CH 18.4 49.9 35.3 60.2 0.59
38 CHCH
2
CHCCH
2
CH
2
0.0 0.0 48.7 0.0 0.00
39 CHCH
2
CHCCH
3
CH 0.0 0.0 53.4 0.0 0.00
40 CHCH
2
CHCH
2
CHCH 0.0 0.0 32.7 0.0 0.00
41 CHCH
2
CHCH
2
CH
2
C 0.0 0.0 45.9 0.0 0.00
42 CH
2
CH
2
CH
3
CH 7.2 18.8 16.2 22.5 0.22
43 CH
2
CH
3
CHCH
4
5.8 19.5 9.0 24.1 0.26
44 CH
2
CH
4
CH
3
CH
3
0.0 0.0 1.7 0.0 0.00
45 CH
2
CH
3
CCHCH
3
CH 19.8 30.0 34.7 33.2 0.19
46 CH
2
CH
3
CCH
3
CH
2
C 0.0 31.4 45.3 42.1 0.60
47 CH
2
CHCHCHCH
2
CH 46.2 38.2 27.6 36.4 0.14
48 CH
2
CHCHCH
3
CHC 19.4 34.5 57.8 38.6 0.27
49 CH
2
CH
2
CCHCH
3
C 32.1 21.1 16.3 17.9 0.20
50 CH
2
CH
2
CCHCH
2
CH 44.2 38.7 14.5 36.9 0.10
51 CH
2
CH
2
CCH
3
CHC 21.2 35.7 40.8 39.3 0.26
152 A.V. Zeigarnik et al. / Surface Science 487 (2001) 146158
Table 2 (continued)
No. H-transfer reaction Cu(1 1 1)
a
Pt(1 1 1)
a
Pt(1 1 1)
b
Fe(1 1 0)
a
Sensitivity
52 CH
2
CHCCHCHCH 0.0 0.0 0.0 0.0 0.00
53 CH
2
CHCCHCH
2
C 1.3 0.2 4.9 0.4 0.01
54 CH
2
CH
3
CH
3
CH
3
CH
3
CH
2
0.0 0.0 4.0 0.0 0.00
55 CH
2
CH
3
CH
2
CHCH
3
CH
3
3.1 13.7 0.0 18.2 0.22
56 CH
2
CH
3
CH
2
CH
3
CH
2
CH
2
0.0 16.3 9.5 23.2 0.33
57 CH
2
CH
3
CH
2
CH
3
CH
3
CH 8.3 15.6 14.5 18.0 0.14
58 CH
2
CH
2
CH
2
CHCH
3
CH
2
20.2 15.1 14.1 13.9 0.09
59 CH
2
CH
2
CH
2
CH
3
CH
2
CH 26.2 41.0 16.6 45.2 0.27
60 CH
2
CH
3
CHCHCH
3
CH
2
7.8 19.7 16.6 23.4 0.22
61 CH
2
CH
3
CHCH
3
CH
3
C 2.6 14.8 11.5 18.6 0.23
62 CH
2
CH
3
CHCH
3
CH
2
CH 10.8 43.3 19.8 55.8 0.64
63 CH
2
CH
2
CHCHCH
2
CH
2
0.0 0.0 15.4 0.0 0.00
64 CH
2
CH
2
CHCHCH
3
CH 11.5 1.6 26.5 0.0 0.16
65 CH
2
CH
2
CHCH
3
CHCH 0.0 0.0 17.5 0.0 0.00
66 CH
2
CH
2
CHCH
3
CH
2
C 0.0 0.0 30.6 0.0 0.00
67 CH
3
CH
3
CH
2
CH
4
4.5 13.0 4.0 15.9 0.16
68 CH
3
CH
3
CCH
2
CH
3
CH 22.3 29.3 39.0 31.4 0.13
69 CH
3
CH
3
CCH
4
CH
2
C 0.0 30.4 35.2 43.1 0.61
70 CH
3
CHCHCH
2
CH
2
CH 56.3 44.0 32.2 40.8 0.22
71 CH
3
CHCHCH
4
CHC 23.9 47.4 60.1 54.5 0.43
72 CH
3
CH
2
CCH
2
CH
3
C 37.7 19.1 17.2 14.9 0.33
73 CH
3
CH
2
CCH
2
CH
2
CH 54.3 44.6 19.0 41.3 0.18
74 CH
3
CHCCH
2
CHCH 0.0 0.0 0.0 0.0 0.00
75 CH
3
CHCCH
2
CH
2
C 3.8 0.7 9.3 0.2 0.05
76 CH
3
CH
3
CH
3
CH
4
CH
3
CH
2
0.0 0.0 5.0 0.4 0.01
77 CH
3
CH
3
CH
2
CH
2
CH
3
CH
3
10.5 19.6 3.0 22.6 0.17
78 CH
3
CH
3
CH
2
CH
4
CH
2
CH
2
0.0 19.3 7.2 27.3 0.39
79 CH
3
CH
3
CH
2
CH
4
CH
3
CH 3.8 11.7 2.7 14.6 0.15
80 CH
3
CH
2
CH
2
CH
2
CH
3
CH
2
30.3 16.1 22.0 14.0 0.23
81 CH
3
CH
2
CH
2
CH
4
CH
2
CH 30.7 54.0 3.5 61.1 0.43
82 CH
3
CH
3
CHCH
2
CH
3
CH
2
9.2 16.8 17.0 19.2 0.14
83 CH
3
CH
3
CHCH
4
CH
3
C 1.0 15.4 4.8 20.1 0.27
84 CH
3
CH
3
CHCH
4
CH
2
CH 9.3 55.4 13.0 71.7 0.89
85 CH
3
CH
2
CHCH
2
CH
2
CH
2
0.0 0.0 17.6 0.0 0.00
86 CH
3
CH
2
CHCH
2
CH
3
CH 14.0 0.8 30.8 0.0 0.20
87 CH
3
CH
2
CHCH
4
CHCH 0.0 0.0 10.9 0.0 0.00
88 CH
3
CH
2
CHCH
4
CH
2
C 0.0 0.0 24.1 0.0 0.00
89 CH
4
CH
3
CCH
3
CH
3
CH 16.3 16.9 30.0 16.9 0.01
90 CH
4
CHCHCH
3
CH
2
CH 51.9 31.1 23.3 24.9 0.38
91 CH
4
CH
2
CCH
3
CH
3
C 33.3 5.1 4.8 0.0 0.47
92 CH
4
CH
2
CCH
3
CH
2
CH 49.8 31.6 10.2 25.4 0.35
93 CH
4
CHCCH
3
CHCH 0.0 0.0 0.0 0.0 0.00
94 CH
4
CHCCH
3
CH
2
C 0.0 0.0 0.4 0.0 0.00
95 CH
4
CH
3
CH
2
CH
3
CH
3
CH
3
6.0 6.6 1.7 7.1 0.02
96 CH
4
CH
2
CH
2
CH
3
CH
3
CH
2
25.9 6.2 17.4 2.2 0.34
97 CH
4
CH
3
CHCH
3
CH
3
CH
2
0.3 0.0 2.9 0.0 0.00
98 CH
4
CH
2
CHCH
3
CH
2
CH
2
0.0 0.0 2.2 0.0 0.00
99 CH
4
CH
2
CHCH
3
CH
3
CH 8.0 0.0 21.7 0.0 0.11
100 CH
3
CCH
3
CCH
3
CHCH
2
C 9.2 43.5 66.8 53.6 0.63
101 CH
3
CCH
3
CH
3
CH
3
CH
2
CH
3
CH 13.4 13.8 29.7 13.8 0.01
102 CH
3
CCH
3
CH
2
CH
3
CH
3
CH
2
C 0.0 34.0 31.0 49.8 0.71
103 CH
3
CCH
3
CH
2
CH
2
CH
2
CH
3
CH 4.6 25.4 25.0 31.7 0.38
104 CH
3
CCH
3
CH
2
CH
3
CHCH
3
CH 22.0 29.0 37.0 31.1 0.13
(continued on next page)
A.V. Zeigarnik et al. / Surface Science 487 (2001) 146158 153
Table 2 (continued)
No. H-transfer reaction Cu(1 1 1)
a
Pt(1 1 1)
a
Pt(1 1 1)
b
Fe(1 1 0)
a
Sensitivity
105 CH
3
CCH
2
CH
2
CH
3
CH
2
CH
2
C 0.0 13.2 40.6 17.9 0.25
106 CH
3
CCH
2
CH
2
CH
3
CHCH
2
CH 45.9 55.5 37.3 58.0 0.17
107 CH
3
CCH
3
CHCH
3
CH
2
CH
2
C 0.0 32.4 45.4 43.2 0.61
108 CH
3
CCH
2
CHCH
2
CH
2
CH
2
C 0.0 0.0 44.0 0.1 0.00
109 CH
3
CCH
2
CHCH
3
CHCHCH 0.0 0.0 35.9 0.0 0.00
110 CH
3
CCH
2
CHCH
3
CHCH
2
C 0.0 0.0 49.0 0.0 0.00
111 CHCHCH
3
CCH
3
CHCHC 39.1 48.9 85.3 51.3 0.17
112 CHCHCH
3
CCH
2
CHCH
2
C 18.6 56.4 47.6 68.0 0.70
113 CHCHCHCHCH
2
CHCHC 75.8 78.5 72.5 79.4 0.05
114 CHCHCH
3
CH
3
CH
3
CH
2
CH
2
CH 45.8 24.4 23.1 18.2 0.39
115 CHCHCH
3
CH
2
CH
3
CH
3
CHC 29.9 54.1 56.8 61.2 0.44
116 CHCHCH
3
CH
2
CH
2
CH
2
CH
2
CH 26.0 44.2 14.2 50.1 0.34
117 CHCHCH
3
CH
2
CH
3
CHCH
2
CH 55.4 42.8 30.2 39.5 0.23
118 CHCHCH
2
CH
2
CH
3
CH
2
CHC 49.7 34.3 70.3 29.3 0.29
119 CHCHCH
2
CH
2
CH
2
CHCH
2
CH 82.5 85.1 30.5 86.0 0.05
120 CHCHCH
3
CHCH
3
CH
2
CHC 20.4 35.7 60.3 39.9 0.28
121 CHCHCH
3
CHCH
2
CHCH
3
C 36.6 29.6 23.1 28.1 0.12
122 CHCHCH
3
CHCH
2
CHCH
2
CH 53.2 86.5 25.5 96.6 0.62
123 CHCHCH
2
CHCH
2
CH
2
CHC 0.0 2.6 58.8 3.4 0.05
124 CHCHCH
2
CHCH
3
CHCHC 22.6 10.6 68.8 7.2 0.22
125 CH
2
CCH
3
CH
4
CHC 21.8 47.9 34.2 55.0 0.47
126 CH
2
CCH
3
CCH
3
CHCHC 37.1 49.5 59.3 51.8 0.21
127 CH
2
CCHCHCH
3
CCHC 57.2 26.9 44.3 22.8 0.49
128 CH
2
CCHCHCH
2
CHCHC 73.7 79.0 46.7 79.9 0.09
129 CH
2
CCH
2
CCH
3
CCHC 55.1 27.2 31.1 23.1 0.46
130 CH
2
CCH
2
CCH
2
CHCHC 71.7 79.6 33.6 80.4 0.12
131 CH
2
CCH
3
CH
3
CH
3
CH
2
CH
3
C 27.3 2.1 3.9 0.0 0.39
132 CH
2
CCH
3
CH
3
CH
3
CH
2
CH
2
CH 43.8 25.0 10.0 18.7 0.36
133 CH
2
CCH
3
CH
2
CH
3
CH
3
CHC 27.9 54.6 30.6 61.7 0.48
134 CH
2
CCH
3
CH
2
CH
2
CH
2
CH
3
C 7.4 1.0 0.0 0.0 0.11
135 CH
2
CCH
3
CH
2
CH
2
CH
2
CH
2
CH 24.0 44.7 3.3 50.6 0.38
136 CH
2
CCH
3
CH
2
CH
3
CHCH
3
C 36.8 18.9 14.8 14.7 0.31
137 CH
2
CCH
3
CH
2
CH
3
CHCH
2
CH 53.3 43.4 17.0 40.0 0.19
138 CH
2
CCH
2
CH
2
CH
3
CH
2
CHC 47.7 34.8 44.0 29.8 0.25
139 CH
2
CCH
2
CH
2
CH
2
CHCH
3
C 63.9 28.7 14.9 18.1 0.65
140 CH
2
CCH
2
CH
2
CH
2
CHCH
2
CH 80.5 85.6 17.4 86.5 0.09
141 CH
2
CCH
3
CHCH
3
CCH
3
C 27.2 16.7 11.2 13.7 0.19
142 CH
2
CCH
3
CHCH
3
CH
2
CHC 21.8 36.5 41.3 40.4 0.26
143 CH
2
CCH
3
CHCH
2
CHCH
3
C 34.6 30.1 9.9 28.6 0.09
144 CH
2
CCH
3
CHCH
2
CHCH
2
CH 51.1 87.0 13.0 97.1 0.65
145 CH
2
CCH
2
CHCH
3
CCHCH 0.0 0.0 4.8 0.0 0.00
146 CH
2
CCH
2
CHCH
2
CH
2
CHC 0.2 4.1 40.1 4.9 0.07
147 CH
2
CCH
2
CHCH
3
CHCHC 20.6 10.8 45.3 7.5 0.19
148 CHCCH
3
CCHCHCH
2
C 0.0 4.8 14.6 11.4 0.16
149 CHCCH
3
CCH
2
CCH
2
C 0.0 4.5 27.7 11.2 0.16
150 CHCCH
3
CH
3
CH
3
CH
2
CHCH 0.0 0.0 0.0 0.0 0.00
151 CHCCH
3
CH
3
CH
3
CH
2
CH
2
C 0.0 0.0 0.1 0.0 0.00
152 CHCCH
3
CH
2
CH
2
CH
2
CHCH 0.0 0.0 0.0 0.0 0.00
153 CHCCH
3
CH
2
CH
2
CH
2
CH
2
C 0.0 0.0 0.0 0.0 0.00
154 CHCCH
3
CH
2
CH
3
CHCHCH 0.0 0.0 0.0 0.0 0.00
155 CHCCH
3
CH
2
CH
3
CHCH
2
C 3.5 0.3 7.3 0.0 0.05
156 CHCCH
2
CH
2
CH
2
CHCHCH 6.8 9.1 0.0 10.0 0.05
157 CHCCH
2
CH
2
CH
2
CHCH
2
C 9.0 10.2 7.6 11.0 0.03
154 A.V. Zeigarnik et al. / Surface Science 487 (2001) 146158
Table 2 (continued)
No. H-transfer reaction Cu(1 1 1)
a
Pt(1 1 1)
a
Pt(1 1 1)
b
Fe(1 1 0)
a
Sensitivity
158 CHCCH
3
CHCH
3
CCHCH 0.0 0.0 0.0 0.0 0.00
159 CHCCH
3
CHCH
3
CCH
2
C 0.0 0.0 0.3 0.0 0.00
160 CHCCH
3
CHCH
2
CHCHCH 0.0 18.5 0.0 24.4 0.35
161 CHCCH
3
CHCH
2
CHCH
2
C 0.0 18.3 2.8 24.2 0.34
162 CHCCH
2
CHCHCHCHCH 0.0 0.0 0.0 0.0 0.00
163 CHCCH
2
CHCHCHCH
2
C 0.0 0.0 0.5 0.0 0.00
164 CHCCH
2
CHCH
2
CCH
2
C 0.0 0.0 13.7 0.0 0.00
165 CH
3
CH
2
CH
3
CH
2
CH
3
CH
3
CH
2
CH
2
0.0 22.8 4.5 31.9 0.45
166 CH
3
CH
2
CH
3
CH
2
CH
3
CH
3
CH
3
CH 9.5 18.4 1.8 21.3 0.17
167 CH
2
CH
2
CH
3
CH
3
CH
3
CH
2
CH
3
CH
2
19.8 3.0 18.0 0.0 0.28
168 CH
2
CH
2
CH
3
CH
2
CH
3
CH
3
CH
2
CH 36.7 60.6 2.5 67.9 0.44
169 CH
2
CH
2
CH
2
CH
2
CH
3
CH
2
CH
2
CH 56.5 40.9 21.0 36.0 0.29
170 CH
3
CHCH
3
CH
3
CH
3
CH
2
CH
3
CH
2
0.0 0.0 5.3 0.0 0.00
171 CH
3
CHCH
3
CH
2
CH
3
CH
3
CH
3
C 4.2 19.0 1.2 23.7 0.28
172 CH
3
CHCH
3
CH
2
CH
3
CH
3
CH
2
CH 12.5 62.0 9.4 78.4 0.94
173 CH
3
CHCH
2
CH
2
CH
3
CH
2
CH
3
C 15.2 10.8 10.0 9.7 0.08
174 CH
3
CHCH
2
CH
2
CH
3
CH
2
CH
2
CH 27.1 42.3 16.0 46.5 0.28
175 CH
3
CHCH
3
CHCH
3
CH
2
CH
3
C 3.2 15.7 12.0 19.6 0.23
176 CH
3
CHCH
3
CHCH
3
CH
2
CH
2
CH 11.5 44.2 20.3 57.1 0.65
177 CH
2
CHCH
3
CH
3
CH
3
CH
2
CH
2
CH
2
0.0 0.0 4.5 0.0 0.00
178 CH
2
CHCH
3
CH
3
CH
3
CH
2
CH
3
CH 5.2 0.0 21.4 0.0 0.07
179 CH
2
CHCH
3
CH
2
CH
3
CH
3
CHCH 0.0 0.0 7.4 0.0 0.00
180 CH
2
CHCH
3
CH
2
CH
3
CH
3
CH
2
C 0.0 0.0 20.6 0.0 0.00
181 CH
2
CHCH
3
CH
2
CH
2
CH
2
CH
2
CH
2
0.0 0.0 9.5 0.0 0.00
182 CH
2
CHCH
3
CH
2
CH
2
CH
2
CH
3
CH 0.0 0.0 14.5 0.0 0.00
183 CH
2
CHCH
3
CH
2
CH
3
CHCH
3
CH 13.7 0.5 28.8 0.0 0.20
184 CH
2
CHCH
2
CH
2
CH
3
CH
2
CHCH 0.0 0.0 12.0 0.0 0.00
185 CH
2
CHCH
2
CH
2
CH
3
CH
2
CH
2
C 0.0 0.0 27.4 0.0 0.00
186 CH
2
CHCH
3
CHCH
3
CH
2
CHCH 0.0 0.0 18.0 0.0 0.00
187 CH
2
CHCH
3
CHCH
3
CH
2
CH
2
C 0.0 0.0 31.1 0.0 0.00
188 CH
2
CHCH
3
CHCH
2
CH
2
CH
3
C 0.0 0.0 10.8 0.0 0.00
189 CH
2
CHCH
2
CHCH
2
CH
2
CHCH 0.0 0.0 16.8 0.0 0.00
190 CH
2
CHCH
2
CHCH
2
CH
2
CH
2
C 0.0 0.0 30.0 0.0 0.00
191 CH
2
CHCH
2
CHCH
3
CHCHCH 0.0 0.0 21.8 0.0 0.00
192 CH
2
CHCH
2
CHCH
3
CHCH
2
C 0.0 0.0 35.6 0.0 0.00
Pseudoisomerizations
193 CH
3
CCH
3
CHCH
3
CHCH
2
CH 23.2 56.9 38.4 68.5 0.64
194 CHCHCH
2
CHCH
2
CHCH
2
C 5.6 6.9 37.0 7.7 0.03
195 CH
2
CCH
3
CCH
2
CHCH
2
C 23.2 56.9 38.1 68.5 0.64
196 CH
2
CCH
2
CHCH
3
CCH
2
C 6.7 0.0 21.6 0.0 0.10
197 CH
2
CCH
2
CHCH
2
CHCHCH 3.5 7.4 10.7 8.2 0.07
198 CHCCHCHCH
2
CCHC 11.4 12.5 37.0 13.3 0.03
199 CHCCH
2
CCHCHCHC 9.3 13.0 10.7 13.8 0.06
200 CH
2
CH
2
CH
3
CH
2
CH
3
CH
2
CH
3
CH 29.4 15.7 20.4 13.5 0.23
201 CH
3
CHCH
3
CH
2
CH
3
CH
2
CH
2
CH
2
0.0 17.1 10.4 24.1 0.34
202 CH
2
CHCH
2
CH
2
CH
3
CHCH
2
CH 29.4 7.0 29.1 3.4 0.37
203 CH
2
CHCH
3
CHCH
2
CH
2
CH
2
CH 0.0 8.4 19.1 14.0 0.20
204 CH
2
CHCH
3
CHCH
3
CHCH
3
C 6.6 0.0 21.9 0.0 0.09
a
UBIQEP binding energies are used as the source data.
b
DFT binding energies are used as the source data.
A.V. Zeigarnik et al. / Surface Science 487 (2001) 146158 155
alternatives to isomerization reactions that cannot
be calculated by the UBIQEP method.
4.2. Combined use of DFT and UBIQEP
Many people believe that UBIQEP predic-
tions of binding energies are qualitatively sound,
but quantitatively inaccurate, whereas the DFT
method works much better. We believe that UBI
QEP predictions are fairly accurate when the
starting data are good enough. However, to test
the idea that there is no great energetic impedi-
ment to hydrogen-transfer steps, DFT binding
energies can be applied together with the analytical
UBIQEP formula for the activation energy. Ta-
ble 3 lists the values of binding energies found
using the interstitial electron surface model devel-
oped by Kua and Goddard together with the
nonlocal DFT method (B3LYP) for the small Pt
8
clusters [33]. The UBIQEP values listed in Table
3 are taken from our previous studies [10,29].
Although the stoichiometry of surface species
listed in Table 3 is the same, the type of binding
varies, so the values dier substantially. Likewise,
we nd a troubling discrepancy between the ac-
tivation energies of hydrogen-transfer steps on
Pt(1 1 1) predicted by UBIQEP and DFT/UBI
QEP (see Table 2). However, this discrepancy does
not undermine the main conclusion drawn from
the UBIQEP calculation alone, which is that
there are many hydrogen-transfer steps that have
low activation energies. Therefore, the combina-
tion of DFT and UBIQEP methods does not lead
to any outcome that justies excluding hydrogen-
transfer steps from hypothesized mechanisms.
4.3. One-step vs. two-step hydrogen transfer
Under certain conditions, a one-step hydrogen-
transfer pathway may compete with its two-step
alternative. Consider the hydrogen-transfer step
(a) CH
2
(ads) CH
3
CH(ads) CH
3
(ads)
CH
3
C(ads)
and the two-step pathway with the formation of
adsorbed hydrogen:
(b) CH
3
CH(ads) H(ads) CH
3
C(ads)
(c) CH
2
(ads) H(ads) CH
3
(ads)
Calculations of the activation energies from the
DFT binding energies of adsorbates for Pt(1 1 1)
and from the UBIQEP analytical formula yield
the following. For the forward and reverse reac-
tion (a), the activation energies are 11.5 and 39.0
kcal/mol, respectively. For reaction (b), the for-
ward and reverse activation energies are 33.0 and
6.2 kcal/mol, respectively. For reaction (c), these
values are 0 and 69.5 kcal/mol, so we may assume
that reaction (c) is irreversible. Let us assume that
the pre-exponential factors of bimolecular reac-
tions are on the order of 10
2
cm
2
molecule
1
s
1
and those of monomolecular reactions are on the
order of 10
13
s
1
[34]. At a temperature of 400 K
and initial coverages of CH
2
and CH
3
CH of
0:1 10
15
molecule cm
2
(0.1 ML) for both, the
characteristic time of their conversion into CH
3
and CH
3
C is on the order of 10
5
s. On the other
hand, the two-step pathway has a characteristic
time of about 75 s, using an initial coverage of
Table 3
Binding energies (in kcal/mol) for adsorbates on Pt(1 1 1) ob-
tained by the DFT method (only the most stable congurations
are considered) [33]
Q D
a
UBIQEP
data
DFT data
H 60 66.7 (1-fold site)
C 176.2 152.0 (3-fold site)
CH 81 120.7 166.6 (3-fold site)
CH
2
183 86.4 104.3 (2-fold site)
CH
3
293 50.1 53.8 (1-fold site)
CH
3
CH
2
576 51.4 45.1 (1-fold site)
CH
3
CH 466 88.9 98.1 (2-fold site)
CH
2
CH
2
538 15.9
b
36.1 (di-r-bonded)
CH
3
C 376 119.8 156.1 (3-fold site)
CH
2
CH 421 18.4 94.6 (g
2
-binding)
CH
2
C 348 62.5
c
96.5
d
(3-fold site)
CHCH 392 17.9
e
78.8
f
CHC 259 43.0
g
94.5
h
a
D is the sum of bond energies for the corresponding species
in the gas phase.
b
Uncertain conguration; maybe an intermediate between p-
bonded and di-r-bonded ethylene.
c
g
2
-binding.
d
Vinylidene.
e
g
2
-(C@C)-binding.
f
Di-r/p-binding.
g
g
2
-(C@C)-binding.
h
Di-r/p-binding.
156 A.V. Zeigarnik et al. / Surface Science 487 (2001) 146158
0.1 ML for H.
1
If we set H to a lower initial
coverage, the characteristic time is even longer.
These numerical estimates show that conditions
are possible under which one-step hydrogen
transfer is faster than the two-step dehydrogena-
tion/hydrogenation process with the formation of
adsorbed hydrogen.
5. Conclusion
We carried out UBIQEP calculations of the
activation energies for three model surfaces repre-
senting substrates with strong, weak, and medium-
strength chemisorption abilities using previous
UBIQEP data, and for the Pt(1 1 1) surface using
DFT data reported by Kua and Goddard [33].
Neither UBIQEP nor combined UBIQEP/DFT
calculations lead to any outcome that justies ex-
cluding all hydrogen-transfer steps when build-
ing mechanisms of hydrocarbon conversions over
metal surfaces. Moreover, kinetics simulations
show that conditions are possible under which
one-step hydrogen transfer is faster than the two-
step process with the formation of adsorbed hy-
drogen.
We conclude that hydrogen-transfer steps
should not be arbitrarily neglected when consid-
ering the mechanisms of hydrocarbon conversions
on metal surfaces. Mechanisms that have been
established while ignoring such steps may need to
be revisited. Unfortunately, allowing such steps
makes mechanism elucidation harder because of
the sheer combinatorics, but it can also make it
more reliable.
Acknowledgements
This research was supported in part by a NATO
Collaborative Research Grant to the rst two au-
thors. RVP was supported in part by grant #IIS-
9988084 from the US National Science Founda-
tion.
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