ISSN 1990-7931, Russian Journal of Physical Chemistry B, 2007, Vol. 1, No. 4, pp. 307–329. © Pleiades Publishing, Ltd., 2007.

Chemisorption Energetics and Surface Reactivity:

UBI–QEP versus DFT Projections
E. Shustorovich
American Scientific Materials Technologies, Inc., 485 Madison Avenue, 24th Floor, New York, NY 10022, USA
E-mail: eshusto1@rochester.rr.com
Received November 12, 2006; in final form, December 21, 2006

Abstract—The wealth of information accumulated recently by ab initio/DFT calculations of adsorption ener-

getics and reactivity on metal surfaces makes it possible to systematically compare projections of the DFT and
UBI–QEP approaches. We make such comparisons covering both qualitative regularities in and the quantitative
accuracy of binding energies and activation barriers. We focus on the following areas: (1) DFT verification of
the UBI–QEP assumptions and rigorous projections concerning atomic and molecular binding energies at low
coverage; (2) coverage effects revealing in the M–A bond energy competition (metal sharing A–M–A) under
atomic co-adsorption; (3) reactivity patterns including both qualitative (periodic dependence of the activation
barriers, barrier vs. reaction enthalpy relationships, geometry of the transition state, etc.) and quantitative
aspects. We demonstrate the broad agreement between the DFT and UBI–QEP projections and point out the
areas where further testing by the ab initio/DFT techniques might be necessary and illuminating. In particu-
lar, while discussing the ab initio/DFT absolute values of the atomic binding energies QA and their periodic
trends, we revised our previous assumptions about monotonic changes of the QA values with the changing
atom A valence and along the VIII and IB group metals, where the periodic trends appear to be complicated.
Accordingly, we make corrections to the original UBI–QEP parameters, summarizing the current recom-
mended values of QA.
DOI: 10.1134/S1990793107040045

1. INTRODUCTION these projections and evaluations are falsifiable (in the

The recent years have seen an explosion of ab ini-
tio/DFT (Density Functional Theory) calculations of
chemisorbed systems exploring adsorption energetics
and metal surface reactivity (see recent reviews [1–4]).
More complex systems have been treated and more
detailed and accurate information has been obtained.
But an interesting recent trend is that the calculated
quantitative (numerical) results more and more often
are used to discern qualitative (periodic and other) reg-
ularities and project simple relationships between phys-
ical entities assumed to be the major factors [5–8].
The phenomenological analytical UBI–QEP model
[9–11] (and its previous version as the BOC–MP model
[12, 13]) allows one to calculate chemisorption energet-
ics (atomic and molecular binding energies and reac-
tion activation barriers) for a wide variety of systems
adsorbed on transition metal surfaces. The analytical
UBI–QEP model is based on a few well-defined
assumptions and provides explicit interrelations
between various entities, energetic and structural, by
minimization of total potential energy. Because these
entities are observable their accuracy can be directly
tested by experiment and/or by accurate ab initio/DFT
calculations. Most importantly, the UBI–QEP model
provides quantitative relationships, which allows one to
directly project periodic and other regularities and eval-
uate the relative importance of various factors. And
Popperian sense) as well.
For the last two decades the BOC–MP/UBI–QEP
model has provided rather accurate estimates of chemi-
sorption energetics and surface reactivity, in broad
agreement with experiment [9, 11–13]. The very fact
that a wide variety of phenomena could be interrelated,
explicitly and quantitatively, within the same analytical
framework provides the major justification of the UBI–
QEP model, certainly for its practical use. Still, until
the UBI–QEP basic assumptions are deduced from the
first principles some intellectual dissatisfaction and
practical uncertainty will remain. This is the major area
where accurate ab initio/DFT approaches might be
uniquely useful. In general, the phenomenological
UBI–QEP model and quantum mechanical ab ini-
tio/DFT approaches are complementary and therefore
synergetic in their applications to chemisorption phe-
nomena. By and large, a good correlation and even
numerical closeness between ab initio/DFT and UBI–
QEP projections has been found [9, 11]. Because the
recent years have provided a wealth of DFT data it
would be informative to make further systematic com-
parisons of the UBI–QEP versus DFT results to get a
better understanding of the theoretical validity and
practical usefulness of the UBI–QEP model.
Before doing this, however, some clarifications
might be necessary. The first principles ab initio calcu-

307
308 SHUSTOROVICH
lations, either DFT or wave function (HF/CI, etc.), are
still approximate and as such they can be more or less
accurate [1–4]. These computational frameworks con-
tain various assumptions, approximations, and con-
straints, so their accuracy, depending on many factors,
can hardly be foreseen a priori. In the present article,
the ab initio calculated entities, if not stated otherwise,
will be the DFT ones. The reader interested in the DFT
technicalities is referred to the original articles. Here
we will mention only three most important factors:
(1) choice of the exchange-correlation functionals,
(2) (finite) cluster or (infinite) periodic slab modeling,
and (3) frozen (fixed) or relaxed (variable) geometry of
the system. Depending on the individual variations
within the computational frameworks used, results of
calculations of the same entities may differ, often sig-
nificantly (see below). Of course, if DFT values of the
molecular binding energies and the activation barriers
are very accurate, comparison with the relevant UBI–
QEP values would be a legitimate test of the UBI–QEP
model accuracy/validity. However, if the DFT values
are not accurate enough (judged by reliable experimen-
tal data or by the spread of calculated values) such com-
parisons might be not informative. Anyway, once the
UBI–QEP versus DFT data set is chosen it is always
prudent to compare those theoretical results with exper-
iment, particularly if there is disagreement between the
data.
With those clarifications in mind, below we will
provide representative UBI–QEP versus DFT compari-
sons, both conceptual/qualitative and numerical/quanti-
tative. We will focus on the following areas:
1.1. DFT verification of the UBI–QEP assumptions
(a) rigorous quantitative UBI–QEP projections:
atomic binding energies at low coverage
(atop/bridge/hollow ratios, site preference, diffusion
barriers);
(b) the M–A bond lengths at different coordination
sites;
(c) the constants r0 and a in QEP.
1.2. Molecular adsorption at low coverage
(a) rigorous qualitative UBI–QEP projections: con-
tact atoms, site insensitivity;
(b) molecular binding energies: quantitative aspects;
(c) UBI–QEP possible deficiency: methylidine CH.
1.3. Atomic coadsorption and coverage effects
(a) M–A bond energy competition in metal atom
sharing A–M–A: coverage dependence;
(b) quantitative aspects.
1.4. Reactivity
(a) barrier vs. reaction enthalpy: “universal” linear
relationships;
(b) geometry of the transition state: preferred sites
for weakly and strongly bound coadsorbates;
(c) UBI–QEP vs. DFT projections: quantitative
comparisons.
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B
2. THE UBI–QEP MODEL ASSUMPTIONS:
A REMINDER
Let us recall the basis of the UBI–QEP model. The
two-center M–A bond energy Q is assumed to depend
only on the M–A distance r, or on some function x(r) of
this distance, expressed in a polynomial form. The gen-
eral potential E(x) has a two-term quadratic form [9]
2
E ( x ) = – Q ( x ) = – Q 0 [ 2x 0 x – x ] (1)
2
with the only one energy minimum of Emin = – Q 0 x 0 at
the equilibrium M–A distance r0 with the equilibrium
value of x(r0) = x0, and Q0 > 0 is a constant. The x(r)
function, called the bond index, BI, is assumed to be
exponential
x ( r ) = exp [ – ( r – r 0 )/a ], (2)
where a is some constant. The equilibrium value of
x(r0) is x0 = 1, so Eq. (1) becomes
2
E ( x ) = – Q ( x ) = – Q 0 [ 2x – x ] (3)
with Emin = –Q0, where Q0 is the maximal (equilibrium)
M–A bond energy.
For atomic A adsorption, there are three model
assumptions.
2.1. The two-center M–A potential is described by
the quadratic exponential potential (QEP), Eq. (3).
2.2. In the many-center Mn–A potential the total BI
xA of all two-center contributions of the M(i)–A bonds is
conserved at (normalized to) unity
xA = ∑x iA = 1, i = 1, 2, …, n. (4)
The constraint expressed by Eq. (4) is called the unity
bond index (UBI).
2.3. The number n is limited to the size of the regular
unit mesh Mn (the nearest neighbor approximation), say
n = 3 (equilateral triangle) for fcc(111) and hcp(0001),
n = 4 (square) for fcc(100) or n = 5 (square pyramid) for
bcc(100). Then, all M(i)–A bonds in Mn–A are equiva-
lent and, therefore, the values of xi are fully determined
by symmetry, namely xi = 1/n, regardless of the values
of two constants, r0 and a, which otherwise should
somehow be determined (see below).
The rest is straightforward algebra of minimizing
the total potential energy of the Mn–A interactions.
For atomic A adsorption within a symmetric Mn–A
unit mesh, the UBI–QEP formalism rigorously
projects that the Mn–A bond energy monotonically
increases with n as
Q A ( n ) = Q 0A ( 2 – 1/n ), (5)
when the equilibrium M–A distance is
r n = r 0 + a ln n. (6)
Vol. 1 No. 4 2007
 CHEMISORPTION ENERGETICS AND SURFACE REACTIVITY 309

Table 1. Binding energies Q of atoms and diffusion barriers Ediff on some fcc(111) surfaces: DFT and UBI–QEP data
Preferred site Q Ediff Ediff/Q
Metal surface Atom
calc. exp. PW91 RPBE PW91 RPBEP PW91 RPBE UBI–QEP
Rh(111) [18] O fcc fcc 4.88 4.31 0.45 0.41 0.09 0.10 0.10
N hcp … 5.31 4.87 0.68 0.64 0.13 0.13 0.10
S fcc fcc 5.42 4.95 0.46 0.46 0.08 0.09 0.10
C hcp … 7.11 6.65 0.60 0.56 0.08 0.08 0.10
Ir(111) [17] O fcc fcc 4.57 4.00 0.55 0.49 0.12 0.12 0.10
N fcc … 4.80 4.40 0.55 0.50 0.11 0.11 0.10
hcp … 4.80 4.40 0.55 0.50 0.11 0.11 0.10
S fcc fcc 5.11 4.67 0.58 0.57 0.11 0.12 0.10
C hcp … 6.71 6.29 0.49 0.47 0.07 0.07 0.10
Pt(111) [15] O fcc fcc 3.87 3.27 0.52 0.47 0.13 0.14 0.10
N fcc … 4.35 3.91 0.85 0.81 0.20 0.21 0.10
S fcc fcc 4.94 4.42 0.56 0.53 0.11 0.12 0.10
C fcc … 6.75 6.27 0.75 0.72 0.11 0.11 0.10
Note: DFT data for two exchange-correlation functionals, PW91 (self-consistent) and RPBEP (non-self-consistent). All energies are in
electronvolts.

3. AB INITIO/DFT VERIFICATION appears to be the hydrogen atom whose energy profiles

OF THE UBI–QEP ASSUMPTIONS
From Eq. (5), it follows that:
(1) Within the Mn–A mesh, the hollow site (n = 3, 4,
or 5) is the only one global energy minimum. At zero
(low enough) atomic coverage, this highest coordina-
tion site is always preferred.
(2) The ratio of binding energies Q in the symmetric
sites, atop (T), bridge (B), and hollow (H), is deter-
mined only by the value of n, namely Q(T) = Q0, Q(B) =
(3/2)Q0, and Q(H) = (5/3), (7/4), and (9/5) Q0 for n = 3,
4, or 5, respectively, the Q(H)/Q(B) ratio being 1.11,
1.17, and 1.20.
(3) Within the Mn–A mesh, the atop site (n = 1) is a
maximum and the bridge site (n = 2) a saddle point
between two adjacent hollow site minima. The lowest-
energy diffusion of A to the adjacent Mn–A unit mesh
corresponds to the hollow-bridge-hollow path with the
barrier
∆E dif = γ n Q nA = Q nA ( n – 2 )/ ( 4n – 2 ). (7)
Thus, the atomic diffusion barrier ∆Edif is propor-
tional to the binding energy QnA with the proportional-
ity coefficient (corrugation ratio) of γn = (n – 2)/(4n – 2),
which is γ3 = 0.10 for fcc(111) and hcp(0001), n = 3,
γ4 = 0.14 for fcc(100), n = 4, and γ5 = 0.17 for bcc(100),
n = 5.
The predictions concerning the preferred coordina-
tion sites are in full agreement with experiment [9, 12]
and DFT calculations. Specifically, at low coverage all
adatoms occupy the hollow sites (of the highest coordi-
nation), which are distinctly more favorable than the
bridge and especially atop sites. The only exception
are rather flat. Typically, hydrogen still prefers the hol-
low sites although the bridge and atop sites are close in
energy [14]. In particular, for the H/Pt(111) system,
several DFT studies (e.g., [15, 16]) found practically no
preference for a coordination site, and in the DFT study
of the adsorption system H/Ir(111) [17] the slightly pre-
ferred hydrogen coordination was found to be atop (in
apparent agreement with the cited experimental data).
Within the UBI–QEP model, deviation from the
highest coordination might occur only if the UBI
(Eq. (4)) becomes incompatible with the QEP (Eq. (2)),
which in turn violates the interrelations between the
hollow vs. bridge vs. atop binding energies, Eq. (5).
This incompatibility can happen if the term (r – r0)/a is
so large that the equivalent M(i)–A bonds in the Mn–A
unit mesh would have the bond indices xi < 1/n. Intu-
itively, this might be expected if the A atom is too small
and the M–M bond lengths are too large (so that the dif-
ference ri – r0 becomes too big). The smallest atom is
hydrogen, and the 5d metals have the largest M–M
bond lengths, which makes such H/M systems most
probable candidates. This reasoning is consistent with
the above DFT results revealing the rather flat energy
profiles of the adsorbed hydrogen (particularly on Ir
and Pt surfaces), and it would be interesting to see if its
validity could be explicitly corroborated by DFT calcu-
lations of the numerical values of xi , that is of the con-
stants r0 and a (see below).
For other atoms, typical examples and numerical
comparisons of the DFT and UBI–QEP energetics are
given in Tables 1 and 2. Table 1 provides results of the
systematic, state-of-the-art DFT calculations of binding
energies QA and diffusion barriers Ediff for adsorption of

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B Vol. 1 No. 4 2007

310 SHUSTOROVICH

Table 2. Atomic binding energies for the hollow H vs. bridge B coordination sites on some fcc(111), fcc(100), and bcc(100)
surfaces: DFT vs. UBI–QEP
DFT energiesa H/B ratio fcc(100)/(111) ratio
Adatom fcc bcc
H siteb B site DFT UBI–QEPc DFT UBI–QEPc
O Cu(111)d 96.9 86.5 1.12 1.11
Cu(100)k 114.0 95.5 1.19 1.17 1.18l 1.05
Ag(111)e 86.3
Ag(100)e 95.3 77.5 1.23 1.17 1.10 1.05
Ni(111)f 114.3 102.0 1.12 1.11
Ni(111)g 114.7
Ni(100)g 129.1 1.12 1.05
Ni(111)q 112.3
Ni(100)q 124.3 1.11q 1.05
Pt(111)i 75.7 63.0 1.20 1.11
Pt(111)h 98.3 83.7 1.17 1.11
Pt(111)m 89.3 77.3 1.16 1.11
75.4 64.6 1.17 1.11
Rh(111)o 112.6 102.2 1.10 1.11
99.4 90.0 1.10 1.11
Ir(111)n 105.4 92.7 1.14 1.11
92.3 81.0 1.14 1.11
N Pt(111)p 107.3 84.4 1.27 1.11
Pt(111)m 100.4 80.8 1.24 1.11
90.2 71.5 1.26 1.11
Rh(111)o 122.5 106.8 1.15 1.11
112.4 97.8 1.15 1.11
Ir(111)n 110.7 98.0 1.13 1.11
101.5 90.0 1.13 1.11
W(100)j 170 147 1.16 1.20
C Pt(111)m 155.7 138.4 1.12 1.11
144.6 128.0 1.13 1.11
Rh(111)o 164.0 150.2 1.09 1.11
153.4 140.5 1.09 1.11
Ir(111)n 154.8 143.3 1.08 1.11
145.1 134.3 1.08 1.11
S Pt(111)m 114.0 101.1 1.13 1.11
102.0 89.8 1.14 1.11
Rh(111)o 125.0 114.4 1.09 1.11
114.2 103.6 1.10 1.11
Ir(111)n 117.9 104.5 1.13 1.11
107.8 94.6 1.14 1.11
Notes: a Calculated at low coverages θ ≤ 1/n (ZCL values). b For all atoms, the energy minimum was found to be in the hollow sites (for
details, see Table 1 ). Double sets for O, N, C, and S atoms on Pt(111), Rh(111), and Ir(111) are DFT data for two exchange-cor-
relation functionals, PW91 and RPBE (see Table 1). All energies are in kcal/mol. c Equation (5). d [19]. e [20]. f [21]. gAb initio
HF/CI [22]. h [23]. i [24]. j [25]. k [26]. l This fcc(100)/(111) ratio corresponds to the values obtained in different DFT studies [19, 26]
and therefore is less informative. m [15]. n [17]. o [18]. p PW91 [27]. q Experimental calorimetric data [28].

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B Vol. 1 No. 4 2007

 CHEMISORPTION ENERGETICS AND SURFACE REACTIVITY
A = O, N, S, and C on fcc(111) surfaces of Rh [18], Ir
[17], and Pt [15].
The calculations were made at low coverage θ ≤ 1/n
(which is the “zero coverage limit” (ZCL) in the UBI–
QEP model) for two most popular DFT exchange-cor-
relation functionals, PW91 (self-consistent) and RPBE
(non-self-consistent). For all atoms, the energy mini-
mum was found in hollow sites, typically in the fcc site
but sometimes in the hcp site (for carbon and nitrogen
on Rh(111) and Ir(111)). From Table 1 one can see that
the PW91 binding energies are systematically larger
than the RPBE ones by ~0.5 eV (12–15 kcal/mol) but
the diffusion barriers (differences between the binding
energies in the hollow H and bridge B sites) are very
similar. This reflects a rather general situation that the
relative DFT values are more reliable than the absolute
ones. Accordingly, Table 2 provides results of various
state-of-the-art DFT calculations of atomic binding
energies Q for the H versus B coordination sites on
some fcc(111), fcc(100), and bcc(100) surfaces. The
relevant UBI–QEP values are given for comparison.
One should mention that the UBI–QEP model (in its
nearest neighbor approximation) does not distinguish
in the fcc(111) surface two adjacent hollow sites, fcc
and hcp (differing by the lack or the presence of a metal
atom in the second layer below the M3–A hollow site).
The ab initio/DFT calculations do distinguish the fcc
and hcp hollow sites, usually finding the fcc site pre-
ferred although the hcp site is comparable and some-
times preferred (for atoms of the highest valency such
as N and C, as seen from Table 1). Because the fcc-hcp
energy difference is small being typically of the order
of few per cent of QnA (see, for example, [15, 17, 18]),
it practically does not affect the UBI–QEP projections
for fcc(111) surfaces. It is worth mentioning that
because the hollow sites are often the only true energy
minima the DFT energies of the top and bridge sites are
obtained by introducing some additional constraints
(see, for example [27]). With all these in mind, the
agreement between the UBI–QEP and DFT values is
excellent.
3.1. Determination of the Constants r0 and a
Within the UBI–QEP model, Eqs. (3)–(7) are exact,
so their accuracy is the most informative test of the
model’s validity. One should stress that the rigorous
consequences of the energy relation Eq. (5) are deter-
mined by symmetry and therefore independent of the
constants r0 and a which define the A–M bond index,
Eq. (2), and determine changes of the A–M bond length
with n, Eq. (6). Because only the hollow sites are exper-
imentally observed the constant r0 cannot be experi-
mentally verified but the constant a can. In particular,
the relation r3 versus r4 for the hollow sites in the
fcc(111) M3–A and fcc(100) M4–A unit meshes
r 4 – r 3 = a ln ( 4/3 ) = 0.287a (8)
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B Vol. 1
311
can be used to estimate the “experimental” value of a
[12]. The value of a can also be determined from fre-
quencies ωn of vibrations normal to the surface for the
Mn–A bonds, namely
1/2
ω n = [ cos ψ n /a ] [ 2Q nA /µ ] , (9)
where ψn is the angle between the M–A vector and the
surface normal, and µ is the mass of an adatom A. Some
estimates of a from the relevant experimental data have
been made (see [12, Table 8]). Those estimates are
qualitatively consistent with the above UBI–QEP rela-
tionships but far from providing quantitative corrobora-
tion. The major reason is that even small errors in the
experimental bond lengths translate into large uncer-
tainties of a. For example, for the O–Ni bond lengths of
1.9–2.0 Å, the typical error bounds ±0.05 Å (<3%)
result in the uncertainty of ±0.2 Å (35–50% of the esti-
mated value of a) [12].
In principle, the UBI–QEP constants, r0 and a, can
be determined by ab initio/DFT calculations along the
lines outlined above. In particular, Eq. (6) can be
explicitly tested by calculating bond lengths rn in all
symmetric sites, atop T, bridge B, and hollow H, which
would give both r0 and a. However, the calculations
should have the accuracy adequate for the testing task.
At present this testing appears to be unrealistic but it
might be possible in the future.
3.2. Atomic Binding Energies
General comments. The atomic binding energies QA
constitute the basic UBI–QEP parameters which are
taken from external sources—experiment (if available)
or ab initio/DFT calculations. Reliable experimental
values of QA exist for H and O on many surfaces and for
N on some surfaces. For C, the experimental values of
QC were reported only for two Ni surfaces, fcc(111) and
(100) [29, 30], but there are serious doubts about their
accuracy (see, e.g., [31]). Thus, most of QN and all QC
are obtained from theoretical calculations and/or some
extra/interpolations.
Some clarifications are worthy. For practical rea-
sons, the major source of adsorbed atoms A is A2
(and/or AB) molecules which should be available in the
gas phase. This is the case for H, O, and N but not for
C. Furthermore, direct and accurate measurements of
QA can be made mainly for metal surfaces which disso-
ciate A2 molecules without or with slight activation.
These conditions are fulfilled for H2 and O2 on most
metals and for N2 on active metals of the V and VI
groups, so one can at least extrapolate the experimental
values of QN to the VIII group metals. At practical con-
ditions, carbon forms not C2 but graphite. The reported
experimental values of QC on Ni(111) and (100),
namely QC = 171 kcal/mol [29, 30], were suspiciously
close to the bond energy of graphite, and in the same
work a smaller estimate of QC ≤ 160 kcal/mol was sug-
gested [30].
No. 4 2007
312 SHUSTOROVICH

Table 3. Selected ab initio/DFT values QO: mutual compar- are best defined for the fcc(111) and hcp(0001) sur-
isons and experimenta faces. Based on the experimental and theoretical data
accepted at the time (see [13, Table 1]), the UBI–QEP
Ab initio/DFT
Experi- values of QA reflected two major periodic regularities:
Surface UBI–QEPa
individual
range menta (1) For a given metal surface, the absolute values of
values QA increase with an increase of the atomic valence
Rh(111) 99.4–112.6b 100–127 102 102 along the period, in particular (mono-H<) di-O < tri-N <
i ii tetra-C.
111.9 113.0 88–102dd
d (2) The values of QA decrease monotonically from
120.4 left to right along the period/row and from top to bot-
116–127bb tom along the column.
Ir(111) 92.3–105.4c 92–105 93 93 These regularities appear to be general enough for
f 112h
Ni(111) 114.3 110–137 115 the VIII group metals whereas for the IB metals the
110.0–124.1 ff 115 periodic trends might be more complicated (see below).
114.7 g Some of the recommended UBI–QEP numerical values
of QA have been changed when the more accurate esti-
125.0i mates became available. The last time these changes
137.0y were made in 2003 (see [32, Table 4]). Now we will dis-
Pd(111) 80.5–94.1ff 80–102 86hh 87 cuss whether the current state of ab initio/DFT calcula-
95.6xx 95.7ii 87
tions makes it necessary and possible to make further
changes/corrections.
102.4i
There are many ab initio/DFT techniques, and they
Pt(111) 75.7k 75–102 85 85 vary, often significantly, in their accuracy, so there is
75.4–89.3m 96z always a range of ab initio/DFT values of QA. Cluster-
83.3yy 87z type calculations of the chemisorption energetics usu-
98.3 l ally are less reliable because they are very dependent on
the cluster size/structure (cf. the accompanying article
101.3x by Gomes et al. [4a]). This size dependence produces
102.2j artifacts due to boundary effects and makes it particu-
Cu(111) 96.9n 97–116 103 103 larly difficult to evaluate surface relaxation effects
99.9 i (often, large). In principle, periodic slab calculations
are preferred but their accuracy depends on how well
116.0x they treat many influencing factors. Not surprisingly,
Ag(111) 72.2i 73.8jj 72–86 80 80 more accurate calculations, being more comprehensive,
80.7zz are more expensive, and practitioners should strike
86.3e affordable balance. In particular, calculations vary in
considering the following major factors:
Notes: a All energies are in kcal/mol. The experimental values and (1) The number of metal layers and surface relax-
references, if not shown otherwise, are from [13, Table 1].
b The RPBE–PW91 range [18]. bb Other DFT values cited ation.
in [18]. c The RPBE–PW91 range [17]. d [38]. dd Other These factors are interrelated. The minimal number
experimental values cited in [38]. e [20]. f [21]. ff The of metal layers is two but slab calculations usually
RPBE–PBE–PW91 range [41]. g Ab initio HF/CI: [22]. employ from three to five (and more) layers. The more
h [28]. hh [42]. i [43]. ii [59]. j [44]. k [24]. l [23]. m The metal layers are considered the more accurate is treat-
RPBE–PW91 range [15]. n [19]. x [45]. y [46]. z The initial ment of surface relaxation, which might be significant,
(θ ~ 0) and average (for θ = 0–0.33) values, respectively especially for more open surfaces and strongly bound
[36]. See text. xx [47]. yy From Q * adsorbates, affecting the binding energies (see, e.g.,
O = 23.8 kcal/mol [48] for
the calculated gas-phase value D(O2) = 130.4 kcal/mol [49]. [27] and references therein).
zz Average value for three coverages in the range of θ = (2) The size and structure of a periodic unit cell
0.11–0.33 (θ ≤ 1/n) [35]. jj [50]. (adsorbate coverage).
Smaller unit cells require smaller computing time
and cost but, by definition, they correspond to higher
In this article we will mainly concentrate on the coverage (the adatom/metal atom ratio). For example,
chemisorption energetics on fcc(111) and hcp(0001) the smallest unit cell A-p(1 × 1), having the size of the
surfaces (having the same M3 unit mesh). They are surface unit mesh Mn, corresponds to θ = 1 ML but cov-
close packed and the least prone to lattice changes after erages of practical interest are usually much lower, typ-
chemisorption. For this reason the experimental bind- ically smaller than θ = 0.3–0.5 (higher coverages often
ing energies and, therefore, the UBI–QEP values of QA cannot be realized and/or adatoms form some under-

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 CHEMISORPTION ENERGETICS AND SURFACE REACTIVITY 313

surface structures (see, e.g., [33]). In particular, on Table 4. Selected ab initio/DFT values (kcal/mol) of QN
fcc(111) surfaces the coverages θ = 0.50, 0.33, 0.25, and QC: mutual comparisons and experiment
0.17, and 0.11 are realized within the rapidly increasing
Ab initio/DFT
unit cells (2 × 1) < ( 3 × 3 )R30° < (2 × 2) < (3 × 2) < Surface UBI–QEPa
(3 × 3), respectively. In general, a given coverage can be individual values range
realized by different atomic A configurations when Atom N
some atoms may be non-equivalent. Such coverage
Rh(111) 112.4–122.5b 112–122 116h
variations are accompanied by changes in the binding q
energies QA, so the choice of coverage and the unit cell 106.6
is of much importance for comparisons of various DFT Ir(111) 101.5–110.7b 102–111 127
calculations among themselves and experiment. Ni(111) 135
(3) The choice of the DFT functionals. Pd(111) 90.7q 91 130
Pt(111) 90.2–100.4 b 90–109 102–116h
There are many of them (see [34] and references
therein), and calculations were often made with only 107.3c 108.9d
one (this or that) functional. Two most popular DFT Ag(111) 7.6p
exchange-correlation functionals are PW91 (self-con- Atom C
sistent) and RPBEP (non-self-consistent). The DFT- o
Ru(0001) 165.1 165–175
PW91 calculations usually overestimate the binding
energies but the DFT-RPBE calculations underestimate 174.6o
them, as seen from Tables 1–3. Co(0001) 152.7e 153–163
(4) An account of the vibrational zero-point energy. 158.7f
162.6f
Most DFT calculations neglect this energy. When
calculated, sometimes it was indeed small but some- Rh(111) 153.4–614.0b 153–168
165.0 m
times it was found to contribute strongly to binding
energies of both atoms and molecules and therefore to 168.5m
the reaction activation barriers. A recent example of the Ir(111) 145.1–154.8b 145–155
zero-point energy effects is DFT calculations of
adsorption of N, O, H atoms and molecules formed by Ni(111) 154.1f 135–155 171
146.5 i
those atoms on Pt(111) [27].
134.0j
It might be useful to clarify the interrelation
between the DFT and UBI–QEP approaches to the QA 156.0l
coverage dependence. In general, the values of QA Pd(111) 151.8g 148–152 160
decreases with coverage, and DFT calculations univer- 147.5 n
sally reveal this decrease, which is caused by the M–A
Pt(111) 144.6–155.7b 145–157 150
bond competition (A–M–A metal sharing). On a sur- k
face with a unit mesh Mn–A for the coverage range of 157
0 < θ ≤ 1/n, there is no co-adsorption in the adjacent Ag(111) 36.9p
Mn–A meshes and therefore, within the nearest neigh-
bors approximation, there is no metal sharing. Accord- Notes: a All the UBI–QEP values are from [13, Table 1], if not
ingly, in the UBI–QEP model, where binding is limited stated otherwise. b From Table 2. c [27]. d [45]. e [51]. f [31,
to nearest neighbors, the atomic binding energy QA for 52]. g [47]. h [53]. i [54]. j [55]. k Evaluated from Fig. 4 in
zero coverage remains constant for coverages up to [16]. l [46]. m The two values for θ = 0.25 and 0.11, respec-
θ ≤ 1/n. However, the DFT calculations include all tively [57]. n [58]. o The two values are for θ = 0.25
neighbors and therefore show the decrease in QA and 0.11, respectively [57, 75]. p [50]. q [60].
already within the range 0 < θ ≤ 1/n. For example, when
the coverage of carbon increased from θ = 0.11 to 0.25,
a decrease in QC was found to be 4 kcal/mol on As said, the zero-coverage UBI–QEP parameter
fccRh(111) but 10 kcal/mol on hcpRu(0001) (see QA(θ = 0) is assumed to be constant within the range
Table 6 below). Another example is the system 0 < θ ≤ 1/n. If QA actually does decrease, the UBI–QEP
O/fccAg(111) where periodic slab DFT calculations QA(θ = 0) should be taken as an average of QA(θ) for
[35] found a monotonic decrease of QO in the range of the range of 0 < θ ≤ 1/n. The same proposition holds
θ = 0.11, 0.25, 0.33, namely QO = 83.3, 81.2, and true for the experimental binding energies if they are
78.0 kcal/mol, respectively. Most periodic DFT calcu- taken as the UBI–QEP parameters QA. However, unlike
lations were made for only one coverage, usually θ = theoretical calculations for an ideal surface, the experi-
0.25 but often for θ = 0.50 or 1.00, which should be mental situation may be more complicated. At very low
taken into account in comparisons. (zero) coverage the measured value of QA may be

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314 SHUSTOROVICH

Table 5. The UBI–QEP parameters QA for the VIII and IB metalsa

Adatom Co Rh Ir Ni Pd Pt Cu Ag Au
Hb ≥63 61 58 63 62 61 56 52 ≤52
Ob ≥115 102 93 115 87 85 103 80 ≤75
Nc >135 116 ≥110 (127) 135 ≥110 (130) 110 – – –
Cd 160 160 155 155 155 155 – – –
Notes: a The values QA (in kcal/mol) are for the metal surfaces (hcp(0001) for Co and fcc(111) for the rest) having the three-fold unit
meshes M3–A. The standard (two-center) UBI–QEP parameter Q0A can be obtained as Q0A = 0.6 QA (Eq. (5)).
b All numbers are the experimental values (taken from [13, Table 1]) with the exception of Co, which are extrapolations. The aver-
aged DFT values (see [14] for QH and Table 3 for QO) are in good agreement with these experimental data.
c The DFT values from Table 4 averaged to be in reasonable agreement with the experimental data [13, Table 1] and to show the
conventional periodic trends. The only exception is Ir and Pd, where the differences are large and therefore we suggest two sets
of values, DFT and experimental (in parentheses). See text.
d The averaged DFT values from Table 4 showing unconventional periodic trends. See text.

affected by inevitable surface defects having a more was chosen as the UBI–QEP value of QO on Pt(111)
open surface and therefore the higher QA. For this rea- (see Table 3). For most systems, however, such
son the initial value of QA may be (artificially) overes- (detailed) coverage data are lacking, which leads to
timated, and the following decline in QA may be (arti- uncertainties in choosing both theoretical and experi-
ficially) much steeper. A probable example is a micro- mental values of QA.
calorimetric study of oxygen adsorption on Pt(111) For these reasons it is not always clear which DFT
[36]. The initial binding energy was measured to be values can be compared with one another and with the
QO ~ 100 kcal/mol but it dropped precipitously to UBI–QEP values and experiment. The systematic anal-
85 kcal/mol at θ = 0.11 and slower to 75 kcal/mol at ysis of the ab initio/DFT calculations of QA is beyond
θ = 0.33. The initial (zero-coverage) value QO(θ = 0) ~ the scope of the present work. Here we will provide
100 kcal/mol, if taken for Pt(111), appears to be only some examples, hopefully representative of the
strongly overestimated but QO(θ = 0.11) ~ 85 kcal/mol state of affairs.
or the average value QO(θ = 0–0.33) ~ 87 kcal/mol are
in good agreement with the generally accepted TDS Numerical values. The experimental range of the
experimental value of QO ~ 85 kcal/mol [37], which hydrogen binding energies for the VIII group metals,
particularly Co–Ir and Ni–Pt, is narrow being QH = 60–
65 kcal/mol [13, Table 1]. The majority of ab ini-
Table 6. Selected DFT versus UBI–QEP binding energies tio/DFT calculations reproduce the absolute values of
a
Q CH3 O QH rather well. However, because the differences in QH
are very small the periodic regularities are not clear
Metal DFT Q CH3 O UBI–QEPb [14]. Also, the accuracy of calculated values of QA for
surface individual range Q CH3 O QO hydrogen does not guarantee the accuracy of QA for
other atoms. Indeed, as seen below, for a given metal
Rh(111) 52c 52 54 102 surface, the calculated values of QA for A = O, N, and
Ni(111) 62c 62 65 115 C usually show a wide spread.
Pd(111) 38h 39–47 43 87 Let us start with oxygen. Experimental low-cover-
39d age values of the oxygen binding energies QO for the
41e
47c VIII group metals cover a wide range of QO = 80–
Pt(111) 34c 34–39 41 85
120 kcal/mol (see [13, Table 1]). Although DFT calcu-
36f lations of oxygen chemisorption are plentiful, only a
39e part of them is suitable for our purpose. First, we are
Cu(111) 48g 48–56 55 103
comparing only the O binding energies at low coverage,
51c θ ≤ 1/n, so we exclude DFT calculations which use unit
56d cells corresponding to high coverage, θ > 1/n. Second,
Ag(111) 44c 44 38 80
in DFT calculations of O/M systems the O binding
energies are presented either as the absolute value QO or
Notes: a All energies are in kcal/mol. b The values of QCH O were
3 as the relative value Q O* = QO – (1/2)D(O2) referred to
calculated from Eq. (10) for k = 1, DAB = 90 kcal/mol (see
text). The atomic binding energies QO are taken from exper- the gas-phase bond energy D(O2) ( Q O* is the heat of
iment (see Table 3). c [67]. d [68]. e [69]. f [70]. g [71]. h [72]. dissociative adsorption O2, gas 2Oads per atom).

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 CHEMISORPTION ENERGETICS AND SURFACE REACTIVITY 315

These values are uniquely interrelated only if the calcu- Table 7. CH3 binding energies: UBI–QEP vs. DFTa
lated value of D(O2) is known. Many DFT calculations,
Metal surface DFTb DFTc UBI–QEPd
however, provide only the values of Q O* without D(O2),
which prevents determination of QO. The fact is that the Ni(111) 47 25–50 48 (40)
DFT values of D(O2) vary strongly, often being in the Pd(111) 41 36–39 42 (40)
range of 130–145 kcal/mol (see, for example [19, 35, Pt(111) 30 40 38 (40)
38, 39]). Therefore the substitution of the DFT D(O2) Rh(111) 41 40–45 ≥42
by the experimental value of D(O2) = 119 kcal/mol [40] Notes: a All energies are in kcal/mol. b Periodic DFT slab calcula-
might be a poor approximation. tions [63]. c Range of other ab initio/DFT values (periodic
and cluster-type) cited in [63]. d From [13, Table 8]. The val-
For further certainty we will limit our comparisons ues in parentheses are for the modified QC = 155 kcal/mol for
to oxygen adsorption on fcc(111) surfaces for which Ni(111), Pd(111), and Pt(111) (see above).
the experimental binding energies and, therefore, the
UBI–QEP values of QO are best determined (the close
packed fcc(111) surfaces are the least prone to surface Table 8. CH2 binding energies: UBI–QEP vs. ab initio/DFTa
reorganization after chemisorption). These selected
data are shown in Table 3 and compared with the rele- Metal DFT
vant (fortunately, still plentiful) DFT values. θ UBI–QEP
surface periodic cluster
Not surprisingly, the more numerous and diverse are
the DFT calculations (using different functionals and Ni(111) 0.25 75b 67–88c 83d (71)
approximations as well as different coverages) the Pt(111) 0.25 92e 68d (71)
wider is the calculated QO range, often comprising tens Rh(111) 0.25 100f 78h
of kcal/mol. This makes agreement with experimental 0.11 101f 81h
data (which usually also form a range) and an evalua-
tion of the DFT accuracy uncertain. For example, as Ru(0001) 0.25 100g 78h
seen from Table 3, the DFT values QO for Pt(111) are 0.11 103g 85h
spread within a range of 75–102 kcal/mol, which is 0.25 99i 85h
much wider than the reported experimental range is 85– Co(0001) 0.25 92i 77h
96 kcal/mol. Actually, the latter may be even smaller,
namely QO = 85–87 kcal/mol, because the cited QO = Notes: a All energies are in kcal/mol. b [74]. c Cluster-type ab ini-
96 kcal/mol is the initial (zero coverage) value which tio/DFT values (their range) cited in [74]. d From [13, Table 8].
might be overestimated (see above). If so, many DFT The value in parentheses is for the modified QC =
values of QO on Pt(111) are not accurate. Another 155 kcal/mol (see above). e Evaluated from [16, Fig. 4].
example is O/Ni(111), where two ab initio calculations, f [57]. g [75]. h The UBI–QEP values of Q
CH 2 are calcu-
DFT [21] and HF/CI [22], are consistent with the nar- lated for the DFT values of QC on those surfaces (see Table 8
row experimental range of QO = 112–115 kcal/mol but in the text). i [76].
two other ab initio DFT calculations, predicting QO =
125 kcal/mol [43] and even 137 kcal/mol [46] are wide
off the mark (see Table 3). One should add that various compared with the assumed UBI–QEP values of QN
DFT calculations may produce not only a spread of the and QC based on experimental data existed at the time and
absolute values of QA but also the different order in the some extrapolations of those data (see [13, Table 1]).
periodic series, which makes specific projections for a
given metal surface problematic. For example, as seen A serious complication is that the nature and
from Table 3, most DFT studies find, in agreement with strength of the metal-adsorbate bonding differ greatly
experiment, that the oxygen binding energy on Cu(111) for the d-band and sp-band metals, so that the regulari-
is distinctly larger than that on Pd(111). However, in the ties found for the VIII group (Co, Rh, Ir, Ni, Pd, Pt)
DFT calculations by Wang et al. [43] the opposite may be different for the IB group (Cu, Ag, Au). From
order Pd > Cu was found (because of a strong overes- Tables 3 and 4 we see that for all the VIII group metals
timation of QO on Pd which was calculated to be over the binding energy QA order follows the atomic
102 kcal/mol whereas the experimental value is QO = valences, namely O < N < C. Until recently, the com-
86–87 kcal/mol), which makes the theoretical projec- mon assumption was that for the IB metals the order
tions for Cu and Pd surfaces and comparisons with should be the same, which determined the choice of the
experiment not convincing. UBI–QEP atomic parameters QA [9–13]. However, this
The accuracy of DFT values QO might give an idea assumption might need correction. A conspicuous
about the probable accuracy of the calculated values of example is the QA order on Ag(111) found in the most
QN and QC, where experimental values are unavailable. recent state-of-the-art ab initio calculations [50]. These
Some data for fcc(111) and hcp(0001) surfaces (having calculations were cluster-type but the cluster size
the same M3 unit mesh) are given in Table 4, which are appears to be large enough (three layers of 91 atoms) to

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B Vol. 1 No. 4 2007

316 SHUSTOROVICH
provide reliable estimates. Although for all atoms the
preferred coordination site is the fcc hollow, the QA
order did not follow the atomic valences, the maximum
being for O (74 kcal/mol), the minimum for N
(8 kcal/mol) and C in-between (37 kcal/mol). The sug-
gested reason was that the sp-metal band of Ag could
not fully utilize the adsorbate unpaired electrons (a
maximum of two metal electrons were shared). This is
fundamentally different from the metal d-band which
can utilize more or even all the adsorbate unpaired elec-
trons, as has been illustrated by comparing the electron
distributions in the similar calculations for Pt(111)
[50]. Below we will also see that the VIII and IB metals
might show the reversed trends in the binding energies
of C versus CH and N versus NH.
Unfortunately, unlike the systematic DFT calcula-
tions for the VIII group metals, the ab initio/DFT calcu-
lations for the IB metals are scarce, mostly limited to
oxygen adsorption (see Tables 3 and 4), which shows
the common periodic trends. But from the discussed
calculations on Ag(111) [50] it appears that for N and
C adsorption the periodic QA regularities for the IB
metals might be different. With no hope for experimen-
tal data, the relevant QN and QC parameters are in urgent
need of accurate ab initio determination.
Within the VIII group metals, as seen from Tables 3
and 4, the periodic trends in the calculated values of QA
are as follows:
(1) For a given metal surface, the absolute values of
QA increase with an increase of the atomic valence
along the period. This increase is best documented for
the series mono-H < di-O < tri-N < tetra-C. (Please note
that the cross-period comparisons are not valid. For
example, divalent sulfur is stronger bound than not only
divalent oxygen but also trivalent nitrogen.)
(2) For a given atom A, the periodic trends are often
obscured because the calculated ranges of QA of neigh-
boring metal atoms usually overlap. For H, the periodic
changes of QH are small (few kcal/mol) [14] and there-
fore insignificant, whether they are monotonic or not.
For oxygen, the values of QO distinctly decrease from
left to right along the period/row and from top to bot-
tom along the column. For nitrogen, by and large the
periodic trends are similar although sometimes it is dif-
ficult to say whether this periodic decrease is mono-
tonic or not. For carbon, the periodic trends appear to
be more complex, in particular suggesting no change or
even a slight increase in the series Ni ≤ Pd ≤ Pt [4b].
Compared to oxygen, the relevant DFT databases
for nitrogen and carbon are not only more limited but
also the QA ranges strongly overlap, with all uncertain-
ties in comparing (the accuracy of) different DFT cal-
culations. Nevertheless, one can distinguish some peri-
odic QA trends, in particular Pt < Ir < Rh for N or Ru >
Rh > Pd, Rh > Ir and Ni ~ Pd ~ Pt for C (see Table 4).
As far as the absolute values of QA are concerned, one
computational result appears to be unambiguous: the
putative experimental value of QC = 171 kcal/mol on Ni
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B
(111) [29, 30] is overestimated, at least by 15 kcal/mol.
This will be consistent with an alternative experimental
estimate of QC ≤ 160 kcal/mol [30].
The recommended UBI–QEP numerical values of
QA may and should change with time when the more
accurate estimates become available (see the last UBI–
QEP set [32, Table 4]). From said above, it would be
prudent to consider separately the parameters for the
VIII and IB metals.
(1) For the VIII metals, for the carbon binding ener-
gies QC now we assume the periodic series Co ≥ Rh > Ir
and Co > Ni ~ Pd ~ Pt. Specifically, we recommend to
take the same value of QC = 155 kcal/mol for Ni(111),
Pd(111), and Pt(111), compared to the previous UBI–
QEP values of QC = 171, 160, and 150 kcal/mol,
respectively [9, 11, 13]. The changes are slight, how-
ever, and do not warrant re-calculations of the UBI–
QEP studies having used the previous QC parameters.
For QN, only few DFT versus UBI–QEP comparisons
can be made. The projections are mutually consistent
with the exception of Ir and Pd, namely the (conven-
tional) DFT periodic order Rh > Ir [17, 18] and Rh > Pd
[59] versus the reversed UBI–QEP order Rh < Ir and Rh
< Pd, based on the experimental data (see [13, Table 1]),
albeit of the uncertain accuracy. Because there were no
UBI–QEP studies involving these (experimental) QN
parameters for Ir and Pd, their accuracy has not been
tested. So, as an exception we suggest for Ir and Pd two
sets of the QN values, old experimental and new DFT
ones. It would be interesting to see in the future which
set would perform better.
(2) For the IB metals, only the oxygen QO parame-
ters are reliable. The nitrogen QN and carbon QC param-
eters should wait for their determination.
The current recommended UBI–QEP parameters QA
for the VIII and IB metals are summarized in Table 5.
4. MOLECULAR ADSORPTION
Compared to the UBI–QEP atomic formalism, the
molecular formalism includes additional assump-
tions/approximations which makes direct verification
by ab initio/DFT calculations less transparent. Indi-
rectly, the UBI–QEP validity can be tested along two
lines: (1) projected qualitative regularities of QAB, and
(2) the numerical accuracy of values of QAB. Consider
first the projected qualitative UBI–QEP vs. DFT regu-
larities.
4.1. Major Qualitative Regularities
of Molecular Binding Energies
Mono-coordination (AB)–Mn. The molecular AB
binding energies QAB depend on (details of) the coordi-
nation (AB)–Mn mode [9, 13]. For mono-coordination
Vol. 1 No. 4 2007
 CHEMISORPTION ENERGETICS AND SURFACE REACTIVITY
via A the analytic expressions for QAB have a general
form
2 Let us start with the O coordination. In order to get
Q AB = Q A / ( k D AB + Q A ), (10)
where DAB is the gas-phase A–B binding energy (con-
stant), k is some numerical coefficient depending on the
type of bonding (strong or weak) [9, 13]. Equation (10)
rigorously projects that of two possible contact atoms,
A and B, A will be preferred if it has a larger atomic
binding energy, QA > QB. Indeed, all DFT studies cor-
roborate this regularity always finding mono-coordi-
nated CO and CN via C, NO via N, etc. (see, for exam-
ple [2, 3] and references therein).
Insensitivity of QAB to coordination sites. Atoms
have a strong preference for the highest coordination
sites (see Eq. (5)). Molecular radicals AB will show the
stronger preference for higher coordination the more
the contact atom A retains its free-atomic features
(unpaired electrons are substantially localized on A).
This is the case of the strong molecular bonding [9, 13].
If AB is a closed-shell molecule (such as CO) or a rad-
ical with delocalized unpaired electrons (such as NO)
or just one localized electron (such as CH3 or NH2), the
molecular bonding is weaker, and the UBI–QEP for-
malism [9, 13] project relative insensitivity of QAB to a
coordination site.
Indeed, DFT studies find such insensitivity for many
molecules when the preferred coordination sites might
be hollow, bridge and/or atop, the energy differences
being rather small, which often makes it difficult to cor-
rectly determine the preferred coordination site. The
example, which became a “cause celebre,” is CO on
Pt(111), when all conventional DFT studies incorrectly
assigned CO to the hollow site (experimentally, the pre-
ferred site is atop), and only a few specially designed
DFT calculations could make the correct assignment
and reproduce the CO binding energy (see a detailed
discussion and references in [11]). Other examples are
DFT studies of NO (see, e.g., [59–62] and references
therein) and CH3 (see, e.g., [57, 63–65] and references
therein), where the preferred coordination sites was
found to vary depending on a metal surface, coverage,
and other factors.
4.2. Molecular UBI–QEP Versus DFT Binding Energies:
Numerical Comparisons
The numerical accuracy of the UBI–QEP molecular
binding energies has already been tested for a wide
variety of adsorbed species and surface reactions by
comparing with experimental data (see, e.g., the
reviews [9, 11, 13]). So, below we will focus on com-
paring the UBI–QEP and DFT results for entities for
which there are no (at all or accurate enough) experi-
mental data. All molecular species are coordinated via
some contact atoms, and we will distinguish situations
whether the relevant atomic binding energies QA are
known or not known from experiment. In the first case
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B Vol. 1
317
the typical contact atom A is oxygen, in the second
case, carbon.
the most unambiguous results, consider the simplest
case of mono-O-coordination of radicals OX. The sim-
plest radical, hydroxyl OH, is known to form hydrogen
bonds which might strongly contribute to the value QOH
(see discussion in [9]). (Hydrogen bonds already affect
the DFT binding energies of H2O (see, e.g., [66]). The
next best case for a model analysis is methoxy CH3O,
whose adsorption has been extensively studied. The
binding energies Q CH3 O obtained by periodic DFT cal-
culations on various fcc(111) metal surfaces (individual
values and their ranges) are shown in Table 6, where
they are compared with the UBI–QEP values. The latter
were calculated for the H3C–O bond energy of DC–O =
D CH3 O – D CH3 = 383–293 = 90 kcal/mol (see [13,
Table 8]).
Given the variety of the DFT calculations, the agree-
ment with the UBI–QEP values is remarkable. This is
another illustration of the well documented conclusion
[9, 11, 13] that the more accurate are the atomic binding
energies QA (here oxygen QO) the more accurate are the
molecular binding energies QAB, which testifies to the
soundness of the UBI–QEP model.
The second case (the lack of experimental data on
QA of the contact atom) includes many N-coordinated
and all C-coordinated species. For a model analysis, the
simplest species, which are also the most studied, are
mono-C-coordinated CHx fragments. The binding ener-
gies of CH3, CH2, and CH on selected fcc(111) surfaces
calculated by the DFT (both periodic and cluster-type)
and UBI–QEP methods are shown in Tables 7, 8, and 9,
respectively.
The UBI–QEP values of QAB for the mono-A-coor-
dinated molecule AB follow the same order as the val-
ues of QA (cf. Eq. (10)). The DFT calculations typically
show the same patterns. Because the periodic changes
for the atomic carbon binding energy QC are compli-
cated (see above), the DFT values of Q CH3 show a com-
plicated picture as well. For example, from Table 4 one
can deduce the Q CH3 order Ni > Pd > Pt or Ni ~ Pd ~ Pt.
(Moreover, there is one cluster-type DFT study [73]
which projects the periodic Q CH3 relations Pt > Pd and
Ir > Rh.) Coming back to the UBI–QEP projections, for
the assumed values of QC decreasing from 171 to 160
to 150 kcal/mol along the series Ni > Pd > Pt [13], the
values of Q CH3 decrease the same way from 48 to 42 to
38 kcal/mol, in good agreement, even quantitatively,
with the periodic DFT calculations giving Q CH3 = 47,
41, and 30 kcal/mol, respectively [63]. If we assume
that there is no change in QC = 155 kcal/mol along the
series Ni ~ Pd ~ Pt, the values of Q CH3 will be the same,
No. 4 2007
318 SHUSTOROVICH

Table 9. C and CH binding energies: UBI–QEP vs. periodic calculations, and they are in reasonable although not
DFTa that good (as for CH3) agreement with the UBI–QEP
DFT UBI–QEPb
values.
Metal Cover-
surface age, θ For CH species, the divergence of the cluster-type
C CH C CH and periodic binding energies becomes more pro-
Ru(0001)c 0.25 165.1 155.1 165.1 111 nounced. For cluster-type calculations of CH on
Ni(111) the ab initio/DFT values form a range from
0.11 174.6 160.1 174.6 119 QCH = 72 kcal/mol [77] to 120 kcal/mol [78, Table 1.9]
Co(0001)d 0.25 162.6 154.0 162.6 109 to 128 kcal/mol [55], which envelops the UBI–QEP value
Rh(111)e 0.25 165.0 155.9 165.0 111 of QCH = 116 kcal/mol (assuming QC = 171 kcal/mol
0.11 168.5 158.1 168.5 114 [13]). However, with the DFT periodic slab calcula-
tions the disagreement is conspicuous. As seen from
Ni(111)d 0.25 154.0 148.7 154.0 101 Table 9, the relevant DFT values of QCH exceed the
Ni(111)f 0.25 146.5 128.5 146.5 94 UBI–QEP ones by a factor of around 3/2.
Pd(111)g 0.33 147.5 136.0 147.5 95 The recurring feature of all periodic DFT calcula-
Pt(111)h 0.25 144.6 136.1 144.6 93 tions is that the binding energies of atom C and methy-
0.25 155.7 148.3 155.7 102 lidine CH are very close whereas the UBI–DFT values
Pt(111)i 0.17 157 150 157 104
differ significantly. This disagreement (accepting that
the periodic DFT calculations of the binding energies
Ag(111)j 36.9 67.4 are more accurate than the cluster-type ones) points out
Notes: a All energies are in kcal/mol. b The UBI–QEP values of to possible deficiency in the UBI–QEP treatment of the
QCH are calculated for the DFT values of QC. c [75]. d [52]. CH radical. The reason should be found in a quantum
e [57]. f [54]. g [58]. h The two values are for the RPBE and mechanical analysis (of the density of states, etc.)
explaining why formation of CH reduces the binding
PW91 functionals, respectively [15]. i Evaluated from [16,
energy of the contact C atom only slightly (binding of 3
Fig. 4]. j Ab initio non-DFT cluster-type calculations [50].
or 4 unpaired electrons makes little difference). Qualita-
tively, the UBI–QEP order should always be QC > QCH,
a and this indeed was found in ab initio calculations
Table 10. Binding energies Q (in kcal/mol) of C2H4 and C 2 H 2 on the VIII metal surfaces. For the IB metals the
order might be different. Table 9 contains an example
Metal Calculated Q Experi- of Ag(111) where the calculated order is reversed,
Adsorbate
surface ab initio UBI–QEP mental Q QC < QCH [50]. We will return to this point below.
di-σ-C2H4 Pd(111) 15b 13 13–14
Within the UBI–QEP model, symmetric hydrocar-
bons, ethylene C2H4 and acetylene C2H2, are treated as
Pt(111) 36c 11 10–17 homonuclear quasi-diatomic A2 molecules formed by
40d quasi-atoms CH2 and CH, respectively. It might be
Cu(111) 7 ~7 interesting to see whether the peculiarities of the CHx
di-σ-C2H2 Pd(111) 17 ~18 binding affect the UBI–QEP binding energies of C2H4
Cu(111) 6e 9 ~16 and C2H2 (in the strongest di-σ mode). They have been
0–41f calculated within two different approximations, namely
with and without bond-energy partitioning, giving sim-
Notes: a All UBI–QEP and experimental data are from [32, Table 2]. ilar results, in broad agreement with experiment albeit
b Periodic DFT calculations [47, 79]. c Cluster-type DFT cal-
scarce (see a discussion in [32]). The scarcity is mainly
culations [80]. d Cluster-type DFT calculations [81]. e Clus- caused by the fact that at low coverage (which is of rel-
ter-type HF/CI calculations [82]. f Cluster-type HF/CI cal- evance to our discussion) ethylene and acetylene can be
culations [83]. adsorbed intact only on few metal surfaces where the
binding is intermediate between too weak (no adsorp-
tion) and too strong (easy decomposition). Some data
Q CH3 = 40 kcal/mol, for all those metal surfaces, which are shown in Table 10 where they are compared with
the proper ab initio values.
would also be within the ranges of Q CH3 obtained by
For C2H4 on Pd(111), the agreement between the
various DFT calculations, as seen from Table 7.
UBI–QEP and (periodic) DFT binding energies and
Table 8 compares the binding energies of CH2. The those with experiment is excellent, all the values being
best studied case is CH2 on Ni(111) where the UBI– within 13–15 kcal/mol. For C2H4 on Pt(111), the UBI–
QEP and (cluster-type) DFT binding energies differ
QEP values of Q CH2 are in good agreement with both greatly, and the latter strongly overestimates the exper-
periodic and cluster-type ab initio/DFT calculations. imental value by 25–30 kcal/mol. For C2H2 on Cu(111),
For other surfaces we cite only results of periodic DFT the UBI–QEP binding energy lies within the wide

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B Vol. 1 No. 4 2007

 CHEMISORPTION ENERGETICS AND SURFACE REACTIVITY
range of the (cluster-type) HF/CI binding energies,
which is too wide (up to 40 kcal/mol) to make meaning-
ful comparisons with experiment.
Within the UBI–QEP model, the binding energies of
C2H4 should follow the order of the binding energies of
the atomic carbon, that is Ni ~ Pd (see Table 4). Usually
the same trend is found in ab initio studies. Therefore it
looks inconsistent that in the periodic DFT calculations
of C2H4 on Ni(111), the binding energy was found to be
4 kcal/mol [84], which is much smaller than the value
of 15 kcal/mol obtained in the similar calculations of
C2H4 on Pd(111) [47, 79]. However, here the apparent
inconsistency might be because in the Ni(111) study
the C2H4 binding energy was calculated for the on
top π-mode but in the Pd(111) study for the bridge
di-σ-mode, the former being usually much weaker than
the latter [47, 79]. Still, the question remains why the
on top π-mode for C2H4 on Ni(111) is preferred.
One may wonder whether the CH behavior is unique
or there are similar cases. The closest analogs are NHx
species. However, interrelations (if any) between the
DFT versus UBI–QEP binding energies of NHx species
are complex. A representative example is the
NHx /Pt(111) system for which one can compare the
DFT, UBI–QEP and experimental values, as illustrated
in Table 11. In the DFT study [27], the experimental
binding energies were cited only for NH3 [85]. In the
UBI–QEP study [86], the experimental binding ener-
gies were cited for all NHx species, x = 0–3 [87]. For N,
the DFT binding energy of QN = 107 kcal/mol is close
to the experimental estimate of QN = 116 kcal/mol,
which is taken as the UBI–QEP value of QN. For NH3,
the calculated DFT and UBI–QEP binding energies
( Q NH3 = 14–16 and 14 kcal/mol, respectively) are very
close, especially for the zero-point energy corrected
DFT value of Q NH3 = 14 kcal/mol, and they all are in
excellent agreement with the cited experimental range
of Q NH3 =12–15 kcal/mol. For NH and NH2, the DFT
binding energies (given only without the zero-point
energy corrections) differ greatly from the UBI–QEP
ones but the latter are in much better agreement with
experiment.
We saw that the atomic binding energies QA of A =
O, N, and C (with the increasing atomic valence) might
have different orders for the VIII (d-band) versus IB
(sp-band) metals. These metals might also show differ-
ent orders of the molecular AB binding energies QAB.
The most striking difference is the relative values of the
binding energies of A and AH, A = N, C. Within the
UBI–QEP model, there should always be QA > QAB. As
seen from Table 8, for the VIII group metals with the
adsorbates in the same three-fold hollow sites, although
the binding energies of C and CH are very close, the
order is always C > CH. By contrast, for the IB metal
Ag with the same adsorbate coordination, the
reversed order C < CH was found [50]. The same pat-
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B Vol. 1
319
Table 11. Binding energies of NHx species on Pt(111): DFT
versus UBI–QEPa
Species DFTb UBI–QEPc Expd
N 107.3 (116) 116
NH 92.5 71 71–74
NH2 71.2 47 >42
NH3 16.2 14 12
13.9 15e
Notes: a All energies are in kcal/mol. b [27]. Only the value of
Q NH = 13.9 kcal/mol is with the zero-point energy correc-
3
tions. c [86]. d [87]. e [85].
tern was found for N versus NH, namely the normal
order N > NH for Pt(111) (see Table 11) but the
reversed order N < NH (7.6 and 39.4 kcal/mol, respec-
tively) for Ag(111) [50]. Again, the reason for this
reversal might be the limit of the amount (maximum
two) of the shared metal electrons in the metal-adsor-
bate binding [50].
For the VIII group metals, the CH radical appears to
be the only example where the UBI–QEP formalism to
calculate the molecular binding energies is conspicu-
ously deficient. This deficiency is quantitative, how-
ever. A more serious, conceptual challenge to the
UBI−QEP modeling might occur if the discussed pat-
terns of the atomic and molecular binding energies on
Ag(111) [50] will be found also on other metals.
5. COVERAGE EFFECTS
5.1. Atomic Coadsorption
So far we considered the binding energies of iso-
lated adsorbates. Now we move to the energetics of co-
adsorption. There is a solid experimental and theoreti-
cal evidence that, at low enough coverage when there is
no steric hindrance, the direct (through space) A–A
interaction is much weaker than the indirect (mediated
by the surface metal atoms) A–M–A interaction (see
references in [12]; for recent work, see, e.g., [88–91]).
This fact is a cornerstone of the UBI–QEP modeling
which treats explicitly only surface-mediated bond
energies.
M–A bond energy competition in the metal atom
sharing A–M–A: What is conserved? The fundamental
feature of metal-adsorbate bonding in Mn–A and M–Am
fragments is competition between the M–A–M and
A−M–A bonds. This competition is omnipresent and
manifests in weakening binding energies, bond length-
ening, changes in preferred coordination sites under
coadsorption, etc. These manifestations are invariably
found in all ab initio/DFT calculations. In particular, it
was said that this competition “is a manifestation of the
bond order conservation principle: The more the
valence electrons of a metal atom at the surface become
No. 4 2007
320 SHUSTOROVICH
Table 12. Coverage dependence of QO for O/fccAg(111):
DFT versus UBI–QEPa
DFT QO(θ)/QO(0) ratio
θ Expc
QO(θ)b QO(0) DFTb UBI–QEPd
0.11 83.3
0.25 81.2
0.33 78.0
80.8e 80
0.50 67.4 0.83 0.83
0.66 59.8 0.74
0.75 52.4 0.65
1.00 45.7 0.57 0.56
Notes: a All energies in kcal/mol. b [35]. c From Table 3. d From
[12, Table 13]. e Average DFT value within the range of θ =
0.11–0.33.
distributed in bonds with neighboring atoms, the
weaker the individual bond becomes” ([92, p. 231].
This formulation, however, is a qualitative statement
about antithetical relations between strengths of the
competing bonds but not a quantitative conservation
relationship (explicitly, what is conserved?). By con-
trast, the UBI–QEP model quantifies the bonding com-
petition in the form of a genuine conservation stating
what is conserved (namely, explicitly defined bond
orders/bond indices) and how this conservation
(namely, at unity) can be quantitatively verified. The ab
initio/DFT studies that find manifestations of the bond
competition can be used to verify/falsify the quantita-
tive UBI–QEP conservation relationships. For the his-
tory of the bond order conservation principle, the inter-
ested reader is referred to [9, 12, 93].
Coverage dependence of QA. Consider now quanti-
tative aspects of the metal atom sharing. In a regular
unit mesh Mn–A all the A atoms occupy the n-fold hol-
low sites. The zero-coverage UBI–QEP binding energy
QA(θ = 0) does not change within the coverage range
0 < θ ≤ 1/n when (in the ground chemisorption states at
0 K) there are no co-adsorbates in the adjacent Mn–A
cells. When the coverage increases at θ > 1/n (and may
be earlier at finite temperatures), some adjacent cells
will be occupied, and some atoms M will be coordi-
nated to more than one adatom A being shared in the
formed A–M–Am fragments, 1 ≤ m ≤ n. As a conse-
quence of the UBI conservation, each initial two-center
A–M bond energy Q0A = QA(n)/(2 – 1/n) (cf. Eq. (5))
decreases, the more so the larger is m. For a given m, the
decrease in QA is the more pronounced the more metal
M atoms are shared. All these lead to the new and
smaller binding energy QA(θ) < QA(θ = 0) [12].
The UBI–QEP analytic formalism allows one to cal-
culate QA(i)(θ) for any atom A(i) in any specific configu-
ration of p co-adsorbed atoms A within any (super)cell
Ap Mq (θ = p/q) [9–12, 94–96]. The original UBI–QEP
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B
analytic formalism to calculate QA(θ) [12] has recently
been extended to better quantify the metal sharing
under co-adsorption. Specifically, two major correc-
tions were introduced [97]:
(1) Rescaling two-center M–A bond energies under
co-adsorption to account for the fact that in the M–Am
cluster each A already sits in the hollow site, so the
lengthening of the shared A–M–A bonds will weaken
other existing bonds and therefore will be resisted.
(2) An adjustment of the binding energies of the co-
adsorbed A atoms left on a surface after removal/de-
sorption of the atom A.
The first correction increases QA(θ), the second cor-
rection decreases it. Some simple cases are transparent
but in general the quantitative estimates require the use
of specially designed computing programs [97].
Although these calculations revealed some new inter-
esting details, the qualitative UBI–QEP projections did
not change, and the numerical corrections were small.
So, for clarity and simplicity, below we will use the
original UBI–QEP QA(θ) values [12].
The UBI–QEP QA(θ) values change (decrease) dif-
ferently for different n-coordination sites—atop, bridge
and hollow. For the range of 0 ≤ θ ≤ 1, the atop binding
energies do not change at all, the bridge binding ener-
gies do not change up to θ = 1/2 and then begin to
decline, and the hollow binding energies do not change
up to θ = 1/n but then decline even faster than the bridge
energies. Because of this steep decline, at some cover-
age θ > 1/n the hollow binding energy formally
becomes smaller than the bridge one. Originally it was
assumed that at this point the bridge sites might start to
be occupied [12, 94, 95]. Later, however, this assump-
tion was abandoned [97] when it was realized that even
at high coverage the hollow sites remain the only
energy minima. Indeed, the atomic occupancy of the
bridge (let alone the on-top) sites have never been
found experimentally (see a discussion and references
in [97]). Although some ab initio/DFT calculations
found the bridge site preferred at high enough coverage
(see, e.g., [44, 98–100], most of them find the hollow
sites preferred regardless of coverage. So below we will
discuss the UBI–QEP projections for a coverage-
dependent decrease of QA(θ) only for the hollow sites.
Only a few DFT calculations were made for a wide
enough coverage range. The periodic slab calculations
of the O/fccAg(111) system [35] are unique by cover-
ing the whole range of θ = 0.11, 0.25, 0.33, 0.50, 0.66,
0.75, 1.00. For all coverages, the preferred coordination
site is fcc-hollow. The results are shown in Table 12.
One can see that the values of QO(θ) monotonically
decrease from the start, slowly in the beginning and
precipitously after θ > 0.33. These data allow one to
calculate the QO(θ)/QO(0) ratios, which are also shown
in Table 12 and compared with the UBI–QEP results.
Because the UBI–QEP value QO(θ) does not change for
the range of θ = 0–0.33, the proper DFT value of QO(0)
for comparisons was taken as the average of three
Vol. 1 No. 4 2007
 CHEMISORPTION ENERGETICS AND SURFACE REACTIVITY 321

QO(θ) values for θ = 0.11, 0.25, 0.33, namely QO(0) ~ Table 13. Coverage dependence of QO for O/fccRh(111):
81 kcal/mol, which is in excellent agreement with the DFT versus UBI–QEPa
experimental value of QO(0) = 80 kcal/mol (see Table 3).
DFT QO(θ)/QO(0) ratio
Within the cited DFT coverage range, the UBI–QEP θ Expc
ratios QO(θ)/QO(0) were calculated for θ = 0.50 and QO(θ)b QO(0) DFTb UBI–QEPd
1.00 (see [12, Table 13]). The agreement with the DFT
ratios is amazingly (better: amusingly) close. 0.25 120.5 120.5 102
Other examples are the DFT periodic calculations of 0.50 113.8 0.94 0.83
O/Rh(111) [38] and O/Pt(111) [48], both starting with 1.00 101.6 0.84 0.56
θ = 0.25. The calculated values of QO(θ) and the Notes: a All energies in kcal/mol. b [38]. c From Table 3. d From
QO(θ)/QO(0) ratios for θ = 0.25, 0.50, and 1.00, are [12, Table 13].
shown in Tables 13 and 14, respectively, and compared
with the UBI–QEP values. In the both cases, the agree-
ment is quantitatively close for θ = 0.50 but only qual- Table 14. Coverage dependence of QO for O/fccPt(111):
itatively consistent for θ = 1.00. DFT versus UBI–QEPa
To summarize, the coverage dependence of the DFT QO(θ)/QO(0) ratio
binding energies is qualitatively similar in the UBI– θ Expc
QEP and DFT approaches for the whole range 0 ≤ θ ≤ 1, QO(θ)b QO(0) DFTb UBI–QEPd Expc
and the agreement is even quantitatively close up to θ =
1/2. After θ > 1/n, the UBI–QEP binding energies typi- 0.25 88.3 88.3 80.0
cally decrease with coverage faster than the DFT ones. 0.50 82.0 0.93 0.83 0.94
Therefore it was suggested to use the DFT values of 1.00 65.9 0.75 0.56
QA(θ) to re-scale the UBI–QEP coverage-dependent
Notes: a All energies in kcal/mol. b [48]. c [36]. d From [12, Table 13].
energetics. This re-scaling, combined with Monte
Carlo simulations, was used in kinetic modeling of var-
ious surface reactions, most exhaustively by Neurock
et al. [91, 100–105]. where
The UBI–QEP analytic formalism [9–12, 94–96] ∆H = D AB + Q AB – Q A – Q B (12)
allows one to calculate also the metal sharing effects on
the binding energies of different co-adsorbates A and B,
is the enthalpy of the dissociation reaction. The interpo-
A ≠ B, both atomic and molecular. This UBI–QEP for-
malism is more complex than that for identical co- lation is accomplished by choosing the proportionality
adsorbates, considered above, and practically can be coefficient k < 1 as
applied only in computer simulations. The primary
importance of such co-adsorption effects is that they ∆E ABa, int = k [ ∆H + Q A Q B / ( Q A + Q B ) ], (13)
affect the coverage-dependent activation barriers of the
dissociation and recombination reactions, ABa which in the simplest (arithmetic mean) form k = 1/2
Aa + Ba. Below we will mention some results, referring give the standard UBI–QEP expression
the reader to the original papers for computational
details. ∆E ABa, int = 1/2 [ ∆H + Q A Q B / ( Q A + Q B ) ] (14)

6. INTRINSIC ACTIVATION BARRIERS or

OF DISSOCIATION AND RECOMBINATION
∆E ABa, int = 1/2 [ D AB + Q AB – Q A – Q B
6.1. Energetic Structure of the UBI–QEP Barrier: (15)
Reminder + Q A Q B / ( Q A + Q B ) ].
In order to compare with the DFT projections let us In the case of a homonuclear diatomic A2, the dissocia-
recall how the UBI–QEP model considers the intrinsic
tion barrier is simply
activation barriers of dissociation ∆E ABa, int and recom-
bination ∆E A–Ba, int reactions, ABa Aa + Ba. ∆E A2a, int = 1/2 [ D A2 + Q A2 – ( 3/2 )Q A ]. (16)
Because the UBI–QEP model calculates only potential
energy minima (binding energies), the saddle For the recombination Aa + Ba ABa, the intrinsic
point/maximum energy (the activation barrier) can only barrier ∆E A–Ba, int is determined by the conservation of
be interpolated within a certain range, whose maximal
value is [9, 13] energy, namely

∆E ABa, max = ∆H + Q A Q B / ( Q A + Q B ), (11) ∆E A–Ba, int = ∆E ABa, int – ∆H. (17)

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B Vol. 1 No. 4 2007

322 SHUSTOROVICH
The intrinsic dissociation barrier ∆E ABg, int from the
gas-phase state is obviously
∆E ABg, int = ∆E ABa, int – Q AB
(18)
= 1/2 [ ∆H g – Q AB + Q A Q B / ( Q A + Q B ) ],
where ∆Hg is the dissociation enthalpy from the gas
phase
∆H g = D AB – Q A – Q B . (19)
In principle, the observed activation barrier may
also include a contribution from diffusion of adsorbates
to and from the transition state [9, 106]. One can argue,
however, that typically this diffusion contribution can
be ignored (although for different reasons for small and
large diffusion barriers) [11]. Thus, the intrinsic barrier
can usually be identified with the apparent (observable)
barrier, ∆Eint = ∆E. Indeed, this identification was quite
successful in numerous UBI–QEP studies of various
reactions including Fischer–Tropsch chemistry, ammo-
nia decomposition and synthesis, methanol synthesis,
WGS reaction, oxygen-assisted X–H bond cleavage,
etc. (see [9, 13, 107] and references therein). This iden-
tification also justifies direct comparisons of the UBI–
QEP ∆Eint with both the experimental and ab ini-
tio/DFT barriers (the latter are also the intrinsic barri-
ers). Below we will discuss both general regularities
and numerical values.
6.2. UBI–QEP Versus DFT: Qualitative Comparisons
Periodic regularities. Since the atomic binding
energies are much larger than the molecular ones,
QA, QB
QAB, the UBI–QEP dissociation barriers are
mainly determined by the values of the atomic binding
energies QA and QB. When the latter show distinct peri-
odic regularities (see Section 3), the periodic regulari-
ties of the dissociation barriers immediately follow. In
particular, if the values of QA and QB decrease from left
to right along the rows and from top to bottom along the
columns, the dissociation barriers ∆EAB increase along
the same lines. These regularities have already been
thoroughly discussed [9–11, 13, 32], and they are in full
agreement with the results of the ab initio/DFT calcula-
tions [1–4].
Here a comment might be useful. Compared with
the original UBI–QEP studies [9, 11, 13, 32] the only
substantial difference is that if earlier we assumed the
periodic decrease of the carbon binding energies QC
along the series Ni(111) > Pd(111) > Pt(111) with QC =
170, 160, and 150 kcal/mol, respectively, now (see
above) we assume that there are no changes in QC along
this series, Ni ~ Pd ~ Pt with QC = 155 kcal/mol. The
question is how much these changes affect the previous
UBI–QEP conclusions concerning the periodic trends
in the dissociation barriers ∆ECA of the C–A bonds
along the series Ni Pd Pt, in particular (and
most importantly) for the CO dissociation. The answer
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B
is: not much quantitatively (few kcal/mol, cf. Eq. (14))
and not at all qualitatively (Ni is more active than Pd
and Pt), because the oxygen binding energies QO show
a very distinct periodic trend decreasing from Ni(111)
to Pt(111) by 30 kcal/mol (see Table 3).
Another periodic UBI–QEP projection was the
effect of (low-coverage) pre-adsorption of oxygen on
the X–H bond cleavage, X = O, N, and C [9, 108]. By
comparing the UBI–QEP activation barriers for direct
X–H and oxygen-assisted X–H…O dissociation it was
predicted that the effect of pre-adsorbed oxygen will be
reversed along the periodic series (e.g., Ag, Cu, Ni, W),
from facilitating X–H bond cleavage on the least active
metals such as Ag and Au to inhibiting this process on
the more active metals such as Ni and W. This UBI–
QEP projection, being in broad agreement with
experiment [109], was corroborated by various DFT
calculations (see, for example, the latest DFT studies
of the oxygen-assisted bond cleavage, N–H…O [27],
O−H…O [43], and C–H…O [110], and references
therein).
Linear relationships: is it a good approximation?
Many DFT studies revealed a “universal” linear depen-
dence of the dissociation barriers on the reaction
enthalpy (see particularly [6–8, 56, 111]). If the refer-
ence point is AB in the gas phase, the claimed depen-
dence (relationship) is
∆E ABg, int = k∆H g + C, (20)
where the proportionality coefficient k and the constant
C may be different for different classes of dissociating
bonds and for different surface types (say, on close-
packed surfaces and on steps). The values of k were
usually found to be close to unity, k = 0.75–0.97, which
was often said to be indicative of the product-like or
“late” transition states (see, for example, [7, 56]). The
dependence of Eq. (20) is similar to the BEP (Brøn-
sted–Evans–Polanyi) relationship
∆E AB = α∆H, (21)
where the proportionality coefficient α is typically
assumed to be around α ~ 1/2 (namely, α < 1/2 if the
reaction is exothermic but α > 1/2 if the reaction is
endothermic [92]).
Within the UBI–QEP framework, the activation dis-
sociation barriers ∆E ABg (Eqs. (18)–(19)) are deter-
mined not only by the reaction enthalpy ∆Hg but also by
the term QAQB/(QA + QB) – QAB, which may be small
or large depending on the relevant Q values. Thus, in
principle, the dissociation barrier ∆E ABg should deviate
from a linear relationship. The ∆EAB versus ∆H rela-
tionship has been found to be non-linear within other
theoretical models as well, in particular for dissociative
oxygen adsorption on various surfaces of Rh, Ag, and
Au [112]. Still, some approximate linear relationships
(with different ad hoc values of k and C) may some-
times be obtained. In particular, the UBI–QEP dissoci-
Vol. 1 No. 4 2007
 CHEMISORPTION ENERGETICS AND SURFACE REACTIVITY
ation barrier for a homonuclear molecule A2 (neglect-
ing a small term Q A2  QA = QB) has a form of
∆E A2g ∼ D A2 – ( 3/2 )Q A . (22)
Thus, for a given molecule A2 ( D A2 = const) the barrier
differences on different metal surfaces will be propor-
tional to the atomic A binding energy QA, which is a
variation of the linear Brønsted–Evans–Polanyi rela-
tionship, Eq. (21).
While claiming the existence of the universal linear
dependence, Eq. (20), it was also stated that the “accu-
racy of the DFT calculations is not such that we can
give a quantitative treatment” [6]. Thus, one should
exercise caution because the conclusions may depend
not only on the accuracy of calculations but also on
their interpretation. In particular, the interpretation
might sometimes be affected by the resolution of the
data set depending on the choice of energy units. For
example, the linear ∆E versus ∆H relationship in elec-
tronvolts has been reported in the DFT studies of the
NHx dehydrogenation (dissociation) reactions by
Michaelidis et al. [7, 56], who found the slope close to
unity (k ~ 1) implying the product-like or “late” transi-
tion states. However, when Offermans et al. [27] re-cal-
culated the DFT reaction energetics with zero-point
energy corrections they found large deviations from the
proposed linear relationship, being around –20, +50,
and +20 kJ/mol for the NH3, NH2, and NH dissociation,
respectively. Moreover, when Offermans et al. [27]
simply magnified the resolution of the data set by
Michaelidis et al. [7, 56] by using the energy units in
kJ/mol instead of eV (1 eV ~100 kJ/mol), similar devi-
ations were found also in the original set, making
meaningless the conclusions concerning the linear rela-
tionship, its slope and “lateness” of the transition state.
Because most of DFT studies reported the linear ∆E
versus ∆H relationship in electronvolts, such a magnifi-
cation of the resolution appears to be warranted in all
those studies, not to mention a necessity of evaluating
the zero-point energy corrections.
Another example is a DFT study of methane disso-
ciation on Rh(111) by Bunnik and Kramer [57]. From
an analysis of the transition state energies and geome-
tries the authors concluded that, unlike the claim by
Michaelidis et al. [7], the different CHx steps do not fall
in the same class, so that there is no universal BEP rela-
tionship and no simple way to predict the “lateness” of
the transition states.
A further example is the DFT calculations of H2O
dissociation on clean and oxygen-pre-adsorbed metal
surfaces [43]. It was demonstrated that even if the O–H
dissociation barrier on the clean surfaces might approx-
imately fit the BEP relationship the latter fails for the
oxygen-pre-adsorbed surfaces, which makes inconclu-
sive any guess concerning the nature of the transition
states.
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B Vol. 1
323
For the purposes of the present review, a more infor-
mative example is the DFT studies of the ethanol
decomposition on Pt(111) by Alcala et al. [111]. For the
dissociation of relevant intermediates, the authors
found the linear relationship, Eq. (20), with the slope of
k = 0.97 ± 0.03 and the constant C = 1.50 ± 0.15 eV. The
∆E ABg versus ∆Hg relations, calculated by the UBI–
QEP formalism, fits Eq. (20) with k = 0.94 ± 0.04 and
the constant C = 0.85 ± 0.20 eV [113]. Pragmatically,
this close agreement with the numerical DFT data man-
ifests the comparable accuracy of the UBI–QEP model
for quantitative estimates of binding energies and acti-
vation barriers (see more details below). At the same
time, because the analytical UBI–QEP model projects
that the ∆EAB versus ∆H relationship should in princi-
ple be non-linear (Eq. (14)), it would be interesting to
see whether the reported DFT linear relationship will
hold if the electronvolts are replaced by kJ/mol.
As said above, Eqs. (14) or (15) with the UBI–QEP
proportionality coefficient k = 1/2 is the standard form
corresponding to the simplest interpolation: the arith-
metic mean between two extremes [13]. (In this respect
k is similar to the BEP coefficient α ~ 1/2 in Eq. (21)).
Of course for particular cases the coefficient k < 1 may
be fine-tuned. For example, in the UBI–QEP studies of
CO and H2 oxidation and the WGS reaction on Rh, a
better fit with experiment was found for the value of
k = 0.8 [114].
Geometry of transition states. The intrinsic UBI–
QEP activation barriers, being determined completely
by the energetics of initial (reactants) and final (prod-
ucts) states, do not require knowledge of geometry of
the transition state (TS). It was claimed [46] that the
UBI–QEP method underestimates the activation barri-
ers because it ignores interaction energies associated
with coadsorption. This is a plain misunderstanding.
The TS energy (activation barrier) is determined by the
UBI–QEP constraint which automatically includes
changes in coadsorption energies from the initial state
when the reactants are infinitely separated on a surface
to the TS where the reactants diffuse close enough to
interact. Thus, the UBI–QEP model is not totally blind
to the TS geometry but can qualitatively project its
some major features determined by the preferred geom-
etry of co-adsorption of non-equivalent species. In par-
ticular, the UBI–QEP model projects that the stronger
bound species prefer a minimal change from their
ground-state adsorption site [9, 12]. For example, in the
TS of the reactions C + H CH or C + O CO,
the hollow site will be occupied by C but H and O will
be close to the bridge site. However, in the TS for the
oxidation reaction CO + O CO2, the hollow site
will be occupied by O but CO will be close to the bridge
or atop site. Indeed, this general pattern and the cited
specific TS arrangements are found in most DFT calcu-
lations providing the co-adsorption geometries along
the (minimum energy) reaction path including those of
No. 4 2007
324 SHUSTOROVICH
the TS (see, e.g. a discussion and references in [16, 44,
56, 115]).
6.3. UBI–QEP Versus DFT: Quantitative Comparisons
Hybrid UBI–QEP/DFT approach. Recall that the
UBI–QEP formalism to calculate the activation barri-
ers, Eqs. (11)–(19), requires only the knowledge of the
relevant atomic and molecular binding energies Q.
They should be as accurate as possible but their origin
does not matter: they might be calculated (by UBI–
QEP or ab initio/DFT or other proper techniques) or
taken from experiment. Numerous examples have
already been discussed [9, 11, 13] confirming the gen-
eral rule that the accurate (enough) values of Q lead to
the accurate (enough) values of ∆E.
This corroboration of the UBI–QEP formalism
prompted a development of some “hybrid” approaches
where the ab initio/DFT binding energies have been
plugged in the UBI–QEP formulas for the barriers,
Eqs. (11)–(19). For example, such an approach was
employed in the analysis of methanol oxidation [116]
and the WGS reaction [117–119], in broad agreement
with experiment. Various examples of this kind are con-
sidered in the accompanying article in this issue [120]).
True, there was also one DFT study of chemisorp-
tion energetics (for low CO coverage on Ni(111))
where the authors used their data to calculate the UBI–
QEP activation barriers and claimed that the latter are
highly inaccurate [46]. This claim, however, is a result
of obvious errors in calculations of the UBI–QEP val-
ues. The calculated DFT binding energies were QC, QO,
QCO = 156, 137, 44 kcal/mol, respectively. For this
DFT energy set, the UBI–QEP barrier for CO disso-
ciation (cf. Eq. (15)) is 39 kcal/mol but the authors mys-
teriously cited the UBI–QEP barrier of ∆ECO =
5 kcal/mol. If one uses the assumed experimental
energy set QC, QO, QCO = 171, 115, 27 kcal/mol, respec-
tively, the UBI–QEP barrier is ∆ECO = 33 kcal/mol
(cf. [13, Table 9]). Clearly, the problem in the work [46]
is not with using the DFT energy numbers (with the
experimental Q values there would be very close
results) but with a gross arithmetic error in calculating
the UBI–QEP activation barrier.
DFT activation barriers. Ab initio/DFT calculations
of the intrinsic barriers are usually obtained by using
the Nudge Elastic Band (NEB) method [121] with fur-
ther improvements and modifications [69, 122, 123].
The NEB method is designed to search for the mini-
mum energy path between the given initial and final
states, where the potential maxima are the saddle points
and the highest saddle point, corresponding to a transi-
tion state, TS, gives the reaction activation barrier ∆E.
But the accuracy, as the proverbial devil, is in
details. Let us mention some of them.
(1) The common GGA exchange-correlation func-
tionals may strongly overestimate the barriers for C–H
bond scission, which lead to questioning whether the
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B
GGA functionals are appropriate for the description of
the C–H bond scission [124].
(2) The zero-point energy effects generally reduce
the DFT activation barriers (see, e.g., [27, 71]) but
many DFT calculations neglect these effects.
(3) In order to reduce computational efforts, varying
constraints on the geometry of the transition state are
common. The commonest constraint is a fixed adsor-
bate–adsorbate distance but it might lead to the incorrect
TS and therefore to the incorrect activation barrier. For
example, in the DFT calculations of the CO + O
CO2 reaction on Pt(111) this constraint lead to the TS
with oxygen in the bridge site while the unconstrained
TS has oxygen in the hollow site (see discussion in [16,
44, 56, 115]).
(4) The coverage effects even at low coverage
appear to be distinct already for atoms (see above), and
they are more important for molecules. Accordingly,
the choice of the periodic unit cell (which determines
the coverage) might strongly affect the geometry and
the binding energy of the molecular precursor AB* and
the AB dissociation activation barrier. For example, the
common (2 × 2) unit cell of the fcc(111) surface might
be too small to properly treat the AB A + B dis-
sociation even for such a small molecule as O2. The
A–(2 × 2) unit cell corresponds to θA = 0.25 (<1/n)
without A–M–A sharing but the A2–(2 × 2) cell leads to
θA = 0.50 (>1/n) with A–M–A sharing and therefore
with much smaller binding energies QO. Moreover, in
the molecular O 2* precursor the O–O bond length
increase might be such that, due to the periodic 2 × 2
boundary conditions, oxygen atoms form a chain struc-
ture on the surface, so that the dissociation process can
be properly studied only using a larger surface cell
[125]. Specifically, this is the case of O2 on Pd(111)
when the DFT dissociation barrier for the 2 × 2 cell was
found to be about 23 kcal/mol [126] but with the
(slightly larger) 3 × 2 cell the dissociation trajectory
changed and the barrier reduced to 20 kcal/mol and
would certainly drop further for a larger cell [125].
For the larger (polyatomic) molecules the size of the
unit cell is even more critical. An example is the
CH3OH/Pt(111) system, where in similar DFT periodic
calculations for slightly differing coverage, θ = 0.11
and 0.25 (the 3 × 3 and 2 × 2 unit cells), the barriers for
O–H bond scission differ by 15 kcal/mol, namely 19
[71] and 34 kcal/mol [72], respectively.
The list of possibly varying details, often hidden in
the chosen assumptions and approximations, is long.
As a result, even the apparently similar DFT calcula-
tions often give dissimilar activation barriers.
All those factors are irrelevant for the UBI–QEP
model. Recall that its AB A + B dissociation bar-
rier (the TS energy) is determined by the ground-state
binding energies of the reactant AB and the products, A
and B (see Eqs. (11)–(19)), so the model is not con-
cerned with the explicit TS geometry and the reaction
Vol. 1 No. 4 2007
 CHEMISORPTION ENERGETICS AND SURFACE REACTIVITY 325

path. For both the reactant and products, there are no
coverage and steric constraints artificially imposed by
the boundary conditions. Furthermore, one can often
ignore the effect of the atomic, A and B, diffusion bar-
riers on the resulting coordination sites when the high
barriers might cause A and B to stay close enough to be
energetically penalized for the forced A–M–B metal
sharing. Indeed, if the AB dissociation is exothermic
(which is typical for O2 on most metal surfaces) the
forming A and B atoms are “hot” enough to travel sev-
eral lattice distances to find the most favorable coordi-
nation sites minimizing the A–M–B competition (see,
for example, Monte Carlo/UBI–QEP simulations of the
O2 dissociation on fcc(111) [127] and fcc(100) [97])
surfaces. Anyway, whatever the final mutual A and B
position, the UBI–QEP coverage-dependent binding
energies automatically take care of the coverage-depen-
dent barrier. (The higher the coverage the smaller are
the product, A + B, binding energies and therefore the
larger AB dissociation barrier.)
Because there is no direct interrelation between the
DFT and UBI–QEP barriers, it is not clear when they
might be similar or different. The comparison is further
obscured by the fact that for the same system usually
there is a variety of DFT calculations producing dis-
tinctly different numerical results. Not surprisingly,
there are examples where there is good agreement
between the UBI–QEP and DFT calculated barriers,
and there are examples where the agreement is not
good. At present, a systematic comparison of the DFT
versus UBI–QEP barriers can hardly be made, and it is
beyond the scope of this review.
Below we will give only few examples to illustrate
these points. After all, the most important is how con-
sistent are the UBI–QEP and DFT projections with
experiment. So, we will limit our illustrations to reac-
tions when the UBI–QEP barriers are in good agree-
ment with experiment and will compare them with the
relevant DFT values. Table 15 shows several such
examples which, in hope to discern some regularities,
are further limited to the same reaction type (recombi-
nation) on the same surface, Pt(111). No regularities
were discerned: in some cases the agreement is good
but in others, not.
The next example, however, is a case of remarkable
correspondence between the UBI–QEP and DFT pro-
jections, and this is for a multi-step process including a
variety of reactions—dissociation, recombination, and
desorption.
DFT vs. UBI–QEP: detailed comparison. The
process is ethanol decomposition on Pt(111) which
comprises bond dissociation (O–H, C–H, C–O, C–C)
and recombination, and desorption of the reactant
(CH3CH2OH) and products (CO, CH4, and H2). It was
studied by Vesselli et al. [113] who applied the UBI–
QEP method and used the results as a benchmark for
evaluating the accuracy of the UBI–QEP model by
comparing with both self-consistent periodic DFT cal-
Table 15. Intrinsic UBI–QEP activation barriers (kcal/mol):
comparison with the DFT and experimental valuesa
Calculated ∆EintExperi-
Reaction
Metal
mental
surface DFT UBI–QEP ∆E
H2O + O 2OH Pt(111) 8c 11 10
H+O OH Pt(111) 23c 10 <13
20d
H + OH H2O Pt(111) 23c 11 16 ± 5
20d
CO + O CO2 Pt(111) 23b 23 25
26e
Notes: a All UBI–QEP and experimental data are taken from [11,
Table 6]. b [128]. c [129]. d [56]. e [115].
culations [111] and diverse experiment. Although DFT
values have been considered as a reference for the UBI–
QEP model, it was stated that because “ab initio frame-
works can fail in the treatment of some interactions…
discrepancies between results from the two frameworks
are therefore not necessarily indicating a failure of the
simple [UBI–QEP] model.”
The tested UBI–QEP quantities were key reaction
parameters such as adsorption energies (of reactants,
intermediates, and products) and activation barriers of
possible elementary steps. Simulation of the whole
decomposition reaction, from CH3CH2OH to CO, CH4,
and H2, was made. Temperature programmed desorp-
tion (TPD) spectra and surface coverage of the stable
species as a function of the temperature have been sim-
ulated to provide a direct comparison with experimen-
tal data. The major findings are as follows:
(1) With practically no exception, there is close
agreement between the DFT and UBI–QEP values of
the adsorption energies, all in all for 24 species (see
[113, Fig. 1]).
(2) Qualitatively, the both theoretical approaches
project practically the same reaction mechanism. For
most part, there is also good agreement between the
activation barriers of various elementary steps. When
poor agreement between the DFT and UBI–QEP acti-
vation barriers was found, the UBI–QEP projections
usually were in better agreement with experiment, and
these were projections concerning such diverse and
important features as temperatures of the C–C and C–O
bond dissociation, temperature dependence of surface
concentration of the stable species, and TPD spectra of
reactants and products.
The importance of this example is that the DFT and
UBI–QEP barriers closely correlate, qualitatively and
even quantitatively, for a variety of reactions. This
might be taken as a corroboration of the UBI–QEP con-
servation along the minimal potential energy path for
molecular dissociation.

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B Vol. 1 No. 4 2007

326 SHUSTOROVICH
7. CONCLUSIONS
The ab initio/DFT and UBI–QEP approaches treat
chemisorption energetics and reactivity on metal sur-
faces in a general and complementary way. The abun-
dance of the DFT calculations makes it possible to eval-
uate their accuracy and systematically compare projec-
tions of the DFT and UBI–QEP approaches. In this
review we made representative comparisons dealing
with both qualitative and quantitative aspects of the
energetics and reactivity.
First, we considered DFT verification of the UBI–
QEP projections concerning atomic A binding energies
at low coverage (no metal sharing A–M–A). These
model projections are most general and rigorous
because they are determined by symmetry of the n-fold
coordination site Mn–A and independent of the nature
of A and M. The UBI–QEP projections of the relative
energies of the hollow, bridge and atop sites (the hollow
site is preferred) and of the diffusion barriers (along the
hollow-bridge-hollow path) are quantitatively corrobo-
rated by numerous DFT calculations of various atoms
(A = O, N, C, S) on various M surfaces (M = Rh, Ir, Ni,
Pt, Cu, Ag, etc.). This quantitative agreement between
the DFT and UBI–QEP values is the most direct cor-
roboration of the validity of the UBI–QEP model.
Other UBI–QEP projections include some addi-
tional assumptions and parameters which make the
model results less rigorous and therefore their DFT ver-
ification less certain. The basic UBI–QEP parameter is
the (zero coverage) atomic binding energy QA in the
hollow site. It’s convenient to distinguish the UBI–QEP
projections by whether they are concerned with the rel-
ative binding energies (expressed in terms of QA) or
they employ the absolute (numerical) value of QA. The
projections of the first kind include coverage effects on
the A binding energies under atomic co-adsorption. The
projections of the second kind deal with molecular QAB
binding energies and the AB reactivity patterns (activa-
tion barriers ∆EAB). In any model projection there are
qualitative and quantitative aspects. It is easy to see the
qualitative agreement or disagreement but it is more
difficult to judge the quantitative closeness. The fact is
that the DFT (and experimental) values of QA, QAB, and
∆EAB usually are not unique but each entity forms a
range of calculated (and measured) values. The UBI–
QEP parameter QA is taken from experiment or theoret-
ical calculations. For all practical purposes, the UBI–
QEP QA should be uniquely numerically defined but
such a single value can hardly be chosen if the theoret-
ical and/or experimental values QA constitute a wide
range. Nevertheless, we tried to make reasonable com-
parisons.
The UBI–QEP projections using the relative bind-
ing energies (expressed in terms of QA) include cover-
age effects revealing the M–A bond energy competition
(metal sharing A–M–A) under atomic co-adsorption.
The coverage dependence of the binding energies is
qualitatively similar in the UBI–QEP and DFT
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B
approaches for the whole range 0 ≤ θ ≤ 1, and the agree-
ment is even quantitatively close up to θ = 1/2. After
θ > 1/n, the UBI–QEP binding energies typically
decrease with coverage faster than the DFT ones. One
can use the DFT values of QA(θ) to re-scale the UBI–
QEP coverage-dependent energetics, and this re-scal-
ing was made in modeling of various surface reactions.
All other UBI–QEP projections use the absolute
binding energies QA. Based on the experimental and
theoretical data of the time, in the original UBI–QEP
studies we assumed a monotonic decrease of QA for all
atoms (H, O, N, and C) along the VIII–IB rows and
from top to bottom along the column. Now, based on
the systematic DFT calculations (no new experimental
data) for the VIII group metals, we re-evaluated the car-
bon binding energies QC and assumed the same value
of QC = 155 kcal/mol for Ni, Pd, and Pt, differing
from the original (non-equal) UBI–QEP values by 5–
15 kcal/mol. These slight changes, however, practically
did not affect the previous UBI–QEP projections. There
were also modifications for some nitrogen QN binding
energies, particularly for Ir and Pd, but so far there were
no UBI–QEP calculations for those metals and there-
fore no projections to correct. For the IB metals the ab
initio/DFT calculations are scarce, mostly limited to
oxygen adsorption. But it looks probable that the peri-
odic QA regularities for the IB metals might be differ-
ent. Accordingly, our revision of QA for the IB metals is
more substantial. Now we recommend using only the
oxygen parameters QO whereas the nitrogen QN and
carbon QC parameters need further ab initio corrobora-
tion. The recommended values of QA are summarized
in Table 5.
The absolute values of QA are used in calculations of
molecular QAB binding energies, and here the UBI–
QEP validity has been tested along two lines: (1) pro-
jected qualitative regularities of QAB, and (2) numerical
accuracy of values of QAB. The qualitative UBI–QEP
projections for molecular AB coordination concern
with the preferred contact atom A (it has a larger atomic
binding energy, QA > QB) and the preferred coordina-
tion site (the higher coordination for the atomic-like
molecular radicals but no preference for weakly bound
molecules). DFT studies fully corroborate these regu-
larities. Typically, there is a good correlation between
the numerical UBI–QEP and DFT values of QAB. The
most conspicuous exception is methylidine CH: while
the (periodic slab) DFT values of QC and QCH are close
the corresponding UBI–QEP values are distinctly dif-
ferent. A quantum mechanical explanation of why the
atom C and the radical CH have very close binding
energies is necessary.
Secondly, the UBI–QEP projections using the abso-
lute binding energies QA and QB (and QAB) deal with
the AB A + B reactivity patterns judged by the cal-
culated activation barriers, dissociation ∆EAB and
recombination ∆EA–B. The atomic binding energies are
the major contributors to the barriers, such that a
Vol. 1 No. 4 2007
 CHEMISORPTION ENERGETICS AND SURFACE REACTIVITY
decrease (increase) of QA and QB results in an increase
(decrease) of ∆EAB. The qualitative projections include
the periodic regularities (changes of ∆EAB along the
VIII–IB group rows and from top to bottom along the
column, both for the direct A–B and oxygen-assisted
A–B…O dissociation), the barrier vs. reaction enthalpy
relationships (in principle, it should be non-linear
although sometimes it may be approximated as linear),
geometry of the transition state (strongly bound adsor-
bates prefer to keep their ground state adsorption site),
etc. All these qualitative UBI–QEP projections are cor-
roborated by DFT calculations.
As far as quantitative aspects are concerned, there is
no explicit interrelation between the DFT and UBI–
QEP barriers, so it’s not clear when they might be close
or different. Still, the DFT and UBI–QEP barriers often
correlate, which may be considered as a corroboration
of the UBI–QEP conservation along the molecular dis-
sociation path.
Given the variety of covered areas of chemisorption
phenomena and uncertainties of the DFT and experi-
mental numbers, the correlations found between the
DFT and UBI–QEP projections are remarkably good,
arguably better than one could expect for those comple-
mentary but totally different approaches. Further com-
parisons and testing are desirable but they will be real-
istic only under two conditions: (1) experimental data
should be more complete and definitive, and (2) the ab
initio/DFT values should be accurate enough and com-
prise a narrow range consistent with experimental data.
ACKNOWLEDGMENTS
I wish to express my gratitude to Dr. A.V. Zeigarnik
for stimulating discussions and help in literature search.
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