Surface Science 452 (2000) 95107

www.elsevier.nl/locate/susc

Simulations of hydrogen diffusion on BCC metal (110)

surfaces; coverage and temperature dependence
E.S. Altshuler a, D.L. Mills a, *, R.B. Gerber b,c
a Department of Physics and Astronomy, University of California, Irvine, CA 92697, USA
b Department of Chemistry, University of California, Irvine, CA 92697, USA
c Department of Physical Chemistry, Hebrew University, Jerusalem 91904, Israel

Received 16 August 1999; accepted for publication 30 November 1999

Abstract

We study the coverage and temperature dependences of the tracer diffusion coefficient for a chemisorbed layer of
interacting hydrogen atoms on a model of a bcc metal (110) surface. The surface is rigid, and the short bridge barriers
between adjacent chemisorption wells are sufficiently low that hydrogen atoms diffuse actively across the surface, on
a time scale compatible with our molecular dynamics simulations. We deduce the coverage dependence of the effective
activation barrier and the prefactor. We also examine, as a function of coverage, the percentage of jumps from singly
occupied to either empty or occupied chemisorption wells, and from doubly occupied wells to empty or singly
occupied wells. Although the effective activation barrier deduced from the numerical data exhibits a weak dependence
on coverage, as found in data on H diffusion on the W(110) surface, the percentage of jumps of the types mentioned
varies dramatically. The prefactor in the diffusion constant extracted from the simulations agrees well with elementary
expectations for the rigid surface, but is much larger than that found experimentally. Finally, the low coverage tracer
diffusivity is found to be appreciably anisotropic. The anisotropy decreases substantially as coverage increases. 2000
Elsevier Science B.V. All rights reserved.

Keywords: Diffusion and migration; Surface diffusion

1. Introduction displacements. As a consequence, very consider-

When atoms are chemisorbed on metal surfaces,
the barriers between adjacent chemisorption wells
are often sufficiently low that the atoms engage in
diffusive motion across the surface. Hydrogen
atoms, with large thermal velocities by virtue of
their light mass, diffuse particularly efficiently. The
motions of these atoms within the chemisorption
well can be quite anharmonic as well, because of
the large amplitudes associated with the thermal
* Corresponding author. Fax: +1 949 824 2174.
E-mail address: dlmills@uci.edu (D.L. Mills)
able effort has been devoted to the study of
hydrogen diffusion on various surfaces.
Additionally, transition metals which incorporate
hydrogen in the bulk as interstitials are of great
technological importance. The study of the
dynamics of hydrogen on and near the surface is
thus a central issue, since hydrogen is introduced
from the gas phase in many circumstances.
Of particular interest, in our view, are the (110)
surfaces of the bcc metals. The reason is that the
basic chemisorption well is quite large, with an
hourglass shape. Within a given well, there are
two equilibrium sites of trigonal symmetry, sepa-

0039-6028/00/$ - see front matter 2000 Elsevier Science B.V. All rights reserved.
PII: S0 0 39 - 6 0 28 ( 99 ) 0 12 5 3 -4
96 E.S. Altshuler et al. / Surface Science 452 (2000) 95107
rated by a barrier referred to as the long bridge
barrier. The physical reason for the barrier is the
presence of an atom in the second layer of the
material, just below the center of the chemisorption
well. In the particular case of W(110), it would
seem that the long bridge barrier is particularly
low, so even at modest temperatures the hydrogen
atoms engage in very large amplitude thermal
motions within the well. The presence of such
highly anharmonic motions renders this a most
interesting system.
That the hydrogen motions are highly anhar-
monic is suggested by the discussion of Norlander
et al. [1]. These authors constructed a hydrogen
tungsten interaction potential, through application
of effective medium theory, to find the long bridge
barrier so low that the bottom of this large chemi-
sorption well is rather flat. Strong evidence for
their picture is provided by the electron energy
loss data reported by Balden and coworkers [2,3].
These authors explored the signature in the
electron energy loss spectrum produced by
hydrogen motions parallel to the surface, and
found very broad loss bands, distinctly different
in nature from those associated by quasi-harmonic
motions. We have explored the frequency spectra
of hydrogen motions in model surfaces with chemi-
sorption wells similar to those proposed by
Norlander et al. [1], to find power spectra close
to those found experimentally [4,5]. In our molecu-
lar dynamics simulations of the hydrogen motions,
it is the appearance of chaotic orbits as temper-
ature is increased which produces the very broad
bands. Further evidence regarding the nature of
the chemisorption well comes from surface entropy
measurements, which show that the adsorption
entropy per hydrogen is very large indeed on this
surface [6 ]. Our model accounts for the data [7].
It would appear that, on Mo(110), the long bridge
barrier is considerably higher than on W(110).
The study of parallel hydrogen motions by the
electron energy loss method shows features much
narrower in width than found on W(110) [8],
suggesting the anharmonicity is much weaker.
Hydrogen may diffuse across such a surface by
surmounting the barrier between adjacent chemi-
sorption wells. This barrier is referred to as the
short bridge barrier. Some years ago, DiFoggio
and Gomer [9] carried out extensive studies of the
diffusion of hydrogen on the W(110) surface.
These authors explored a wide range of coverages
and temperatures. Save for temperatures below
roughly 150 K, thermally activated diffusion was
observed, with an activation energy quite insensi-
tive to coverage. Interestingly, at fixed temperature
the diffusion coefficient increased as coverage
increased. The hydrogen is thus more mobile at
high coverages than at low coverages. Further data
and a more detailed discussion may be found in
the subsequent papers of Gomer and coworkers
[10,11].
In this paper, we discuss theoretical studies of
hydrogen diffusion, for a model of a bcc metal
(110) surface, by the method of molecular
dynamics. Our aim is to explore, within a model
accessible to molecular dynamics, the dependence
of the diffusion rate on coverage, along with the
nature of correlated motions of the adsorbates
over a range of coverages. Although our study is
motivated by the interesting physical picture dis-
cussed above, in fact the model surface we employ
is not a realistic representation of the real W(110)
surface. We need to lower the short bridge barrier
to a value substantially below that appropriate to
W(110) for our atoms to diffuse far enough to
obtain reliable results, in the maximum time we
can utilize for the simulations.
Once this is done, however, we can explore a
wide range of temperatures and coverages, along
with a number of issues of central interest, as
follows. The adsorbed hydrogen atoms interact via
a realistic potential constructed by us earlier [7],
so we may examine correlations in the motions of
nearby hydrogen atoms. We may then extract an
effective short bridge barrier height from the tem-
perature variation of the diffusion constant, and
inquire if this is related in any simple way to the
barrier in our model substrate potential (the
answer is in the negative). We also explore the
coverage dependence of the nature of the jumps
between adjacent chemisorption wells. Clearly, at
low coverages the dominant event must be a jump
into an empty neighboring well. As coverage
increases, however, a hydrogen in a singly occupied
well will make transitions into an already occupied
well, pushing the hydrogen found there to its other
 E.S. Altshuler et al. / Surface Science 452 (2000) 95107
side. We also examine the coverage dependence of
the anisotropy in the diffusion. Thus, although our
model is artificial in the sense that we have short
bridge barriers much lower than found on the
W(110) surface that motivates the study, it is our
view that the above issues are of general interest.
The outline of this paper is as follows. In
Section 2, we discuss the model we have employed,
and also describe the procedures we have utilized
in our simulations. We present the results in
Section 3, and discuss their implications.
Concluding comments are in Section 4.
2. The model and computational procedures
2.1. The model and related comments
We briefly review the model which we have
employed in the studies reported below. We only
summarize its physical content here. Detailed
descriptions, along with explicit expressions for
the model potentials contained in it are to be
found in Refs. [4,5].
We have constructed two model potentials for
the hydrogensubstrate interaction, with the H
W(110) system in mind. As discussed in Section 1,
the chemisorption well is in the shape of an
hourglass, with two equilibrium sites of trigonal
symmetry separated by the long bridge barrier.
The first of these models can be used to reason-
ably represent the interaction of H atoms with the
actual W(110) surface. The short bridge barrier is
250 meV, close to values inferred from data on H
diffusion [911], and the long bridge barrier has
a height of 50 meV, compatible with the potential
put forward in Ref. [1]. It is the case as well that
the various harmonic vibration frequencies for H
motion about the equilibrium sites are close to
those found in electron energy loss studies at low
coverage and reduced temperature.
Although the H motions in this model chemi-
sorption well are indeed highly anharmonic at
elevated temperatures such as the vicinity of room
temperature or above, in our earlier work we also
explored a model in which the underlying anhar-
monicity was very much larger. This model poten-
tial has the short barrier potential set at 50 meV,
97
with the long barrier potential at 10 meV. The
bottom of the chemisorption well is thus very flat,
for this second model. We refer to the two poten-
tials as the high and low barrier models respec-
tively. For both, to reproduce the very high
frequency for the hydrogen vibration normal to
the surface, we add a harmonic potential for
motions in the direction normal to the surface. All
simulations in our previous work and those
reported here are full three-dimensional molecular
dynamics calculations, it should be remarked.
Although the high barrier model can be used
to represent the interaction of H with the actual
W(110) surface, if we were to attempt to study H
diffusion on this surface with molecular dynamics,
far too much time is required for the adsorbates
to diffuse distances sufficient for us to extract
information on the diffusion constant. All of the
calculations reported here have been carried out
for the low barrier model where, as we demonstrate
below, the hydrogen atoms diffuse readily in the
appropriate time scale, at room temperature and
above. Thus, when we discuss the comparison
between our calculations and data, we will focus
our attention on overall trends, rather than quanti-
tative contact between theory and experiment. We
note, however, that it may prove possible to
address the more realistic high barrier model by
rescaling the potential to lower the barriers, and
then also rescale the time; a suitable adjustment
of the strength of the interaction between the
hydrogen atoms is required as well. We are explor-
ing this possibility at present.
We incorporate interactions between the
hydrogen adsorbates within the framework we
developed in our previous paper [5]. There is
charge transfer between the hydrogen adsorbates,
and the substrate, with the consequence that the
hydrogen atoms are partially charged. Thus, the
interactions between the hydrogen atoms on the
surface will have the character of a Coulomb
interaction, screened by the nearby substrate. We
utilize an interaction of Yukawa (or Debye
Huckel ) form for the lateral interactions between
adsorbates. The effective charge per adsorbate is
constrained by the coverage dependence of the
work function. This, along with the screening
length, is chosen so that the dispersion relation
98 E.S. Altshuler et al. / Surface Science 452 (2000) 95107
measured [2,3] for the perpendicularly polarized
hydrogen surface mode is reproduced.
The calculations reported here are thus carried
out for our earlier low barrier model of the
hydrogensubstrate interaction, combined with
lateral interactions between hydrogen adsorbates
modeled as just described.
There is one final point. As emphasized by
Wang and Gomer [10], distinctly different diffusion
coefficients enter discussions of the mobility of
adsorbates on surfaces. One encounters the tracer
diffusion coefficient, defined as follows. One partic-
ular adsorbate atom is selected, its motion is
followed over the surface for a time long enough
for the square of its distance from its starting point
to be linear in time. The tracer diffusion constant
is found from this relation. However, experiments
such as those reported in Refs. [911] monitor not
the motion of a single adsorbate, but rather detect
fluctuations in coverage surely caused by transport
of absorbates from unit cell to unit cell. These
fluctuations are described by a diffusion equation
controlled by a transport coefficient referred to as
the chemical diffusion coefficient. In his review,
Gomer presents a detailed discussion of the rela-
tionship between the two diffusion coefficients [12].
Attention in the present paper is directed to the
tracer diffusion coefficient. It would be of consider-
able interest to calculate both, for the precisely
same model described of the interacting adsorbate
array. As we discuss below, we have encountered
convergence difficulties in an attempt to calculate
the chemical diffusion coefficient.
We turn next to a description of our computa-
tional procedures.
2.2. Computational procedures
We employed the same substrate configuration
used in our earlier work. We have a surface which
contains a total of 400 chemisorption wells,
arranged in a 2020 diamond-shaped array.
Periodic boundary conditions are utilized.
We wish to run simulations at various temper-
atures; as is standard, in our classical molecular
dynamics simulations, the temperature is related
to the time average of the kinetic energy of all the
atoms using 3Nk T. There is a roughly linear
2 B
relationship between the temperature defined in
this manner and the total energy (kinetic plus
potential ) of the array of atoms for each coverage
sampled. Our first step was to determine this
relationship, so that we could pre-select a desired
temperature by setting the array of adsorbates up
with the appropriate total energy. In all runs,
energy conservation was monitored, and main-
tained to the level of 0.01% for the entire system,
over the course of a given run.
We set up an initial configuration for the atoms
as follows. We divided our array of chemisorption
wells into 100 clusters of four neighboring wells.
If we wished to simulate 50% coverage, we would
then place two atoms in each such cluster. At the
beginning of the simulation, the atoms were
arranged so that the total energy of the array was
partitioned equally among the individual atoms.
We calculate the contribution of each atom to the
potential energy of the array. If this is less than
its share of energy, we provide it with a randomly
directed velocity so its kinetic energy accounts for
the deficit. The atom is moved if its contribution
to the potential energy is greater than its energy
fraction.
This provides us with an initial configuration.
We then integrate the classical equations of motion
forward in time, with time steps used in the
underlying integration routine in the range of 50 fs.
We monitor the total kinetic energy until it settles
down to a well defined value according to the
criterion put forward by Allen and Tildesley [13].
If DT is the temperature fluctuation, determined
from fluctuations in total kinetic energy, then we
require DTT(3/2N )1/2, with N the number of
particles. The system would equilibrate in roughly
1000 time steps, in a typical run. We attempted
simulations at coverages lower than 25%, as low
as 10%, to find that, at such low coverages, we
encountered difficulties in reaching a stable equilib-
rium state, as just defined. For these reasons, we
confine our attention to coverages greater than
25%.
At each of the four coverages explored (25, 50,
75 and 100%), we examined the diffusion the
adsorbates at eight temperatures: 200, 250, 300,
350, 400, 450, 500 and 600 K. The total length of
the runs ranged from 100 ps at the higher temper-
 E.S. Altshuler et al. / Surface Science 452 (2000) 95107 99

atures, to 600 ps at the lower temperatures. It is
essential for the adsorbates to diffuse across the
surface far enough, on average, for a diffusion
constant to be defined sensibly. For each atom in
the array, we monitored the quantities,
y2 and
x2. In Fig. 2a, for 25 and 100%
[ x (t)x (0)]2, [ y (t)y (0)]2, and [r (t)r (0)]2,
i i i i i i
where r is the projection of the position vector of
i xx
atom i onto the xy plane. When these quantities,
averaged over the array of atoms, became linear
in time, we could then extract diffusion constants
D , D and D for diffusion in the x direction, the
xx yy
y direction and that associated with the mean
square distance from the starting point.
3. Results and discussion
In Fig. 1, for a coverage of 25% and the eight
temperatures mentioned above, we show the mean
square displacement
r2 of a hydrogen atom as ally coincides with that at 100%, whereas at 50%
a function of time. Of course, for diffusive motion,
we expect this to be linear in time. We see that,
for the time scale shown, indeed we have a linear
dependence on time. Also, the runs cover enough
time so that the H atom has traversed a number
of unit cells. Thus, we may extract a meaningful
diffusion coefficient from the slope of these curves.
For the three other coverages we consider, we find
results quite similar in nature to those given in
Fig. 1.
We may extract D and D from similar plots
yy xx
of
coverages, we display D as a function of temper-
yy
ature, and in Fig. 2b we display D . Two things
are immediately apparent upon comparing the two
sets of results.
First, the diffusion rate in the y direction (the
y axis is parallel to the long dimension of the
hourglass-shaped chemisorption well ) displays a
clear coverage dependence, whereas diffusion in
the x direction (transverse to the long axis of the
well ) is rather insensitive to coverage over a very
wide range of coverages. Our results at 50 and
75% coverages confirm this conclusion. For the
case of diffusion parallel to the y axis, we remark
that at 75% coverage, the diffusion constant virtu-
we find that D falls between that for 25% cover-
yy
age and that for coverages above 75%.
Second, at low coverages, the diffusion across
the surface is quite anisotropic, whereas the anisot-
ropy decreases markedly as coverage increases.
Above 75% coverage the diffusion is virtually
isotropic in nature, despite the fact that the under-

Fig. 1. The mean square displacement of a hydrogen atom from its starting point, in (angstroms)2, for the eight temperatures
considered for the case where the adsorbate coverage is 25%. Temperatures range from 200 to 600 K, as discussed in Section 2.2.
100 E.S. Altshuler et al. / Surface Science 452 (2000) 95107

Fig. 2. For 25 and 100% coverages, we show the temperature variation of the diffusion coefficients for (a) diffusion in the y direction,
parallel to the long axis of the chemisorption well, and (b) diffusion perpendicular to the long axis of the chemisorption well.

lying substrate is itself highly anisotropic. If we
imagine a lattice gas model of the diffusion of an
isolated, single atom on the surface, then the
prefactors of D and D may be expected to scale
xx yy
as follows. Let r =x x+y y be a vector from a
0 0 0
chemisorption site in a given chemisorption well
to the closest chemisorption site in a nearest neigh-
bor well (recall that there are two chemisorption
sites in our hourglass-shaped well ). Then, in a
lattice gas model, the prefactor of D will be
xx
proportional to (x )2, and D is proportional to
0 yy
( y )2. When we discuss our analysis of the diffusion
0
coefficients below, we shall see that, at 25% cover-
age, the ratio of the prefactors in D and D
xx yy
coincides with this expectation, to within the
numerical accuracy of our simulations. Clearly, at
 E.S. Altshuler et al. / Surface Science 452 (2000) 95107 101

all higher coverages this simple picture is violated. Table 1

The prefactors in the various diffusion coefficients, deduced by
One may argue that interactions between the
fitting the numerical data to the activated form D=d exp(D/
hydrogen adsorbates drive the diffusion constants k T ), and similarly for the remaining diffusion coefficients
to an isotropic limit at high coverage. Consider a B
substrate potential with fixed corrugation. Then Coverage (%) d (A2/ps) d (A2/ps) d (A2/ps)
xx yy
imagine increasing the strength of the interaction
25 23.6 42.5 66.1
between adsorbates. In the limit, when the average 50 20.2 23.4 43.3
interaction strength becomes large compared with 75 17.2 20.2 37.3
the modulations of the substrate potential, the 100 26.4 29.4 55.6
latter become irrelevant, and the adsorbate array
behaves as a two-dimensional interacting gas that
is isotropic in character. For a fixed adsorbate 100% coverage as well, though it is somewhat
adsorbate interaction potential, increasing the cov- subdued. The data for D and D are very similar
erage increases its average strength and influence, xx yy
to that displayed in Fig. 3.
thus driving the system toward a limit where its We have fitted curves, such as those just dis-
diffusion is isotropic. cussed, to extract values for both the prefactor
In Fig. 3 we display plots of ln(D) as a function and the effective average diffusion barriers. The
of 1/k T, to inquire if the diffusion coefficient may results are summarized in Tables 1 and 2. To the
B
be fitted by the often-used activated form accuracy of our simulation, we find the diffusion
D=d exp(D/k T ). The answer is yes, with some barrier to be the same in the three diffusion
B
qualification. At the lowest coverage we see that, constants D , D and D. Thus, as we see from
xx yy
with numerical error, we do realize a straight line. Table 1, the anisotropy in the diffusion present at
However, at 50 and 75% we see a clear and distinct lower coverages has its origin in the prefactor, not
kink that we believe is a real feature, and not in the effective barrier for diffusion. Several com-
simply numerical error. This feature is evident at ments follow from the data in Tables 1 and 2.

Fig. 3. The logarithm of the diffusion constant D, plotted as a function of l/k T, for the four coverages considered. The constants
B
D and D behave similarly, when graphed in this manner.
xx yy
102 E.S. Altshuler et al. / Surface Science 452 (2000) 95107
Table 2
The activation barrier D as a function of coverage, found by
fitting the diffusion constants to the activated form D=
d exp(D/k T ). To within the accuracy of the fit, all three
B the range we investigate, then in the units used
diffusion constants considered are described by the same activa-
tion barrier
Coverage (%) Activation barrier (eV )
25 0.080
50 0.069
75 0.071
100 0.088
First of all, the effective diffusion barrier is
remarkably insensitive to coverage. At the higher
coverages, the interactions included between the
H atoms affect the barrier in a remarkably modest
manner. It is not clear to us that the small decrease
in the effective barrier from 25% through 75% is
significant. The fit here may be influenced by the
structure present in the plots of the logarithm of
the diffusion coefficient. A second point is that the
effective diffusion barriers are not related in any
simple way to the model substrate potential. One
expects the H atoms to transfer from one unit cell
to the next across the short bridge barrier. This is
0.05 eV in our model substrate potential, as men-
tioned earlier, and the effective barrier heights are
larger by roughly 50%. The simulation suggests
that, even in the limit where the substrate may be
viewed as rigid, the activation energy in the diffu-
sion constant cannot be taken as a quantitative
measure of features in the substrate potential.
It is also interesting to examine the magnitude
of the prefactors displayed in Table 1. When this
is done, one realizes they lie quite close to the
values expected from very elementary considera-
tions. The prefactor in the diffusion coefficient
should lie in the range nl2 , where n is the attempt
0
frequency, and l a microscopic length characteris-
0 B
tic of the well within which the particle is confined.
There is a factor less than unity which multiplies
this expression, dependent on the precise confor-
mity of the well, for a chemisorption well of
complex shape. One may identify the combination
nl as the mean velocity of the particle in the well,
0
if to a good approximation we have a well with a
very flat bottom, as we do in the present case. If
we take the mean velocity of the H atom in the
well to be that of a hydrogen atom with kinetic
energy of 450 K, a temperature in the middle of
here, the mean velocity is 33.6 A/ps. If we take l
0
to be 2 A, a length characteristic of the long
dimension of the chemisorption well, then we can
see that the prefactors which appear in Table 1 are
quite close indeed to the values expected from the
simple argument just stated. This will be significant
when we review the data in Section 4.
When we initiated these calculations, we
expected to see a strong coverage dependence of
both the diffusion coefficients, and the parameters
that characterize it. It is apparent from the discus-
sion above that the coverage dependence is rather
modest. Consider, for the moment, ones expecta-
tion for the coverage dependence. In the lowest
coverage explored, an adsorbate is surrounded
largely by empty wells, and we expect a tracer
diffusion coefficient quite close to that to be found
for a single, isolated adatom. At 100% coverage,
of course, any given adsorbate is surrounded by
filled chemisorption wells on average. Thus, as it
diffuses, it will hop into a filled well. Suppose it
does so, and suppose also it encounters the resident
adsorbate sitting at the chemisorption site farthest
removed from the well the diffusion atom has just
left. (Recall our hourglass-shaped potential well
has two minima.) Finally, let the newly arrived
atom sit on the second chemisorption site. The
hydrogenhydrogen repulsive interaction used in
our simulations is an empirically determined
screened Coulomb interaction; the adsorbates are
endowed with an effective charge of 0.15e [4]. The
interaction energy between the two hydrogen
atoms, each at a chemisorption minimum in a
single well, is a bit above 150 meV; the two minima
are separated by a distance close to 1 A. This is
an energy very large compared with k T. Thus, at
the higher range of coverages we have explored,
we would expect diffusion to be inhibited by
interactions between adsorbates. In the presence
of such substantive repulsive interactions between
adsorbates, and at high coverages where most
diffusion jumps take the adsorbate into an occu-
pied well, one would expect (in our minds) an
appreciable increase in the effective barrier height.
 E.S. Altshuler et al. / Surface Science 452 (2000) 95107
The results suggest that, at high coverages,
diffusion is highly correlated. As an atom enters
an occupied well, the repulsive interaction with the
resident atom will cause it to push the atom it
encounters into the next well, which is occupied.
We can imagine a chain of such events, with the
adsorbate array adjusting to the appearance of a
new atom in a previously occupied well, in a
collective manner. Such a collective readjustment
would greatly lower the contribution of the repul-
sive interactions between adsorbates on the effec-
tive barrier, since, on average, the mean separation
between adsorbates will remain roughly unchanged
by the collective rearrangement.
The considerations just presented have led us
to inquire into the nature of the jumps made by
an adsorbate, at the various coverages we have
explored. We follow all the atoms motions, and
record whenever any atom surmounts any of the
four short bridge barriers that border the well
within which it is located. We then record whether
it has just left a singly or doubly occupied well,
and whether the well it has just entered is empty
or already occupied by an adsorbate. We thus have
four basic events. (a) The adsorbate leaves a single
occupied well, and enters an empty well. We desig-
nate such an event by the symbol 10. (b) The
atom may leave a singly occupied well, and enter
an occupied well; this event is designated 11. (c)
The atom may leave a doubly occupied well, and
enter an empty well; this is a 20 transition. (d )
The atom may leave a singly occupied well, and
enter an already occupied well; this event is desig-
nated 12.
In Fig. 4a, out of the total number of transitions
an adsorbate makes out of its unit cell during a
run, we show as a function of temperature the
percentage associated with each of the four types
of jump (discussed in the previous paragraph) for
the case where the coverage is 25%. We see that
transitions from an occupied to an empty chemi-
sorption well (10 jumps) strongly dominate at
all temperatures considered. One might then think
that interactions between adsorbates play a minor
role, at this coverage. This is in fact not the case.
Clearly, we have correlated diffusion in this cover-
age range. The reason is that, at 25% coverage, on
average, one of the four nearest neighbor chemi-
103
sorption wells should be occupied. Thus, if the
jumps are entirely random in nature, uninfluenced
by interactions between the adsorbates, the 11
jumps should be 25% of the total. Even at the
highest temperature considered, such processes
only amount to roughly 5% of the total. Thus, the
repulsive interactions between the adsorbates are
forcing a given adatom to have a very strong
preference to move into an empty well, as it
engages in diffusive motion across the surface.
Notice that the number of 11 events, and the
number of 20 are equal at all temperatures. If
our model system is in true thermal equilibrium,
this must be the case if the population of empty
and doubly occupied wells is independent of time,
on average. It will be apparent that these two rates
balance in the remainder of our simulations as
well. This is evidence that indeed we have achieved
thermal equilibrium in our simulations.
In Figs. 4b and 5b(b), we show the percentage
of each class of jump, for the remaining coverages
we have explored. At both 50 and 75% coverages,
the number of jumps into empty wells remains
appreciable; at 75% coverage, nearly half of the
events are of this nature. By the time we reach full
coverage, virtually 70% of the events involve trans-
itions in which either the initial or the final well
are doubly occupied; nonetheless, at the highest
temperature explored, it remains the case that a
bit below 30% remain transitions from single occu-
pied wells, into empty wells.
The information displayed in Figs. 4 and 5
illustrates that as we move from 25% coverage to
100% coverage the nature of the diffusion process
changes dramatically, with a very substantial
increase in processes in which either the initial or
final configuration is a doubly occupied well. This
is perhaps not so surprising. However, we find it
striking that in the face of the very different nature
of the fundamental transitions involved in the
diffusion process, the effective activation barrier
varies little with coverage, and the overall diffusion
constants change by only a factor of three or so
at fixed temperature as one scans this range of
coverages. Two conclusions can be drawn from
this model study. The first is that diffusion con-
stants provide us with rather little information on
the nature of the surface potential felt by this
104 E.S. Altshuler et al. / Surface Science 452 (2000) 95107

(a)

(b)

Fig. 4. Out of the total number of jumps an adsorbate makes out of its chemisorption cell in the course of diffusion, we show, as
a function of temperature, the percentage associated with each of the categories discussed in Section 3, for (a) a coverage of 25%,
and (b) a coverage of 50%.

adsorbates (this conclusion follows from the fact 4. Final remarks

that our effective barrier height differs substantially
from the height of the short bridge barrier); the
second is that the coverage dependence of the
diffusion constant reveals rather little about the
microscopic nature of the processes that control
diffusion.
As we noted earlier, DiFoggio and Gomer [9]
have carried out extensive studies of the temper-
ature and coverage dependence of the diffusion of
hydrogen on the W(110) surface. Further studies
are reported by Gomer and coworkers [10]. At
 E.S. Altshuler et al. / Surface Science 452 (2000) 95107 105

(a)

(b)

Fig. 5. The same as Fig. 4, except that we show the results for the coverages of (a) 75%, and (b) of 100%.

the higher range of temperatures explored in these
studies, it is evident that the diffusion is thermally
activated, so, in principle, one can compare results
of classical molecular dynamics simulations like
those reported here with the data. As we pointed
out above, however, there are two reasons why a
direct and quantitative comparison of our results
with the data cannot be made. First, while we
employ a realistic picture of the nature of the
interactions between the hydrogen adsorbates [5],
we have set the short bridge barrier height far too
low to simulate the actual W(110) surface. This
must be done for our adsorbates to move suffi-
ciently far, on the time scale of our simulations.
Second, our results are for the tracer diffusion
coefficient, whereas the experiment probes a some-
what different transport coefficient, the chemical
diffusion coefficient. Nonetheless, a comparison
106 E.S. Altshuler et al. / Surface Science 452 (2000) 95107
between the trends in our results and the data is
most interesting, in our view. We continue this
section with such a comparison.
One of our principle conclusions is that the
effective barrier for diffusion varies very little with
coverage, over the wide range we have explored.
The data reported in fig. 10 of Ref. [9] shows
virtually no coverage dependence of the effective
barrier height whatsoever, for either hydrogen or
deuterium diffusion, in the coverage range from
10 to 90%, in agreement with the conclusion of
our simulations.
We also find that, in the range of coverages we
have explored, diffusion constants do not depend
very strongly on coverage. At the highest temper-
atures we have explored, at 100% coverage, the
tracer diffusion constant is perhaps a factor of two
smaller than that at 25%. For hydrogen on
W(110), one sees from the activation barriers and
prefactors given in table 1 of Ref. [9] that, at
300 K, at 30% coverage, and at 90% coverage, the
diffusions constants differ by only a factor of three.
Thus, as in our simulations, the coverage depen-
dence of the diffusion constant found experimen-
tally is also rather modest.
However, there is a clear and qualitative dis-
agreement between our simulations and the data
in this regard. We find, with increasing coverage,
that the diffusion constant decreases. The data
show that although the coverage dependence is
not dramatic in the range we have covered, in fact
the diffusion constant increases with coverage.
Surprisingly, the adsorbates diffuse more rapidly
at high coverage.
One may suggest that the coupling between the
adsorbate, and lattice motions in the substrate
may produce this dramatic difference, a notion
also set forward in Ref. [9]. An isolated atom in
its chemisorption well will produce a local lattice
distortion, which must accompany the adatom as
it diffuses, thus increasing its effective mass, possi-
bly substantially. At 100% coverage, where each
adatom on average is surrounded by occupied
chemisorption wells, symmetry forbids such a local
distortion, and the adatom diffuses more readily.
In fig. 9 of Ref. [9], we note that although the
coverage dependence of the prefactor in the acti-
vated form of the diffusion constant is modest in
the range 30 to 90%, in fact it plummets by over
two orders of magnitude as one moves down to
10% coverage. Perhaps by the time one reaches
30% coverage, this polaron effect is partially sup-
pressed. Notice also that, over the entire range of
coverages, the prefactor in the diffusion coefficient
for deuterium increases continuously and dramati-
cally throughout the entire range of coverages.
One may suppose that, for this heavier adsorbate,
in fact coupling to the lattice is substantially
stronger. We also note, of course, that as the
coverage increases the substrate potential may be
altered as well, possibly substantially. Clearly,
there is charge transfer between the adsorbates
and the substrate, with the consequence that the
adsorbatesubstrate potential will in fact be cover-
age dependent, in a manner difficult to model
reliably.
We have seen in our simulations that the pre-
factor in the diffusion coefficient is quite close to
the value one expects for a simple particle in a
box picture of the adatom motion in its chemi-
sorption well. In fact, if we examine table 1 of
Ref. [9], the prefactors are smaller than those we
find by roughly two orders of magnitude. For
example, at 60% coverage the value of the prefactor
in the thermally activated regime is, in our units,
0.5 A/ps, whereas our Table 1 gives 43.3 A/ps.
Perhaps this is further evidence for the role of
substrate distortions. We note that Freed [14],
within a very simple picture of surface lattice
vibrations, has presented a theory of the influence
of lattice distortions on the diffusion of an isolated
H atom on W(110), and Auerbach et al. [15] have
examined the applicability of such a picture to the
data, with emphasis on isotope effects. Clearly,
studies of the coverage dependence of the influence
of coupling to substrate vibrations will prove of
great interest.
We remark that Kurpick et al. [16 ] have
explored the influence of lattice vibrations in the
self-diffusion of single adatoms on noble metal
surfaces. They explore not the polaron effects
discussed above, but rather the influence of lattice
vibrations on the free energy difference between
the adatom as it vibrates about its equilibrium
position in its chemisorption well, and when it
resides in its transition state at the top of the
 E.S. Altshuler et al. / Surface Science 452 (2000) 95107
barrier. These authors argue such effects reduce
the prefactor dramatically, though there is not
universal agreement that this is so: see Ref. [17]
and also the earlier papers in Refs. [18,19]; for a
response to the remarks in Ref. [17], see Ref. [20].
It would be of interest to see if such effects also
influence the diffusion of a light adsorbate such as
hydrogen. We note, of course, that the basic chemi-
sorption well we have used is highly anharmonic,
a statement true of our high barrier model as well.
The conclusions of Ref. [16 ] are based on the use
of harmonic lattice dynamics. More generally, it
is clear that the coverage dependence of the effects
of the coupling between the hydrogen adatoms
and the substrate atom motions is clearly a topic
that requires further study. We hope to address
these issues in future work.
It would be of great interest to calculate the
chemical diffusion coefficient and the tracer diffu-
sion coefficient, within the same model, to see how
the two differ at larger coverages. As noted earlier,
we have attempted to use our method to calculate
the chemical diffusion coefficient, without success.
If D and D denote the chemical and tracer
c t
diffusion coefficients respectively, then if V (t) is
i [6 ] T.U. Nahm, R. Gomer, Surf. Sci. 380 (1997) 434.
the velocity of atom i at time t [12]
P
C D
2 10 895.
V (0)V (t) [9] R. DiFoggio, R. Gomer, Phys. Rev. 23 (1981) 3490.
D N i j
c= 1+ 0 ij . (1)
P
D
(dN)2 2
t
V (0)V (t) [12] R. Gomer, Rep. Prog. Phys. 53 (1990) 917.
i i
0 i
Since, for our model, we have recently evaluated
the power spectra of velocityvelocity correlation
functions [5], we addressed the calculation of the
chemical diffusion coefficient through the use of
Eq. (1), which in essence requires the zero fre-
quency limit of various velocity power spectra.
The autocorrelation function in the denominator
converged nicely, as did the correlation functions
in the numerator beyond the first neighbor shell.
107
However, the correlation functions between near-
est neighbors contained damped oscillations that
decayed somewhat too slowly for us to evaluate
the integrals accurately and reliably, for the run
lengths available to us.
Acknowledgements
The research of E.S.A. and D.L.M. was sup-
ported by the US Department of Energy, through
grant no. DE-DG03-84ER45K083.
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