Surface Science 474 (2001) 114±128

www.elsevier.nl/locate/susc

Adsorption dynamics of CO on Cu(1 1 0): a molecular beam

study
M. Kunat, Ch. Boas, Th. Becker, U. Burghaus *, Ch. W
oll
Physikalische Chemie I, PC 1, Ruhr-Universitat Bochum, Universitatsstrasse, 44780 Bochum, Germany
Received 30 September 2000; accepted for publication 27 November 2000

Abstract
Molecular beam measurements of initial adsorption probabilities, S0 , as well as the coverage dependence of the
adsorption probability, S…H†, of CO on Cu(1 1 0) are presented. The in¯uence of kinetic energy, polar impact angle, ai ,
azimuthal orientation ([1 0 0] and [1 1 0]), and adsorption temperature, Ts , on the adsorption dynamics have been
studied. With regard to microkinetical models used to describe processes in heterogeneous catalysis, the dependence of
the adsorption probability on the density of defects has been investigated. The surface has been characterized by
measuring He atom angular distributions, He atom re¯ectivity curves, and LEED. The shape of the S…H† curves are
consistent with a precursor mediated adsorption mechanism. For low temperatures Ts 6 90 K, the adsorption dynamics
are dominated by adsorbate assisted adsorption. Despite the pronounced di€erence in the surface corrugation along the
di€erent high-symmetry directions no signi®cant di€erences in S0 and S…H† were observed for the di€erent azimuths
studied. Ó 2001 Elsevier Science B.V. All rights reserved.

Keywords: Adsorption kinetics; Catalysis; Chemisorption; Sticking; Copper; Single crystal surfaces; Surface defects; Solid±gas
interfaces

1. Introduction single crystal) were collected in the course of a long

A detailed knowledge of the adsorption dy-
namics (see e.g. [1,2]) of prototype molecules (such
as CO, CO2 , H, etc.) adsorbed on metal/metal-
oxide substrates [3±6] is necessary for unraveling
the fundamental mechanisms in heterogeneous
catalysis. Technically important examples are the
water±gas shift reaction [7], methanol synthesis [7],
and the CO oxidation reaction [8±11]. The data
presented here (CO adsorption on a Cu(1 1 0)
*
Corresponding author. Fax: +49-234-32-14182.
E-mail address: burghaus@pc.ruhr-uni-bochum.de (U. Burg-
haus).
term investigation about CO adsorption dynamics
on ultrathin copper layers deposited on ZnO single
crystals. Consequently, we have ®rst studied the
adsorption of CO on the corresponding clean
surfaces. Recently, molecular beam measurements
about the adsorption dynamics of CO on the polar
surfaces of ZnO [12±14], as well as the interaction
of CO with atomic hydrogen on ZnO [15] have
been conducted. In this study, we present adsorp-
tion probability measurements of CO on Cu(1 1 0)
along the two high-symmetry crystallographic
directions ([1 1 0] and [0 0 1]), parametric in po-
lar angle, ai , total impact energy, Ei …ai ˆ 0°†, ad-
sorption temperature, Ts , and density of defects.

0039-6028/01/$ - see front matter Ó 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 3 9 - 6 0 2 8 ( 0 0 ) 0 1 0 4 1 - 4
 M. Kunat et al. / Surface Science 474 (2001) 114±128
Additionally, the coverage dependent re¯ectivity
[12,13,16,17], I…H†, of the surface for He atoms
has been measured for the Cu(1 1 0) surface, as
well as for Cu(1 1 0) sputtered by Ar‡ ions.
1.1. Survey of the literature
Although the adsorption dynamics [18±20] of
CO has been investigated in considerable detail for
most of the catalytic active metal surfaces (see,
e.g., Pt [21±23], Pd [18,24], Ag [21], Ni [25], Rh
[22], Ir [26,27], Ru [28,29], etc.), to the best of our
knowledge, no detailed study about adsorption
probabilities has been performed so far for Cu
single crystals. Most of the reports about CO ad-
sorption on Cu surfaces have been carried out
using IRAS [30±33], HREELS [34], XPS [34,35],
and TDS [36±39]. Most of these studies have fo-
cussed on the Cu(1 1 1) surface. Stimulated in part
by technical applications related to heterogeneous
catalysis [7,11,40], a large number of publications
(see, e.g. [20,34,35,41]) deals with the coadsorption
of alkali metals and prototype molecules on cop-
per surfaces. Additionally, a number of studies
about CO adsorption are related to bimetallic Cu/
metal systems (see, e.g. [28,29,36,41]) and Cu/
metal-oxide systems (see, e.g., [4,5]).
Adsorption probabilities of CO on Cu single
crystal surfaces have so far only been estimated by
TDS, with numerical values of S0 (for Cu(1 1 0))
ranging from 0.46 [39] up to one [36,38] under
apparently identical measuring conditions. The
results presented here can be best compared (see
discussion) with the molecular beam study of
Kneitz et al. [28,29]. In that work CO adsorption
on a Cu(1 1 1) multilayer epitaxially grown on
Ru(0 0 0 1) has been studied. The molecular and
non-activated adsorption dynamics [28,29] were
generally found to be consistent with a precursor
mechanism. Additionally, at very large impact
energies …Ei > 1:0 eV† an increase in S with H has
been detected (frequently called ``adsorbate as-
sisted adsorption'') which was found to be largely
independent of adsorption temperature.
A heat of adsorption decreasing from 54 to 42
kJ/mol (with a pre-exponential factor of m ˆ
2  1013 1/s) with increasing coverage has been
determined for CO/Cu(1 1 0) [35,39] by TDS,
115
thereby indicating a repulsive interaction of the
CO molecules [35]. For adsorption of CO below 35
K (on Ag(1 1 1)), multilayer formation has been
observed by TDS and HREELS [42].
According to LEED [35], He atom di€raction
[43], and photoelectron di€raction [44] studies,
adsorption of CO at low temperatures (below 110
K) leads to the formation of a disordered overlayer.
Annealing at higher temperatures (170 K) [39] re-
sults in the formation of an ordered …2  1†-over-
layer. According to previous LEED-studies further
exposure leads to compressed structures [35].
1.2. Possible in¯uence of impact angle and azimuth
on S0 and S…H†
The dependence of adsorption probabilities on
the azimuthal orientation of the substrate has been
investigated experimentally (see e.g. [45±47]) only
in a very limited number of studies. However,
knowledge about the in¯uence of the azimuthal
orientation on adsorption probabilities or, in other
words, detailed information about the in¯uence of
parallel and perpendicular momentum of the im-
pinging particles on the corresponding adsorp-
tion probabilities is of fundamental interest in
gaining a deeper understanding about the mecha-
nisms for energy transfer processes in gas±surface
interactions [1,2]. Therefore, we extended the
measurements and have determined adsorption
probabilities along the two high symmetry crys-
tallographic orientations of the Cu(1 1 0) surface.
The dependence of S0 and S…H† on the polar angle
has also been studied. (Note, that for normal in-
cidence (ai ˆ 0°) the two azimuths are equivalent,
di€erences are expected only for polar angles dif-
ferent from 0°.) Regarding the larger corrugation
of the surface along the [0 0 1] azimuth as com-
pared to the [1 1 0] azimuth, in the former case
total energy scaling, S0 …Ei ; ai †  S0 …Ei ; 0°†, of S0
might be expected while in the latter case nor-
mal energy scaling, which obeys S0 …Ei ; ai † 
S0 …Ei cos2 ai ; 0°†, should be ful®lled. The situation
might become more complicated if energetic
(magnitude of barrier height varies along the sur-
face) and geometric (constant barrier height but
variations in the vertical location) corrugations of
the surface come into play [2,48]. In previous
116 M. Kunat et al. / Surface Science 474 (2001) 114±128
studies the presence of a small anisotropy of the
CO/Cu(1 1 0) potential energy surface has been
reported [43,49]. A small change in the energies of
the frustrated translation parallel to the surface (T-
mode) of isolated CO molecules along [0 0 1] and
[1 
1 0] has been observed [43], as well as a di€erent
temperature dependence of the ESDIAD desorp-
tion patterns [49]. Therefore, the Cu(1 1 0) surface
is a promising system to observe an in¯uence
of the azimuthal orientation on the adsorption
probability. Furthermore, due to changes in the
surface corrugation induced by CO adsorption on
Cu(1 1 0) (which depends on the azimuth) [31,43,
44,50] a variation of S…H† with the azimuthal
orientation and polar angle of incidence can also
be expected. To the best of our knowledge, so far
only two systems are known where S0 showed a
dependence on the azimuth and polar impact an-
gle, namely the dissociative adsorption of O2 on
Ag(1 1 0) [45,51] and the molecular adsorption of
propane on Pt(1 1 0) [46].
2. Experimental procedures
The measurements were conducted using a su-
personic molecular beam system. Brie¯y, the mo-
lecular beam source is attached to a scattering
chamber and to a di€erentially pumped drift tube.
The total scattering angle, ai ‡ af , is ®xed to 90.5°.
However, incidence (polar), ai , and scattering an-
gles, af , respectively, can be changed by rotating
the sample. Furthermore, the azimuthal and tilt
angle of the surface can be varied in situ. The
scattering chamber contains a quadrupole mass
spectrometer (Balzers QMA 112A) with its en-
trance aperture positioned behind the crystal for
adsorption probability measurements (by means of
the King and Wells method [52]), a LEED system
(Omicron), and a di€erentially pumped sputter gun
(Leybold, EQE12/38). At the end of the drift tube a
second magnetic mass ®lter, optimized for the de-
tection of He atoms, is mounted. The alignment of
the whole beam-surface geometry has been opti-
mized and controlled by He atom scattering. The
diameter of the CO beam at the sample position is
4 mm and the size of the square shaped ZnO
sample amounts to 10  10 mm2 .
The translational energy of the CO was varied
between Ei ˆ 0:045 and 0.575 eV by adjusting the
nozzle temperature in the range of 300±500 K and
by seeding 3% of CO in Ar or He, 20% CO in He,
and by using a pure CO beam. The beam energy
has been determined by time of ¯ight measure-
ments of the He carrier gas (assuming equal ve-
locities for the seeded and carrier gas). The
experimentally determined values agreed within
10% with impact energies as calculated by the
approximation [53]
XCO CCO ‡ XHe CHe
Ei …CO† ˆ kB mCO TN …1†
XCO mCO ‡ XHe mHe
(Xxx percentage of CO and He in the beam gas, Cxx
heat capacity at constant pressure of CO or He,
mxx mass of He or CO, kB BoltzmannÕs constant,
TN gas temperature.) Therefore, this approxima-
tion has been used for calculating the energies of
the CO/Ar mixtures in those cases where the ve-
locity distribution of the carrier gas could not be
measured. For the pure CO beam (with TN ˆ 300
K and similar expansion conditions), a kinetic
energy of 85 meV has been reported elsewhere (see
Ref. [10]). The expansion conditions used (nozzle
diameter 20 lm and nozzle pressure < 15 bar)
guarantee that a signi®cant velocity slip with v(rare
gas) 6ˆ v(seeding gas) can be excluded.
By using seeded beams, the coverage depen-
dence of the He atom re¯ectivity, I…H†, and ad-
sorption probability, S…H†, of the surfaces,
respectively, could be determined simultaneously,
thus providing complementary information about
scattering cross-sections for di€use He atom scat-
tering, R, adsorption probabilities, and the in¯u-
ence of defects on the adsorption process [12,16].
For the calculation of the initial adsorption
probability from the King and Wells curves, the
vacuum time constant is taken into account by
ignoring the ®rst data points after the initial
pressure rise and by extrapolating linearly back to
the beginning of the re¯ectivity curve, when the
beam-¯ag was opened.
Crystal heating is accomplished by electron
bombardment of the back of the sample holder.
A He cryostat allows measurements for adsorp-
tion temperatures down to about 35 K. Crystal
temperature is monitored using a cromel/alumel
 M. Kunat et al. / Surface Science 474 (2001) 114±128
thermocouple which is attached to the edge of the
crystal. The temperature reading is calibrated
in situ to within 10 K by TDS (heating rate 2
K/s) measurements of multilayers of n-butane
(desorption temperature TD ˆ 111 K) and iso-
butane …TD ˆ 107 K) in agreement with Ref. [54].
The crystal was cleaned by cycles of Ar‡ sput-
tering (900 V, 1 lA, 30 min, Ts ˆ 300 K) fol-
lowed by annealing in an oxygen ambient and in
UHV (Ts  900 K, 1 min), using procedures al-
ready employed in previous investigations [55].
The preparation cycles were continued until a
sharp LEED pattern, distinct He atom di€raction
peaks, and a day-to-day reproducibility of S0
within an uncertainty of 0.05 was achieved.
Additionally, the Cu(1 1 0) crystal used here has
been characterized in the same apparatus by in-
elastic He atom scattering [43,55]. The gases em-
ployed were of research purity (99.9999% for He
and 99.99% for CO from Messer Griesheim).
3. Data presentation
3.1. Structure of the surface
Fig. 1 presents He atom angular distributions of
the clean and the CO covered Cu(1 1 0) surface
Fig. 1. He atom angular distributions recorded for the clean and CO covered Cu(1 1 0) surface. Panels A and B shows the results for
the [1 
1 0] azimuth; and in C and D those for the [0 0 1] azimuth.
117
along the two high-symmetry azimuthal directions.
Whereas the corrugation of the clean surface along
the [1 1 0] azimuth is extremely small, as evidenced
by the absence of any di€raction peaks along this
direction (see Fig. 1B); along the [0 0 1] azimuth
distinct ®rst and second order di€raction peaks
could be observed (see Fig. 1D).
Adsorption of CO for Ts < 90 K results in a
strong attenuation of the specular He atom in-
tensity without the formation of additional dif-
fraction peaks (not shown). Adsorption of CO for
higher substrate temperatures …Ts P 90 K† yields
an increase in the intensity of the di€raction peaks,
as compared to the clean surface, along the [0 0 1]
azimuth (Fig. 1C). Along the less corrugated [1 1 0]
direction of the Cu(1 1 0) surface, adsorption of
CO at Ts P 90 K resulted in the formation of dif-
fraction peaks (Fig. 1A).
3.2. Initial adsorption probability
Figs. 2 and 3 summarize the dependence of S0
on impact energy, adsorption temperature, and
polar angle, respectively.
Fig. 2A shows the impact energy dependence of
S0 for normal incidence of the CO beam and
Ts ˆ 90 K. S0 is decreasing with Ei , as indicated
by the solid line, which is provided as a guide for
118 M. Kunat et al. / Surface Science 474 (2001) 114±128
the eye. The results of Kneitz et al. [28,29] for CO
adsorption on Cu(1 1 1)/Ru(0 0 0 1) and S0 values,
as determined in prior studies by TDS [36,38,39],
are also displayed. Fig. 2B depicts typical exam-
ples of the temperature dependence of S0 , para-
metric in impact energy (measured at ai ˆ 45° and
along both azimuthal directions). It is evident that
S0 is independent of Ts in the temperature
range of 35±190 K within the experimental un-
certainty.
Fig. 2. (A) Energy dependence of the initial adsorption prob-
ability for normal incidence and Ts ˆ 90 K. The solid line is the
result of an exponential ®t to the data, included as a guide for
the eye. Results from Refs. [28,29] (dashed line) and Refs.
[36,38,39] (as indicated) are additionally shown. (B) Tempera-
ture dependence of S0 , parametric in impact energy (for
ai ˆ 45°) and for both azimuths studied.
Fig. 3 presents the initial adsorption probability
of CO at Ts ˆ 90 K (Fig. 3A) and at Ts ˆ 50 K
(Fig. 3B), as a function of polar angle, parametric
in total impact energy and along both high-sym-
metry azimuthal directions. For impact energies
below 0.077 eV, S0 is independent of ai for both
azimuthal orientations. For Ei > 0.357 eV a small
decrease in S0 has been observed with increasing
ai , which is slightly more pronounced along the
[0 0 1] azimuth than along the [1 1 0] direction. Al-
though this trend could be well reproduced, the
change in S0 with ai is still within the experimental
uncertainties.
Fig. 3. Initial adsorption probability of CO as a function of
polar angle and for both high symmetry azimuthal directions,
parametric in impact energy. (A) High and (B) low adsorption
temperature, respectively.
 M. Kunat et al. / Surface Science 474 (2001) 114±128 119

3.3. Coverage dependence of the adsorption proba-

bility

Figs. 4±6 summarize the coverage dependence of

S. Fig. 4 depicts the dependence of S…H† on total
impact energy and for both azimuths (at ai ˆ 45°)
for high (Fig. 4A) and low (Fig. 4B) adsorption
temperatures, respectively. For a better compari-
son of the curve shapes, the actual numerical val-
ues of S0 are normalized with respect to the [0 0 1]
azimuth. Fig. 5 shows the polar dependence of
S…H† for high (Fig. 5A) and low (Fig. 5B) ad-
sorption temperatures, respectively, but for con-
stant total impact energy. Finally, Fig. 6A depicts
typical examples for S…H†, parametric in adsorp-
tion temperature, but for constant impact para-
meters. The thin solid lines, which are additionally
included, are the result of a ®t with the Kisliuk
model [56]. Fig. 6B shows the temperature de-
pendence of the saturation coverage of CO and He
atom re¯ectivity, respectively.
The saturation coverages have been determined
by integrating the King and Wells curves. Within
the temperature range of Ts ˆ 35±50 K the result-
ing coverages were within an uncertainty of 20%
independent of Ts (see Fig. 6B). For this temper-
ature range the saturation coverages, Hsat , are in
all ®gures set to 1 ML …ˆ maximum coverage† and
the curves for larger temperatures (cf., Fig. 6A) are
Fig. 4. Coverage dependent adsorption probability as a func-
normalized accordingly. According to the He atom tion of impact energy (for ai ˆ 45° along both azimuthal ori-
angular distributions, CO forms a …2  1† struc- entations). (A) At high adsorption temperature (90 K) and (B)
ture under the present conditions. Therefore, the at low adsorption temperature (50 K).
largest saturation coverage obtainable amounts
absolutely to a density of 5:4  1014 particles/cm2 ,
At Ts ˆ 90 K and for ai ˆ 0° an initial increase
i.e. the coverage amounts to 0.5 ML with respect
of S with H has been detected (see solid line in Fig.
to the density of Cu-atoms in the top surface
5A presented as a guide for the eye). Although no
plane.
dependence of S…H† on the azimuth has been ob-
served (Fig. 4A), S starts to decrease for more
3.3.1. High adsorption temperatures
glancing angles of incidence faster with increasing
For 90 < Ts < 120 K and a P 45°, S…H† remains
H than for normal incidence (Fig. 5A).
approximately constant and is independent of H
(see Fig. 4A and also Fig. 6A). Only when the
coverage approaches saturation S drops to zero, as 3.3.2. Low adsorption temperatures
expected. The curve shapes show no signi®cant For 35 < Ts 6 90 K the curve shapes are domi-
dependence on azimuthal orientation (see Fig. 4) nated by an initial increase of S with H (see Fig.
and are independent of the total impact energy; 4B, the curve for ai ˆ 0° in Fig. 5A and B), again
only the initial adsorption probability is found to independent of the azimuthal direction (Fig. 4B),
decrease with Ei (cf., Fig. 2). but with a weak dependence of the slope, c, of
120 M. Kunat et al. / Surface Science 474 (2001) 114±128
Fig. 5. Polar angle dependence of S(H). (A) At high adsorption
temperature (90 K, cf., Fig. 3A, S0 normalized to the averaged
value) and (B) at low adsorption temperature (50 K, cf., Fig.
3B).
S…H† vs. H on impact energy (Fig. 4B). The in-
crease in S with H is most distinct for normal
angles of incidence (Fig. 5). A closer inspection of
the curve shapes shows that the S…H† curves con-
sist for Ts 6 90 K and large impact energies of two
di€erent regimes (see Fig. 5B): a linear initial in-
crease of S with H is followed by a linear attenu-
ation of S with H (the turning points are labeled
by short arrows in Fig. 5B), until S drops to zero
when the saturation coverage has been reached.
With increasing angle of incidence, the turning
point, where S starts to decrease, shifts to slightly
smaller CO coverages.
Fig. 6. (A) Coverage dependent adsorption probability as a
function of adsorption temperature for ai ˆ 45°, Ei ˆ 0:077 eV
and along the [1 1 0] azimuth. The thin lines are a result of a ®t
with the Kisliuk model. According to Eq. (2), K is in the range
of 0.025±0.45 for Ts ˆ 90±190 K with a functional form which
might be expressed as K ˆ 5  10 6  exp…0:058  Ts † with Ts
in K. (B) Temperature dependent saturation coverage of CO
(symbols) and temperature dependent specular He atom in-
tensity (solid line) as well as the 1st derivative (thin line) of the
He atom re¯ectivity curve.
3.4. Adsorption kinetics
The steady-state saturation coverages, as deter-
mined by integrating the King and Wells curves
(see Fig. 6B), are decreasing slowly with increasing
Ts , until the thermal desorption temperature of
CO (TD  200 K for a heating rate of 2 K/s) is
reached and Hsat drops to zero. The temperature
dependence of the He-atom re¯ectivity (sometimes
called inverse TDS or He-TDS) shows the oppo-
site trend (see Fig. 6B), as expected. The step-like
 M. Kunat et al. / Surface Science 474 (2001) 114±128 121

increase of the re¯ectivity with Ts is followed by an
exponential decay towards higher surface temper-
atures, which is due to the temperature dependence
of the Debye±Waller factor.
3.5. In¯uence of defects induced by sputtering
The in¯uence of defects as generated at low tem-
peratures by Ar‡ ion sputtering of the Cu(1 1 0)
surface on S…H† and I…H† is summarized in Fig. 7.
For comparison, the corresponding results of
the system CO/Zn±ZnO [12,13] are also shown.
The data depicted in Fig. 7 for the CO/Cu(1 1 0)
system corresponds to a Cu(1 1 0) surface sput-
tered at a temperature of Tsp ˆ 50 K (normal
incidence, Ar-ion energy of 2 keV) and CO ad-
sorption at Ts ˆ 50 K.: To inhibit di€usion of Cu
surface atoms a low sputtering temperature has
been chosen. However, virtually identical results
for S…H† and I…H† have been obtained for Ts and
Tsp up to 150 K. The Ar‡ ¯uence, v…Ar‡ †, as in-
dicated in Fig. 7, is normalized [17] with respect
to the particle density, [ML], of the surface, i.e.,
v…Ar‡ † ˆ …sputtering current  sputtering time†=
…e  ‰MLŠ†, with e denoting the electron charge.
To detect the coverage dependence of the He atom
re¯ectivity, I…H†, (as shown in Fig. 7A) and the
coverage dependent adsorption probability (see
Fig. 7B) simultaneously, a seeded CO beam (3%
CO in He) incident at a polar angle of 45° has been
used. To compare the curve shapes, the S…H†
curves as well as the I…H† curves obtained for
Cu(1 1 0) were normalized to one. To estimate the
size of terraces on the Cu(1 1 0) surface, the
transfer width for He atoms, C, has been deter-
mined from the width of the elastic peak of the
corresponding He atom angular distributions (in-
dicated in Fig. 7).
Fig. 7A reveals that fairly large ¯uences of Ar‡ -
ions are required to cause signi®cant changes in
the CO adsorption dynamics relative to the perfect
surface. For normalized ¯uences of 0.6 ML, hardly
any di€erence is visible, whereas for ¯uences of 3.0
ML noticeable changes are present. The shape of
the I…H† curves for the sputtered surface also ex-
hibits signi®cant di€erences to the results obtained
for a Zn±ZnO surface, the latter showing a much
slower attenuation of I…H† with H [12]. (Sputtering

Fig. 7. In¯uence of defects as generated by Ar‡ sputtering of the surface at 50 K. (A) He atom re¯ectivity and (B) coverage dependent
adsorption probability (normalized to S0 ˆ 1). The corresponding results for a Zn±ZnO surface (open spheres) from Refs. [12,13] are
included for comparison as well as the result of a simple kinetic model (solid lines in panel A).
122 M. Kunat et al. / Surface Science 474 (2001) 114±128
of the Zn±ZnO surface did not change the shape of
the I…H† or S…H† curves signi®cantly [14].) Addi-
tionally displayed (solid lines) in Fig. 7A are the
results of a simple kinetic model (see discussion).
In Fig. 7B the coverage dependent adsorption
probabilities for CO/Cu(1 1 0) and CO/Zn±ZnO
are shown. For both adsorbate systems an initial
increase in S with H has been observed for the
non-sputtered surfaces which was for both systems
most distinct for low Ts and high Ei (see Section
3.3). With increasing density of defects, however,
the initial increase in S with H is strongly sup-
pressed for the CO/Cu(1 1 0) system. Although S0
was independent of v…Ar‡ † for CO adsorption on
Cu(1 1 0) and Zn±ZnO [14], S0 decreased with
v…Ar‡ † for O±ZnO [12].
4. Discussion
4.1. Structure of the CO overlayers
The object of the present He atom di€raction
measurements was a characterization of the sur-
face structure under conditions typical for the
presented King and Wells adsorption probability
measurements, rather than a full characterization
of the CO overlayer structures, which have already
been studied in detail (see Refs. [31,42±44,49,50]).
The LEED-patterns and the He atom angular
distributions reveal the presence of a structurally
well de®ned Cu(1 1 0) surface. The high angular
resolution of the molecular beam system allows the
determination of the coherence length, C, (average
terrace size) of the surface from the width of the
di€raction peaks. After extensive sample prepara-
tion C amounts to 200±300 A  for the clean surface;

values of C150 A have been regularly achieved.
For adsorption of CO at temperatures below
approximately 50 K the strong attenuation of the
specular He atom intensity without the formation
of di€raction peaks indicates the presence of a
disordered CO layer (in agreement with Refs.
[31,40,45]); i.e., the formation of ordered overlay-
ers appears to be kinetically hindered at these low
temperatures.
Adsorption of CO at 90 K resulted in the de-
velopment of distinct di€raction peaks (in the case
of [1 1 0] see Fig. 1A and C). The di€raction pat-
tern is fully consistent with a …2  1†-CO overlayer
with Hsat ˆ 0:50 ML. The slightly larger temper-
atures reported before (120 K [39]) which were
necessary to induce an ordering of the CO layer
might be related to the calibration of the thermo-
couple reading rather than to di€erences in the
adsorption kinetics.
4.2. Initial adsorption probabilities
4.2.1. S0 (Ei ) and S0 (Ts )
The initial adsorption probabilities for CO are
for most transition metal surfaces (see, e.g. Pt
[21,22], Pd [24], Ir [26,27]) and thermal impact
energies (Ei equals approximately 0.05 eV for a
room temperature Maxwellian beam) close to one.
The same result is reported here for CO on
Cu(1 1 0) (Fig. 2A) namely S0 ˆ 0:95  0:05 (for
normal incidence and Ei ˆ 0:046 eV), in agreement
with careful estimates of S0 from TDS [36,38]
studies. Commonly a decrease of S0 with Ei has
been detected for CO adsorption on di€erent
substrates. However, di€erences in the functional
form of this decrease have been reported, indicat-
ing thereby di€erences in the details of the energy
accommodation processes. The present results
for CO/Cu(1 1 0) can be best parameterized by
an exponential function …S0 …Ei † ˆ 0:72 exp … Ei =
0:39† ‡ 0:31, with Ei in eV† rather than by a linear
decrease of S0 with Ei , as observed e.g. for CO/
Ir(1 1 0) [26,27]. Despite the fact that parameter-
izations of adsorption probability data are fre-
quently rather arti®cial, we have included this type
of information since it is required for the modeling
of surface reactions involving CO. (Examples for
kinetic models of this kind can be found e.g. in
Refs. [40,57].)
The numerical values for the initial adsorption
probabilities of CO as measured for a Cu(1 1 1)
surface (obtained by multilayer adsorption of Cu
on Ru(0 0 0 1) in Refs. [28,29]) are in perfect
agreement with the data presented here for CO/
Cu(1 1 0) (see dashed line in Fig. 2A from Ref.
[28]). However, extrapolating the exponential ®t of
the data for CO/Cu(1 1 0) leads for large Ei to
slightly larger (by about 20% at Ei ˆ 1:0 eV) val-
ues of adsorption probabilities (higher reactivity
 M. Kunat et al. / Surface Science 474 (2001) 114±128
towards CO adsorption) as compared to Cu(1 1 1).
Regarding the surface corrugation which is sig-
ni®cantly larger for Cu(1 1 0) than for Cu(1 1 1),
this trend might be expected, and should indeed be
most pronounced for large impact energies. The
decrease of S0 with increasing Ei is consistent with
the following standard model (see e.g. [26±28]):
With increasing velocity of the impinging particles
also the interaction time with the surface is de-
creasing. Therefore, the adsorption probability in
a precursor state will decrease with Ei . The results
reported here are thus consistent with a precursor
mediated adsorption of CO on Cu(1 1 0).
Adsorption of CO on Cu(1 1 0) turned out to be
non-activated, i.e., S0 is independent of adsorption
temperature (see Fig. 2B), as commonly observed
for CO adsorption on surfaces of other metals and
on Cu [36,38]. Note, however, that Harendt et al.
[39] reported a decrease of S0 with Ts by estimating
adsorption probabilities from TDS data. Note,
however, that a precise determination of adsorp-
tion probabilities by TDS is challenging and fre-
quently leads to large uncertainties.
4.2.2. S0 (ai ,Ei )
The corrugation along the two high symmetry
directions of the clean Cu(1 1 0) surface is quite
di€erent (see Fig. 1B and D). As a result, one
would expect an in¯uence of the azimuth orienta-
tion on S0 . More precisely, deviations from total
energy scaling should be more pronounced along
the less corrugated [1  1 0] direction than for the
[0 0 1] azimuth. Surprisingly, however, S0 is (see
Fig. 3) within the experimental uncertainties for
the [1 
1 0] and [1 0 0] azimuths independent of the
angle of incidence (irrespective of Ts and Ei ). Only
a slight decrease …DSmax  0:1† in S0 with polar
angle (for large Ei ) might be concluded from Fig.
3, which is for the [0 0 1] azimuth slightly more
distinct than for the [1 
1 0] azimuth, independent of
Ts . Therefore we tentatively conclude that the CO
induced variation of the surface corrugation along
the [1 1 0] azimuth induces a more ecient cou-
pling of the parallel and perpendicular compo-
nents of the momentum (of the impinging CO
molecules) than the CO induced corrugation along
the [0 0 1] direction. Under this assumption a
slightly more distinct deviation from total energy
123
scaling along the [0 0 1] direction as compared to
the [1 1 0] azimuth would be expected.
Another explanation for the observed total en-
ergy scaling might be to consider impact-induced
rotational excitations of the CO molecules (cf., e.g.
[58,59]). The energetically activated CO molecules
might then be trapped in a precursor state, a sit-
uation well known from studies about bound state
resonances of rare gas atoms. The energy transfer
to the substrate of molecules with excess rotational
energy trapped in a precursor state might than be
dominated by surface defects rather than by the
surface corrugation.
However, in the molecular beam studies about
O2 /Ag(1 1 0) [45,51] and propane/Pt(1 1 1) [46] a
much more distinct variation in S with polar angle
and/or azimuthal orientation has been observed
(DSmax  0:25 for both systems).
4.3. Coverage dependence of the adsorption proba-
bility
4.3.1. Adsorption dynamics for Ts > 90 K
That the adsorption of CO on Cu(1 1 0) can be
described by a precursor-mediated and non-acti-
vated molecular adsorption mechanism (see Sec-
tion 4.2.1) is nicely demonstrated by the shape of
the coverage dependent adsorption probabilities:
For a simple direct adsorption mechanism of
Langmuirian type kinetics, the coverage depen-
dence of the adsorption probability is given by
S…H† ˆ S0 …1 ‡ c0 H† with c0 ˆ 1 for randomly
distributed admolecules without lateral interac-
tions. As evident from Fig. 4A, even for the larg-
est impact energies used in this work the slope of
the S vs. H curves c ˆ S0 c0 is close to zero …c ˆ
0:05  0:02 for Ei ˆ 0:077 eV up to 0.575 eV†
independent of the azimuth, i.e., S…H†  S0 until
saturation is reached and S drops to zero. This
curve shape is consistent with the traditional Kis-
liuk type precursor mechanism which for molecu-
lar adsorption yields [56]:
  1
H Pe
S ˆ S0 1 ‡ K and K ˆ
…2†
1 H Pi ‡ Pia
Here Pe and Pi denote the desorption probability
into the gas phase from an extrinsic and intrinsic
124 M. Kunat et al. / Surface Science 474 (2001) 114±128
precursor state, respectively, and Pia denotes the
adsorption probability from the intrinsic precursor
state. When precursor states are present, S be-
comes independent of H, especially at low Ts (due
to large lifetimes of the precursor state) and low Ei
(due to large adsorption probability into the pre-
cursor states). The smaller the numerical value of
K is (with 0 < K 6 1:0), the smaller becomes the
decrease in S with increasing H, i.e., the more
important are the precursor states for the ad-
sorption dynamics. (In the limit of K ˆ 1, i.e.,
without assuming precursor states, Eq. (2) yields
the Langmuirian kinetics.) A parameterization of
the S…H† curves in Fig. 4A according to Eq. (2)
yields K ˆ 0:07  0:02 approximately independent
of Ei , indicating thereby the importance of pre-
cursor states. This result is in contrast, e.g. to NO/
Ni(1 0 0) [60] where a more pronounced cross-over
from Kisliuk to Langmuirian (direct) kinetics has
been observed with increasing impact energy.
4.3.2. In¯uence of polar impact angle for Ts > 90 K
on S…H†
For 90 < Ts < 120 K and for glancing incidence
of the CO molecules S…H† decreases faster with H
as in the case of normal incidence (see Fig. 5A). A
numerical analysis yields that the slope of S vs. H
curves, c, decreases from c ˆ 0:05 (for ai ˆ 0°) to
c ˆ 0:19 (for ai ˆ 60°). Thus, despite the fact
that total energy scaling is obeyed for the initial
adsorption probabilities (see Fig. 2 and Section
4.2), the normal momentum component is appar-
ently enhancing the energy transfer process for
larger coverages of CO. This e€ect is not generally
observed, for example in the case of O2 /Ir(1 1 0)
[47] S…H† was found to be independent of the
impact angle. Another explanation for the depen-
dence of the S…H† curve shapes on polar impact
angle at constant total impact energy (Fig. 5A)
might be a ¯ux dependence of S…H†, as suggested
in Ref. [47]. Indeed variations in the ¯ux (in this
case simply resulting from changing the polar an-
gle) of the particles impinging on the surface can in
principle lead to di€erent local adsorption con®g-
urations, which might in¯uence S…H†. However,
this e€ect might be expected for dissociative ad-
sorption [47] rather than for molecular adsorption.
4.3.3. Adsorption dynamics for Ts 690 K
At low adsorption temperatures (see Fig. 4B,
Ts ˆ 50 K, ai ˆ 45° and Fig. 5A, Ts ˆ 90 K,
ai ˆ 0°) an initial increase of S…H† with H has been
observed. This result which is opposite to the de-
crease predicted from the Langmuirian model, is
commonly called adsorbate assisted adsorption.
This e€ect is of general interest since it has already
been observed for e.g. NO/W(1 1 0) [61], ethane/
Ir(1 1 0) [62], ethane/Pt(1 1 1) [1,63], CO/Cu(1 1 1)/
Ru(0 0 0 1) [28,29], CO/Pt(1 1 1) [64], rare gases on
metal surfaces (e.g. Cu(1 1 0) [65], Pt(1 1 1) [66],
Ru(0 0 1) [67]), CO/O±ZnO [12], and CO/Zn±ZnO
[13]. As an explanation di€erent models have been
proposed (a) analytical models such as modi®ca-
tions of the Kisliuk model [1,61,64,65,68], (b)
Monte Carlo simulations (MCSs) [62], and (c)
trajectory calculations [63]. In the following the
results obtained here will be compared with these
di€erent models.
(a) Di€erent modi®cations of the Kisliuk model
have been proposed [1,61,64±68]. Bowker and
King, for example, included a coverage depen-
dence of the heat of adsorption in the traditional
Kisliuk model [1,61,68], i.e. the increase in S with
H is related to kinetic e€ects, in contrast to the
commonly observed enhancement of the e€ect
with increasing impact energy. In the case of
CO/Cu(1 1 0), the slope c of S…H† vs. H (within
H ˆ 0±0:7 ML) increases indeed only slightly from
c ˆ 0:10 to 0.16 in the impact energy range of
Ei ˆ 0:046±0.575 eV (Fig. 4B, Ts ˆ 90 K, a ˆ 45°).
This is in contrast to other systems. For example
for CO adsorbed on Zn±ZnO [12±14], a more
distinct adsorbate assisted adsorption with c in-
creasing from 0.25 to 0.37, within approximately
the same impact energy range as studied here, was
observed.
In other versions of modi®ed Kisliuk models,
adsorption probabilities on clean and covered
parts of the surface are distinguished [64,66,67].
In those models a stochastic adsorption of the
impinging particles are assumed and lateral in-
teractions are neglected. In the version proposed
by Zeppenfeld, Comsa et al. [65] the morphol-
ogy of the adlayer has additionally been taken
into account. In particular, the in¯uence of an is-
land formation of the adsorbates on adsorption
 M. Kunat et al. / Surface Science 474 (2001) 114±128
probabilities has been identi®ed to be responsible
for the adsorbate assisted adsorption for Xe on
Cu(1 1 0) [65]. Although, an island formation can
for CO adsorption on Cu(1 1 0) not completely be
ruled out, the shape of the S…H† curves observed
for Xe on Cu(1 1 0) and CO on Cu(1 1 0) di€er
signi®cantly. Additionally, the decrease of the heat
of adsorption with coverage for CO on Cu(1 1 0)
[35,39] indicates clearly a repulsive lateral inter-
actions of the CO molecules, at least for large
coverages, which renders an island formation in
the case of CO adsorption on Cu(1 1 0) rather
unlikely.
(b) In order to explain the increased eciency of
the energy transfer with increasing coverage in
Monte Carlo simulations (MCSs) [69,70] an in-
crease in the mass-mismatch, g ˆ m(adsorbate)/
m(substrate), with increasing coverage (``dynamic
e€ect'') has been considered. In the present case,
for example, the mass-mismatch increases from
g ˆ m…CO†=m…Cu† ˆ 0:44 to g ˆ 1:0 (for CO im-
pinging on adsorbed CO molecules). The com-
monly observed increase of c with increasing
impact energy can be explained by the MCS [62].
For example, the di€erences in the S…H; Ei † curve
shapes as observed for the systems CO/O±ZnO
and CO/Zn±ZnO could qualitatively be explained
by the di€erences in the mass-mismatch [14].
However, the mass-mismatch g is for the CO/Zn±
ZnO system (g ˆ 0:43 neglecting a possible in¯u-
ence of the oxygen atoms in the second surface
layer) about the same as for CO/Cu, in contrast to
the adsorbate assisted adsorption, which is for the
former system much more pronounced than for
the latter (at the same Ei ). Thus, the adsorption
scenario can for CO/Cu(1 1 0) not be quantitatively
explained by the idea of mass-matching. This ob-
servation is thus a strong indication that the en-
ergy transfer processes are for CO on Cu(1 1 0) not
dominated by the excitation of surface phonons.
In the case of metal surfaces another pathway for
the energy dissipation is the creation of electron
hole pares which should be negligible for metal
oxides because of the ®nite band gap. A chemical
e€ect with the adsorbate acting as a promotor is
unlikely in the case of the rather inert CO mole-
cules but might become important for more reac-
tive adsorbates e.g. alkali metals.
125
Consistent with the idea of standard MCS are
the two di€erent regimes observed in the S…H†
curves (see discussion in Section 3.3.2 and Fig.
5B). This curve shapes are surprising at ®rst sight,
since the adsorbate assisted adsorption should be
more distinct for larger coverages and S…H† should
therefore simply increase until saturation has been
reached and S drops to zero (as observed for CO/
Zn±ZnO). Instead of this expected curve shape, the
slope of the initial linear increase in H (related to
adsorbate assisted adsorption) changes at a certain
coverage (see short arrows in Fig. 5B) followed by
an approximately linear decrease of S with H, until
saturation is reached and S drops to zero. A likely
explanation for this observation is a compensation
of the adsorbate assisted adsorption by the in¯u-
ence of the repulsive lateral interactions for larger
coverages, leading in turn to di€erent regimes of
the S…H† curves (see Ref. [70]). The slight shift of
the turning points (as labeled by short arrows in
Fig. 5B) in the S…H† curves with ai indicates,
however, additionally a dynamic e€ect.
(c) According to previously published trajectory
calculations [63] the enhancement of adsorption by
pre-adsorbates can be related to a modi®cation of
the surface corrugation by the adsorbate (``struc-
tural e€ect''). This model has successfully been
applied to the system ethane/Pt(1 1 1)-S [63]. In
this case, total energy scaling has been observed
for S0 , but for glancing angle of incidence the
trapping probability was reduced by the pre-
adsorbate (sulphur) [63]. Thus, the results obtained
for ethane/Pt(1 1 1)-S agree qualitatively with the
measurements presented here for CO/Cu(1 1 0)-CO:
The numerical values of the initial slopes of S vs. H
curves, c, are indeed largest for normal incidence
(see Fig. 5B) and the adsorbate assisted adsorption
can in this case already be observed at 90 K (see
solid line as a guide for the eye in Fig. 5A for
ai ˆ 0°). More quantitatively, the initial slopes, c,
decreases from c ˆ 0:18 to 0.1 in the polar impact
angle range of ai ˆ 0±60° (within the coverage range
as indicated by the arrows in Fig. 5B).
Based on the trajectory calculations [63] the
following conclusions have been drawn which
can explain the e€ect of pre-adsorbates on ad-
sorption probabilities in the case of the system
ethane/Pt(1 1 1)-S: First, the parallel momentum
126 M. Kunat et al. / Surface Science 474 (2001) 114±128
component of the impinging molecules enhances
trapping. Second, for glancing impact angles the
pre-adsorbate steers the impinging particle to-
wards bare surface sites. In turn, the initial parallel
momentum of the impinging particles is converted
into perpendicular momentum which is reducing
the trapping probability.
According to this model we would, however, also
expect an in¯uence of the azimuth on S…H†, since
the corrugation of the two high symmetry direc-
tions di€ers considerably. However, as evident
from Fig. 4B the magnitude of c (slope of S vs. H
curves) is in the case of CO/Cu(1 1 0) independent
of the azimuthal orientation of the surface.
In conclusion, the main features of the results
obtained here for the energy and angular depen-
dence as well as the di€erent regimes in the S…H†
curves can be explained by all of the previously
proposed models for adsorbate assisted adsorption
(see Refs. [62,63,70]). However, a complete and
consistent theoretical description of all details is
not yet available.
4.3.4. Adsorption kinetics
While the strong increase in the He-re¯ectivity
I…H† with surface temperature simply indicates
thermal desorption of CO at about TD ˆ 200 K
(see Fig. 6B); the decrease in I…H† above 200 K is
related to a Debye±Waller attenuation. As pointed
out e.g. in Refs. [71,72] the ®rst derivative of the
temperature dependent He atom re¯ectivity curve
(inverse TDS) can be compared directly to TDS-
results. Therefore, a simple Redhead estimate of
the heat of adsorption might be applied as a con-
sistency test with respect to the TDS studies. By
assuming a pre-exponential factor of 1  1013 1/s
(with a heating rate of 2 K/s), Ed amounts to 52
kJ/mol. This value is in good agreement with the
results obtained in Refs. [35,39] where values in the
range of 54±42 kJ/mol, depending on coverage,
have been reported. (The adsorption of CO is for
Cu(1 1 0) not thermally activated, i.e., Ed equals
the adsorption enthalpy.)
As expected Hsat (Ts ) (under steady state con-
ditions) remains approximately constant above
the condensation temperature, but far below the
thermal desorption temperature, TD , and decreases
sharply in approaching TD .
4.4. In¯uence of defects
4.4.1. He atom re¯ectivity curves
Frequently it has been speculated that special
adsorption sites (e.g. defect sites) exhibit special
properties with regard to chemical reactions at
surfaces. Inducing defects by sputtering surfaces
represents a simple way to contribute to this re-
search topic (cf., e.g. Ref. [17]), especially in the
light of the growing interest in metal/metal oxide
systems (e.g. [5±7]) which are typically character-
ized by very large densities of defects. The e€ect of
defects is also important regarding microkinetical
models in technical catalysis where attempts are
made to correlate the reactivity of catalysts with
details of their microscopic structure. A compari-
son of S…H† (determined by the King and Wells
method) and I…H† curve shapes (measured using
He-atom scattering, see Fig. 7) can present evi-
dence for the e€ect of defects on the adsorption
dynamics, since S…H† is always an average over
adsorption events on all surface sites, including
defect and terrace sites, whereas I…H† samples only
the clean and crystallographically perfect parts of
the surface.
Fig. 7A shows that moderate Ar‡ ¯uences …see
curve for v…Ar‡ † ˆ 0:6 ML† give rise to small
variations in the He atom re¯ectivity curve shapes
only. The decay of I…H† with H is approximately
exponential, as expected for randomly adsorbed
CO molecules [16]. This observation provides
strong evidence that the CO molecules are not
adsorbed preferentially at defect sites. In the latter
case a signi®cantly slower decay of intensity with
coverage is seen, since the scattering cross-sections
of surface defect and CO adsorbate overlap. (See
e.g. the case of CO adsorption on Zn±ZnO [14].)
From the decrease of the specular intensity as well
as from the decrease of the transfer width, C,
(average terrace size) for He atom scattering with
increasing v…Ar‡ † (indicated in Fig. 7) it can be
concluded that moderate sputtering at low tem-
peratures induces already eciently defects. The
numerical value of C for the Cu(1 1 0) surface
sputtered by v…Ar‡ † ˆ 0:6 ML agrees already ap-
proximately with C as obtained for Zn±ZnO [12]
(see Fig. 7). Furthermore, even after large ¯uences
of Ar‡ only a slight broadening of I…H† has been
 M. Kunat et al. / Surface Science 474 (2001) 114±128
observed for Cu(1 1 0) …see the curve for v…Ar‡ † ˆ
3:0 ML† as compared to Zn±ZnO. The results are
either consistent with small di€erences in the
binding energies of CO adsorbed on defect and
terrace sites, or with a large activation energy
for di€usion of CO along the Cu(1 1 0) surface.
Regarding the weak temperature dependence of
I…H; v…Ar‡ †† the latter explanation, however, ap-
pears to be unlikely.
More quantitatively, the reduction in He-re-
¯ectivity resulting from randomly adsorbed CO
RN
molecules is given by I…H† ˆ …1 H† (with R
denoting the cross-section for di€use He atom
scattering and N the density of the surface) [16].
This formula is only valid for randomly adsorbed
and non-interacting particles without overlapping
of the cross-sections. For the non-sputtered sur-
face R amounts to 85 A 2 (see solid lines in Fig.
7A), which is a typical value for CO adsorption on
¯at metal surfaces [16]. After moderate sputtering
…v…Ar‡ † ˆ 0:6 ML† R amounts to 75 A 2 and after
extensive sputtering R decreases to 45 A 2 for
‡
v…Ar † ˆ 3:0 ML. The decrease in the measured
total cross-section by sputtering the surface is at-
tributed to the overlap of cross-sections for di€use
He atom scattering of surface defects and adsor-
bates [16].
4.4.2. Adsorption probabilities
Although S0 does not change signi®cantly with
v…Ar‡ † for CO/Cu(1 1 0), the variation in the shape
of S…H† with v…Ar‡ † is obvious (Fig. 7B). The fact
that S0 is approximately independent of v…Ar‡ † is
consistent with small di€erences in the CO binding
energies on defect and terrace sites. We conclude
tentatively that the decrease in the initial slope of
S…H† with v…Ar‡ † might be explained by the tra-
jectory model discussed above [63] if we assume
that also defects can induce a steering of CO
molecules to free adsorption sites. However, the
coverage dependence of the steering e€ect has not
yet been considered theoretically.
5. Summary
The initial adsorption probability for CO/
Cu(1 1 0) decreases from 0.95 (at Ei ˆ 0:046 eV) to
127
0.5 (at Ei ˆ 0:575 eV), a result which agrees very
well with measurements on CO/Cu(1 1 1) [28,29].
The adsorption turned out to be non-activated,
i.e., S0 is independent of adsorption tempera-
ture. The overall adsorption dynamics of CO on
Cu(1 1 0) is dominated by the presence of precur-
sor states. Additionally, adsorbate assisted ad-
sorption (increase in S with H) could be observed
for Ts 6 90 K. Despite the fact that CO adsorption
on Cu(1 1 0) was a promising system to observe an
e€ect of the crystallographic orientation on the
adsorption dynamics, S0 obeyed approximately
total energy scaling. The adsorbate assisted ad-
sorption was independent of the azimuth and most
distinct for normal angle of incidence. To investi-
gate the in¯uence of defects on the adsorption
dynamics the Cu(1 1 0) surface has been sputtered
by Ar-ions at low temperatures. It turned out that
S0 is essentially independent of the defect density
and CO adsorbs randomly on terrace and defect
sites. However, the adsorbate assisted adsorption
seen for the perfect surface is suppressed by sur-
face defects.
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