Viewpoints: Chemists on Chemistry
The Flexible Surface
The Flexible Surface:
Molecular Studies Explain the
Extraordinary Diversity of Surface
Chemical Properties
Outline
Historical Perspective
External Surfaces
Surface Concentration
Clusters and Small Particles
Thin Films
Internal Surfaces—Microporous Solids
Clean Surfaces
Interfaces
Adsorption
Techniques of Surface Science
Phenomena Discovered by Molecular
Surface Chemistry
Surface Structure Is Different from Bulk Structure
Adsorbate-Induced Restructuring of Surfaces
Rough Surfaces Do Chemistry
Clusterlike Bonding of Adsorbed Molecules
The Flexible Surface
Technological Impact of Molecular Surface
Chemistry
Future Directions in Surface Chemistry
Coadsorption on Surfaces
High-Pressure Surface Science
Monitoring Surface Chemistry at Ever-Improving
Spatial Resolution and Time Resolution
Studies of the Buried interfaces, Solid–Liquid
and Solid–Solid
Achieving 100% Selectivity in Surface
Reactions—the Environmental Imperative
Nanoparticles: Surfaces in Three Dimensions
Other Material on
Surface Chemistry in This Issue
On the Surface 176A
Mini-Activities Exploring Surface
Phenomena: JCE Classroom Activity #6
Flying over Atoms CD-ROM
JCE Software Special Issue 19,
by John R. Markham
JChemEd.chem.wisc.edu • Vol. 75 No. 2 February 1998 • Journal of Chemical Education
Gabor A. Somorjai and Günther Rupprechter
162
About Viewpoints
V iewpoints is a major feature of the celebration of the Journal
of Chemical Education’s 75th year. It is being supported by The
Camille and Henry Dreyfus Foundation, Inc., which recently cel-
ebrated its own 50th anniversary. Each paper in the Viewpoints se-
ries will be written by a chemist or group of chemists with special
expertise in a particular field, with the aim of providing an overview
of that field’s accomplishments, importance, and prospects. The goal
is to reflect on developments during the past 50 years and to predict
how each field will evolve over the next 25 years. The total perspec-
tive encompassed by Viewpoints corresponds with the 75 years of
this Journal’s lifetime and reflects its comprehensive interest in all of
chemistry. The 50-year retrospective view of each field corresponds
with the period during which the Camille and Henry Dreyfus Foun-
dation has been supporting the chemical sciences.
Authors of Viewpoints papers will provide perspectives on what
chemistry has done during the lifetime of the Dreyfus Foundation
and to set the stage for what chemistry will become well into the
next century. The papers will be written at a level appropriate for
upper-division undergraduate chemistry students and will extend and
enhance the Journal’s role as, in the words of an early editor, “a liv-
ing textbook of chemistry”. In addition, they will be published in
electronic format via JCE Online (whose founding was also supported
by the Dreyfus Foundation). In the Journal, Viewpoints papers will
take full advantage of color graphics, which will also appear in the
electronic version. In JCE Online there also will be links to the au-
thors’ and other related Web sites, and video and animations when
relevant.
The Viewpoints series begins this month with “The Flexible Sur-
face”, a paper from the laboratories of Gabor A. Somorjai of the Uni-
versity of California, Berkeley. Somorjai and his co-author, Günther
Rupprechter, discuss concepts related to external and internal sur-
faces and interfaces and the dynamic nature of surfaces during chemi-
cal processes. A broad overview of the most frequently used surface
science techniques is also included, along with references for each
technique. Somorjai and Rupprechter close with a discussion of the
present and future technological impact of surface chemistry on ca-
talysis and semiconductor devices, and the chemist’s role in surface
science in the coming years.
Glenn T. Seaborg, Chair of the Viewpoints Editorial Board
247
161
 Viewpoints
The Flexible Surface: Molecular Studies Explain
the Extraordinary Diversity of Surface Chemical Properties
Gabor A. Somorjai and Günther Rupprechter
Department of Chemistry, University of California at Berkeley, and Materials Sciences Division, E. O. Lawrence Berkeley
National Laboratory, Berkeley, CA 94720; http://www.cchem.berkeley.edu/~gasgrp
Historical Perspective
Surface science in general and surface chemistry in par-
ticular have a long and distinguished history. The spontane-
ous spreading of oil on water was described in ancient times
and was studied by Benjamin Franklin. The use of surface-
chemical processes on a large industrial scale began in the
early part of the 19th century. The application of catalysis
started with the discovery of the platinum-surface-catalyzed
reaction of H2 and O2 in 1823 by Döbereiner. Döbereiner
used this reaction in his portable “flame source”, of which he
sold a large number. By 1835 the discovery of heterogeneous
catalysis was complete, thanks to the studies of Kirchhoff,
Davy, Henry, Philips, Faraday, and Berzelius (1). It was about
this time that the Daguerre process was introduced for photog-
raphy. The study of tribology, which includes friction, lubrica-
tion, and adhesion, also started around this time; this coin-
cides with the industrial revolution, as machinery with mov-
ing parts became prevalent (although some level of under-
standing of friction appears in the work of Leonardo da Vinci).
Surface-catalyzed-chemistry-based technologies first appeared
in the period of 1860 to 1912, starting with the Deacon pro-
cess (2HCl + 1/2 O2 → H2O + Cl2), SO2 oxidation to SO3
(Messel, 1875), the reaction of methane with steam to produce
CO and H2 (Mond, 1888), ammonia oxidation (Ostwald,
1901), ethylene hydrogenation (Sabatier, 1902), and ammonia
synthesis (Haber, Mittasch, 1905–1912). Surface tension
measurements and recognition of equilibrium constraints on
surface chemical processes led to the development of the thermo-
dynamics of surface phases by Gibbs (1877).
The existence of polyatomic or polymolecular aggregates
that lack crystallinity and diffuse slowly (gelatine and albu-
min, for example) was described in 1861 by Graham, who
called these systems “colloids”. Polymolecular aggregates that
exhibit internal structure were called “micelles” by Nageli,
and stable metal colloids were prepared by Faraday. The colloid
subfield of surface chemistry gained prominence in the be-
ginning of the 20th century with the rise of the paint industry
and the preparation of artificial rubbers. Studies of high-surface-
area gas-absorber materials for gas masks and other gas-separation
technologies and investigations of the lifetime of the light bulb
filament led to the determination of the dissociation prob-
ability and adsorption probability of many diatomic molecules
on surfaces as a function of gas pressure (adsorption isotherm)
and temperature (Langmuir 1915). The properties of chemi-
sorbed and physisorbed monolayers, adsorption isotherms,
dissociative adsorption, energy exchange, and sticking upon
gas–surface collisions were studied. Studies of electrode sur-
faces in electrochemistry led to detection of the surface space
charge (2). Surface diffraction of low-energy electrons was
discovered by Davisson and Germer in 1927, and atom dif-
fraction (helium) from surfaces, somewhat later. Major aca-
162 Journal of Chemical Education • Vol. 75 No. 2 February 1998 • JChemEd.chem.wisc.edu
demic and industrial laboratories focusing on surface studies
have been formed in Germany (Haber, Polanyi, Farkas,
Bonhoefer), the United Kingdom (Rideal, Roberts, Bowden),
the United States (Langmuir, Emmet, Harkins, Taylor, Ipatief,
Adams), and many other countries. They have helped to bring
surface chemistry into the center of development of chemistry,
both because of the intellectual challenge to understand the
rich diversity of surface phenomena and because of its im-
portance in chemical and energy conversion technologies.
Up to the 1950s, studies of surfaces were mostly on the
macroscopic scale. Then the rise of the solid-state-device-
based electronics industry and the availability of economical
ultra-high-vacuum systems—developed by research in space
sciences—provided surface chemistry with new challenges
and opportunities and resulted in explosive growth of the dis-
cipline. Clean surfaces of single crystals could be studied for
the first time and the development of a large number of new
techniques (cf. section on Techniques of Surface Science) from
the 1960s onwards made possible the investigation of surfaces
at atomic and molecular levels.
As a result, macroscopic surface phenomena (adsorption,
bonding, catalysis, oxidation, and other surface reactions; dif-
fusion, desorption, melting, and other phase transformations;
growth, nucleation, charge transport; atom, ion, and elec-
tron scattering; friction, hardness, lubrication) are being re-
examined on the molecular scale. This has led to a remark-
able growth of surface chemistry that has continued unin-
terrupted up to the present. The discipline has again become
one of the frontier areas of chemistry. The newly gained
knowledge of the molecular ingredients of surface phenomena
has given birth to a steady stream of high technology prod-
ucts, including new hard coatings that passivate surfaces;
chemically treated glass, semiconductor, metal, and polymer
surfaces to which the treatment imparts unique surface proper-
ties; newly designed catalysts, chemical sensors, and carbon
fiber composites; surface-space-charge-based copying; and
new methods of electrical, magnetic, and optical signal pro-
cessing and storage. Molecular surface chemistry is being uti-
lized increasingly in biological sciences.
External Surfaces
Surface Concentration
The concentration of atoms or molecules at the surface
of a solid or liquid can be estimated from the bulk density.
For a bulk density of 1 g/cm3 (such as ice or water), the mo-
lecular density ρ, in units of molecules per cubic centimeter,
is ≈ 5 × 1022. The surface concentration of molecules σ (mol-
ecules/cm2) is proportional to ρ2/3, assuming cubelike pack-
ing, and is thus on the order of 1015 molecules/cm2. Because
the densities of most solids or liquids are all within a factor
of 10 or so of each other, 1015 molecules/cm2 is a good order-

of-magnitude estimate of the surface concentration of atoms
or molecules for most solids or liquids. Of course, surface
atom concentration of crystalline solids may vary by a factor
of two or three, depending on the type of packing of atoms
at a particular crystal face.
Clusters and Small Particles
All atoms in a three- or four-atom cluster are by necessity
“surface atoms”. As a cluster grows in size, some atoms may
become completely surrounded by neighboring atoms and
are thus no longer on the “surface” (Fig. 1). We frequently
describe a particle of finite size by its dispersion D, where D
is the ratio of the number of surface atoms to the total number
of atoms:
D = number of surface atoms
total number of atoms
For very small particles, D is unity. As the particle grows
and some atoms become surrounded by their neighbors, the
dispersion decreases (Fig. 1). Of course, D also depends some-
what on the shape of the particles and how the atoms are
packed. The dispersion is already as low as 10᎑3 for particles of
10-nm (100-Å) radius.
Many chemical reactions are facilitated by surface atoms
of heterogeneous catalysts. These catalysts increase the rate of
formation of product molecules and modify the relative dis-
Figure 1. Clusters of atoms with cubic packing having 8, 27, 64,
125, and 216 atoms. While in an 8-atom cluster all of the atoms
are on the surface, the dispersion rapidly declines with increasing
cluster size, as shown in the lower part of the figure.
JChemEd.chem.wisc.edu • Vol. 75 No. 2 February 1998 • Journal of Chemical Education
The Flexible Surface
tribution of products. Most catalysts are in small-particle
form, including those used to produce fuels and chemicals
ranging from high-octane gasoline to polyethylene.
Thin Films
Consider a monolayer of gold atoms (a layer of gold atoms
one atom thick) deposited on iron (Fig. 2). This film has a
dispersion of unity, since all the atoms are on the surface. About
50 layers of gold atoms (D = 1/50) are needed to obtain the
optical properties that impart the familiar yellow color char-
acteristic of bulk gold.
Thin films are of great importance to many real-world
problems. Their material costs are very little compared to cost
of the bulk material, and they perform the same function
when it comes to surface processes. For example, a monolayer
of rhodium (a very expensive metal), which contains only
about 1015 metal atoms per square centimeter, can catalyze
the reduction of NO to N2 by its reaction with CO in the
catalytic converter of an automobile, or it can catalyze the
conversion of methanol to acetic acid by the insertion of a
CO molecule.
Thin ordered silicon layers optimize electron transport
in integrated electronic circuits and thin films of organic
molecules lubricate our skin or the moving parts of internal
combustion engines. A green leaf is a high-surface-area system
designed to maximize the absorption of sunlight in order to
carry out chlorophyll-catalyzed photosynthesis at optimum rates.
Often the surface of a thin film is roughened deliber-
ately. Automobile brake pads are designed to optimize the
desired mechanical properties of surfaces in this way, as is
the corrugated design of rubber soles of tennis shoes. The
large number of folds of the human brain helps to maximize
the number of surface sites, which also facilitate charge trans-
port and transport of molecules. These are some examples
that show how external surfaces are used in nature. External
surfaces are a key element of technology, ranging from cata-
lysts and passivating coatings to computer-integrated circuitry
and the storage and retrieval of information.
Figure 2. An iron particle with one surface covered with a mono-
layer of gold atoms. When it comes to surface properties such as
adsorption or catalysis, one monolayer of atoms is all that is needed
to carry out the necessary chemistry.
163
 Viewpoints

Internal Surfaces—Microporous Solids

Microporous solids are materials that are full of pores of
molecular dimensions or larger. These materials have very
large internal surface areas. Many clays have layer structures
that can accommodate molecules between the layers by a pro-
cess called intercalation. Graphite will swell with water vapor
to several times its original thickness as water molecules be-
come incorporated between the graphitic layers. Crystalline
alumina silicates, often called zeolites, have ordered cages of
molecular dimensions (3), where molecules can adsorb or
undergo chemical reactions (Fig. 3). These materials are also
called molecular sieves, because they may preferentially adsorb
certain molecules according to their size or polarizability. This
property is of great commercial importance and may be used
to separate mixtures of gases (air) or liquids or to carry out
selective chemical reactions. Bones of mammals are made out
of calcium apatite, which has a highly porous structure, with
pores on the order of 10 nm (100 Å) in diameter. Coal and
char have porous structures, with pore diameters on the order
of 102–103 nm (103–104 Å). These materials have very large Figure 3. Alumina silicates with pores of molecular dimensions
internal surface areas, in the range of 100–400 m2 per gram (zeolites) are used as selective absorbers of gases or liquids (mo-
of solid. As this short survey shows, nature has provided us lecular sieves) and as catalysts in chemical and petroleum tech-
with many useful microporous materials; and many synthetic nologies. The figure shows a synthetic zeolite, zeolite A. The
microporous substances are used in technology, both to sepa- red spheres represent oxygen atoms and the yellow spheres rep-
resent either silicon or aluminum atoms. For each aluminum there
rate gas and liquid mixtures by selective adsorption and to
is a corresponding Na+ ion somewhere in one of the open chan-
carry out surface reactions selectively in their pores, which nels. The molecular formula of this molecular sieve is
are often of molecular dimensions. Because surface reaction Na12(Al 12Si 12O 48) ⴢ27H 2O.
rate (product molecules formed per second) is proportional
to surface area, materials with high internal surface areas carry
out surface reactions at very high rates.
10᎑6 torr) and using the values M = 28 g/mol (for N2) and T
Clean Surfaces = 300 K, we obtain F ≈ 1015 molecules/cm2/s. Thus, at this
pressure the surface is covered with a monolayer of gas within
To study atomically clean surfaces, we must work under seconds, assuming that each incident gas molecule “sticks”.
so-called ultrahigh vacuum (UHV) conditions (4, 5), as the fol- For this reason the unit of gas exposure is 1.33 × 10᎑4 Pa-s
lowing rough calculation shows. We know that the concentra- (10᎑6 torr-s), which is called the Langmuir (L). Thus, a 1-L
tion of atoms on the surface of a solid is on the order of 1015 exposure will cover a surface with a monolayer amount of
cm᎑2. To keep the surface clean for 1 s or for 1 h, the flux of gas molecules, assuming a sticking coefficient of unity. At
molecules incident on the initially clean surface must therefore pressures on the order of 1.33 × 10᎑7 Pa (10᎑9 torr), it may
be less than ≈ 1015 molecules/cm2/s or ≈ 1012 molecules/cm2/s, take 103 s before a surface is covered completely.
respectively. From the kinetic theory of gases (6), the flux, F, of In practice, one usually wants to study a surface with-
molecules striking the surface of unit area at a given ambient out worrying about contamination from ambient gases. Cur-
pressure P is rent surface science techniques can easily detect contamina-
N AP tion on the order of 1% of a monolayer. This then will be
F= our operational definition of “clean”. Thus, ultrahigh vacuum
2πMRT conditions (< 1.33 × 10᎑7 Pa = 10᎑9 torr) are required to main-
or tain a clean surface for about 1 h, the time usually needed to
20
perform experiments on clean surfaces.
2.63 × 10 ⋅ P (Pa)
F (atoms/ cm2 ⋅ s) = Interfaces
M (g / mol) T
or In most circumstances, however, and certainly in Earth’s
environment, surfaces are continually exposed to gases or liq-
22 uids or placed in contact with other solids. As a result, we
2
3.51 × 10 ⋅ P (torr)
F (atoms/ cm ⋅ s) = end up investigating the properties of interfaces—that is, be-
M (g / mol) T tween solids and gases, between solids and liquids, between
solids and solids, and even between two immiscible liquids.
where M is the average molar weight of the gaseous species, Thus, unless specifically prepared otherwise, surfaces are al-
T is the temperature (in Kelvin), R is the gas constant, and ways covered with a layer of atoms or molecules from the
NA is Avogadro’s number. Substituting P = 4 × 10᎑4 Pa (3 × environment.

164 Journal of Chemical Education • Vol. 75 No. 2 February 1998 • JChemEd.chem.wisc.edu


Adsorption
On approaching the surface, each atom or molecule en-
counters an attractive potential that ultimately will bind it
to the surface under proper circumstances. The process that
involves trapping of atoms or molecules incident on the sur-
face is called adsorption. It is always an exothermic process.
For historical reasons, the heat of adsorption ∆Hads is always
denoted as having a positive sign—unlike the enthalpy ∆H,
which for an exothermic process would be negative according
to the usual thermodynamic convention. The residence time
τ of an adsorbed atom (7) is given by
τ = τ0 exp(∆Hads/RT)
where τ0 is correlated with the surface-atom vibration times
(it is frequently on the order of 10᎑12 s), T is the tempera-
ture, and R is the gas constant. The value of τ can be 1 s or
longer at 300 K for ∆Hads > 69 k J/mol (16.5 kcal/mol). The
surface concentration σ (in molecules/cm2) of adsorbed mol-
ecules on an initially clean surface is given by the product of
the incident flux F and the residence time τ:
σ = Fτ
The surface of the material on which adsorption occurs
is often called the substrate. Substrate-adsorbate bonds are
usually stronger than the bonds between adsorbed molecules.
As a result, the monolayer of adsorbate bonded to the sub-
strate is held most tenaciously and is difficult to remove.
Therefore, the properties of real surfaces are usually deter-
mined in the presence of an adsorbed monolayer.
Figure 4. Schematic diagram of a scanning tunneling microscope
capable of operating in a pressure range from UHV to 1 atmo-
sphere. The STM is located inside a high-pressure chemical reac-
tor, which is attached to a UHV surface characterization chamber.
The two sections are separated by a gate valve. For surface clean-
ing and analysis, a transfer system is used to move the sample
from the high-pressure cell to the UHV part of the apparatus (and
vice versa).
JChemEd.chem.wisc.edu • Vol. 75 No. 2 February 1998 • Journal of Chemical Education
The Flexible Surface
Techniques of Surface Science
Over the last three decades, a large number of techniques
have been developed to study various surface properties, in-
cluding structure, composition, oxidation states, and changes
of chemical, electronic, and mechanical properties. The em-
phasis has been on surface probes that monitor properties
on the molecular level and are sensitive enough to detect ever-
smaller numbers of surface atoms. The frontiers of surface
instrumentation are constantly being pushed toward detec-
tion of finer detail: atomic spatial resolution, ever-smaller
energy resolution, and shorter time scales. Because no single
technique provides all necessary information about surface
atoms, the tendency is to use a combination of techniques.
The most commonly used techniques (Table 1) involve the
scattering, absorption, or emission of photons, electrons, at-
oms and ions, although some important surface-analysis tech-
niques cannot be classified this way.
Most surface probes require high vacuum during their
application, which prevents their use during high-pressure
studies. To circumvent this restriction, UHV-compatible
high-pressure cells (“environmental cells”) were developed (8).
The sample to be analyzed is first subjected to the usual high-
pressure and/or high-temperature conditions encountered
during reactions in the environmental cell. Afterwards the
sample is transferred, without exposure to air, into the evacu-
ated UHV chamber where the surface probe is located for
subsequent surface analysis (generally the sample surface
should be characterized before and after any treatment).
During the past five years, two new surface science tech-
niques in particular proved capable of obtaining molecular-
level surface information during chemical change at both low
and high ambient pressures (9, 10): scanning tunneling micros-
copy (STM) and infrared–visible sum frequency generation
(SFG) surface vibrational spectroscopy. Both of these techniques
can operate within a 14-order-of-magnitude pressure range
(10᎑10–104 torr) without significant change in signal quality
in terms of spatial or energy resolution. Using these two tech-
niques, we can monitor both substrate and adsorbate structures
during reactions at high pressures. One such apparatus,
designed for in situ STM, is shown in Figure 4.
Sample preparation is always an important part of surface
studies. Single crystals are oriented by X-ray back-diffraction,
cut, and polished. They are then ion-bombarded or chemi-
cally treated to remove undesirable impurities from their sur-
faces. Thin films are deposited from vapor by sublimation,
sputtering, or the use of plasma-assisted chemical vapor depo-
sition. Materials of high internal surface area are prepared
from a sol-gel or by calcination at high temperatures. The
genesis and environmental history of the surface is primarily
responsible for its structure and composition and must al-
ways be carefully monitored.
Table 1 lists a selection of the surface-science techniques
used most frequently in recent years to learn about the inter-
face on the atomic scale. The names of the techniques, their
acronyms, and brief descriptions are provided (along with
some references [11–39], if a more detailed study of the ca-
pabilities and limitations of a particular technique is desired).
We also indicate the primary surface information that can
be obtained by the application of each technique.
165
 Viewpoints
Table 1. Selection of Most Frequently Used Surface Science Techniques
Acronym Name (References)
— Adsorption or selective
chemisorption (11)
AD Atom or helium diffraction
(12 )
AES Auger electron
spectroscopy (12– 14 , 23,
24, 26 )
AFM Atomic force microscopy
(15, 16 )
ELS or Electron energy loss
EELS spectroscopy (14, 17– 19 )
ESCA Electron spectroscopy for
chemical analysis (12, 20 )
EXAFS Extended X-ray absorption
fine structure (21, 22 )
FEM Field emission microscopy
(12, 20, 21 )
FIM Field ionization microscopy
(12, 20, 21, 23 )
FTIR Fourier transform infrared
spectroscopy (13, 24 )
HREELS High-resolution electron
energy loss spectroscopy
(12, 21, 23 )
IRAS Infrared reflection
absorption spectroscopy
(21, 25 )
ISS Ion scattering spectroscopy
(12, 13, 21, 23, 24, 26 )
LEED Low-energy electron
diffraction (12– 14, 20, 21,
23, 24, 26 )
166 Journal of Chemical Education • Vol. 75 No. 2 February 1998 • JChemEd.chem.wisc.edu
Primary Surface
Description
Information
Atoms or molecules are physisorbed; the amount of gas adsorbed is a Surface area, adsorption
measure of total surface area. Chemisorption of atoms or molecules yields site concentration
surface concentration of selected elements or adsorption sites.
Monoenergetic beams of atoms are scattered from ordered surfaces and Surface structure
detected as a function of scattering angle, giving structural information on
the outermost layer of the surface. Method is extremely sensitive to surface
ordering and defects.
Core-hole excitations are created, usually by 1– 10-keV incident electrons, Chemical composition
and Auger electrons of characteristic energies are emitted through a
2-electron process as excited atoms decay to their ground state. AES gives
information on the near-surface chemical composition.
Similar to STM. An extremely delicate mechanical probe is used to scan Surface structure
the topography of a surface by measuring forces exerted by surface atoms.
Light interference is used to measure the deflection of the mechanical
surface probe. This is designed to provide STM-type images of insulating
surfaces or to detect mechanical properties at the molecular level.
Monoenergetic electrons ~5– 50 eV are scattered off a surface and the Electronic structure,
energy losses are measured. This gives information on the electronic surface structure
excitations of the surface and the adsorbed molecules (see HREELS).
Now generally called XPS (see XPS). Composition, oxidation
state
Monoenergetic photons excite a core hole. Modulation of the absorption Local surface structure
cross-section with energy at 100– 500 eV above the excitation threshold and coordination
yields information on radial distances to neighboring atoms. The cross numbers
section can be monitored by fluorescence as core holes decay or by the
attenuation of the transmitted photon beam. EXAFS is one of the many "fine-
structure" techniques.
A strong electric field (on the order of V/Å ) is applied to the tip of a sharp, Surface structure
single-crystal wire. Electrons tunnel into the vacuum and are accelerated
along radial trajectories by Coulomb repulsion. When the electrons
impinge on a fluorescent screen, variations of the electric field strength
across the surface of the tip are displayed.
A strong electric field (on the order of V/Å ) is created at the tip of a sharp, Surface structure and
single-crystal wire. Gas atoms, usually He, are polarized and attracted to surface diffusion
the tip by the strong electric field, then ionized by electrons tunneling from
the gas atoms into the tip. These ions, accelerated along radial trajectories
by Coulomb repulsion, map variations in the electric field strength across
the surface, showing the surface topography with atomic resolution.
Broad-band IRAS experiments are performed, and the IR absorption Bonding geometry and
spectrum is deconvoluted by using a Doppler-shifted source and Fourier strength
analysis of the data. This technique is not restricted to surfaces.
A monoenergetic electron beam, usually ~2– 10 eV, is scattered off a Bonding geometry,
surface, and the energy losses below ~0.5 eV to bulk and surface phonons surface
and vibrational excitations of adsorbates are measured as a function of atom vibrations
angle and energy (also called EELS).
IR photons are reflected off a surface and the attenuation of IR intensity is Molecular structure
measured as a function of frequency yielding a spectrum of the vibrational
excitations of adsorbed molecules. Recent improvements in sensitivity allow
IRAS measurements to be made on single-crystal surfaces.
Ions are inelastically scattered from a surface, and the chemical Surface structure,
composition of the surface is determined from the momentum transfer to composition
surface atoms. The energy range is ~1 keV to 10 MeV, and the lower
energies are more surface sensitive. At higher energies this technique is
also known as Rutherford back-scattering (RBS).
Monoenergetic electrons below ~500 eV are elastically back-scattered Atomic and molecular
from a surface and detected as a function of energy and angle. This gives surface structure
information on the structure of the near surface region.
Continued on next page
 The Flexible Surface

Table 1. Selection of Most Frequently Used Surface Science Techniques —Continued

Primary Surface
Acronym Name (References) Description
Information

— Neutron diffraction (27 ) Neutron diffraction is not an explicitly surface-sensitive technique, but Molecular structure
experiments on large surface-area samples have provided important
structural information on adsorbed molecules and surface phase
transitions.

NMR Nuclear magnetic NMR is not an explicitly surface-sensitive technique, but NMR data on large Chemical state
resonance (28 ) s u r f a c e - a r e a s a m p l e s ( ⱖ 1 m 2) h a v e p r o v i d e d u s e f u l i n f o r m a t i o n o n
molecular adsorption geometries. The nucleus magnetic moment interacts
with an externally applied magnetic field and provides spectra highly
dependent on the nuclear environment of the sample. The signal intensity
is directly proportional to the concentration of the active species. This
method is limited to the analysis of magnetically active nuclei.

RHEED Reflection high-energy Monoenergetic electrons of ~1– 20 keV are elastically scattered from a Surface structure,
electron diffraction surface at glancing incidence and detected as a function of angle and structure of thin films
(13, 20, 21, 23, 24 ) energy for small forward-scattering angles. Backscattering is less important
at high energies and glancing incidence is used to enhance surface
sensitivity.

SFG Sum frequency generation Similar to SHG, but the laser output is split into a visible laser beam and a Molecular structure
(29, 30 ) tunable IR beam. The two beams meet at the surface. The sum frequency
signal is monitored as a function of IR frequency. In this way the vibrational
spectrum of adsorbed molecules is obtained.

SHG Second harmonic A surface is illuminated with a high-intensity laser, and photons are Electronic structure,
generation (29, 31 ) generated at the second harmonic frequency through nonlinear optical molecular orientation
processes. For many materials only the surface region has the appropriate
symmetry to produce an SHG signal. The nonlinear polarizability tensor
depends on the nature and geometry of adsorbed atoms and molecules.

SIMS Secondary ion mass Ions and ionized clusters ejected from a surface during ion bombardment Surface composition
spectrometry (12, 13, 21, are detected with a mass spectrometer. Surface chemical composition and
23, 24, 32 ) some information on bonding can be extracted from SIMS ion fragment
distributions.

STM Scanning tunneling The topography of a surface is measured by mechanically scanning a Atomic surface structure
microscopy (12, 13, 16, probe over a surface. The distance from the probe to the surface is
24, 33 ) measured by the probe-surface tunneling current. Angstrom resolution of
surface features is routinely obtained.

TEM Transmission electron TEM can provide surface information for carefully prepared and oriented Surface structure
microscopy (13, 24, 34, bulk samples. Real images have been formed of the edges of crystals where
35 ) surface planes and surface diffusions have been observed. Diffraction
patterns of reconstructed surfaces, superimposed on the bulk diffraction
pattern, have also provided surface structural information.

TDS Thermal desorption An adsorbate-covered surface is heated, usually at a linear rate, and the Composition, heat of
spectroscopy desorbing atoms or molecules are detected with a mass spectrometer. This adsorption, surface
(21, 23, 36, 37 ) gives information on the nature of adsorbate species and some information structure
on adsorption energies and the surface structure.

TPD Temperature programmed Similar to TDS, except the surface may be heated at a nonuniform rate to Composition, heat of
desorption (21, 36, 37 ) obtain more selective information on adsorption energies. adsorption, surface
structure

UPS Ultraviolet photoemission Electrons photoemitted from valence and conduction bands are detected Valence band structure
spectroscopy as a function of energy to measure the electronic density of states near the
(12, 14, 20, 21, 23 ) surface. This gives information on the bonding of adsorbates to the surface.

XPS X-ray photoemission Electrons photoemitted from atomic core levels are detected as a function Composition, oxidation
spectroscopy (12, 13, 20, of energy. Shifts of core-level energies give information on the chemical state
21, 23, 24, 26, 38 ) environment of the atoms.

XRD X-ray diffraction (39 ) X-ray diffraction has been carried out at extreme glancing angles of Surface structure
incidence where total reflection ensures surface sensitivity. This provides
structural information that can be interpreted by well-known methods. An
extremely high X-ray flux is required to obtain useful data from single-crystal
surfaces. Bulk X-ray diffraction is used to determine the structure of organo-
metallic clusters, which provide comparisons to molecules adsorbed on
surfaces. X-ray diffraction has also given structural information on large
surface-area samples.

JChemEd.chem.wisc.edu • Vol. 75 No. 2 February 1998 • Journal of Chemical Education 167

 Viewpoints

Figure 5. Restructuring at a step site on a clean surface. Each atom Figure 6. Side (a) and top (b) views on the Fe3O4(111) surface
attempts to optimize its coordination and “cracks” open to close structure with the spacing relaxations shown. The corresponding
the step edges. bulk values are ∆ = 0.63 Å, and d12 = d23 = 1.19Å. The A and B
layers are strongly expanded by ~ 0.46Å.

Phenomena Discovered by Molecular Surface Chemistry
Surface Structure Is Different from Bulk Structure
Two dominant phenomena occurring at clean surfaces
of materials distinguish their atomic structure from that in
the bulk: relaxation and reconstruction (40). Upon relaxation
of metal surfaces, the first layer of atoms moves inward, and
this contraction leads to a much shortened interlayer spac-
ing between the first and second layer of the surface. The
more open (“rougher”) the surface, the larger the relaxation.
Often, but not always, the contraction in the first layer is
followed by a small expansion in the second layer. At rough
edges, such as at stepped surfaces, the atoms at the step relax
by a large amount in order to smooth the surface irregular-
ity. This is shown schematically in Figure 5.
At ionic surfaces, the nature of surface relaxation is very
different. Figure 6 shows what happens at iron oxide surfaces
(41). Iron oxide, in its bulk structure, shows alternating layers
of oxygen ions and iron ions, where the iron ions are in tetra-
hedral or octahedral positions. At the surface, the two ions
move in such a way that the positive and negative ions are
almost coplanar. Presumably because of the necessary condition
of charge neutrality, this type of surface structure is thermo-
dynamically more stable than having alternating oxygen-ion
and iron-ion layers. Such an expansion at the surface is clearly
a property of ionic solids, and future studies will prove how
general this type of relaxation is.
Because of directionality of bonding in most solids, such
contraction or relaxation at the surface moves atoms from their
position of optimum bonding. As a result, the atoms not only
move perpendicular to the surface, but also parallel to the sur-
face. This leads to the formation of new surface unit cells, a
phenomenon called surface reconstruction. Perhaps the most cel-
ebrated example is the (7×7) surface structure that forms on the
Si(111) crystal face. Figure 7a shows the low-energy electron dif-
fraction (LEED) pattern from this surface. The complex unit
cell has 49 different locations of surface atoms that are distin-
guishable. The Si(100) surface shows a (2×1) reconstruction (Fig.
7b). It shows the formation of staggered dimers differing from
the arrangement of Si atoms in the bulk near the surface.

Figure 7. Left: Low-energy electron diffraction (LEED) pattern of the reconstructed Si(111) crystal face, exhibiting a (7×7) surface structure.
Right: The reconstructed Si(100) crystal face as obtained by LEED surface crystallography. Note that surface relaxation extends to three
atomic layers into the bulk.

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Pt, Au, and Ir (100) surfaces that should have square
unit cells reconstruct to form hexagonal surface unit cells (40,
42). This is shown in Figure 8. STM studies have imaged
both reconstructed and unreconstructed surfaces (some domains
may be unreconstructed because of contamination by adsor-
bates of various types).
The water molecules at the ice surface vibrate with a much
larger amplitude (0.24 Å) than molecules in bulk ice (0.1 Å)
(43). This motion causes surface “softness”, which is likely
responsible for the anomalously low friction coefficient of ice
(i.e., it makes ice so slippery).
Molecules at the liquid–vapor interface also show restruc-
turing, as shown in Figure 9 for the arrangement of molecules
at liquid alcohol surfaces (44). The alcohol molecules are ori-
ented with their O–H bonds pointing inward, presumably
for optimum hydrogen bonding. The alkane chains stick out
from the surface. This orientation has been readily detectable
by nonlinear laser optics sum frequency generation (SFG).
Adsorbate-Induced Restructuring of Surfaces
When the clean surfaces are covered with a near mono-
layer of chemisorbed molecules, the structure of the surface
undergoes profound alterations. This is perhaps best shown
in the field ion microscopy (FIM) studies carried out by Kruse
and coworkers (45) with rhodium field emission tips (Fig. 10).
When carbon monoxide is chemisorbed on these tips, every
crystal face restructures as shown by the figure. This massive
restructuring is reversible if CO is removed when the surface
is heated in vacuum.
Our new STM system (Fig. 4) is placed in an environ-
mental cell that can be pressurized and heated to elevated
temperatures. It shows surface restructuring of the Pt(110)
surface when this surface is exposed to atmospheric pressures
of hydrogen, then oxygen, and then carbon monoxide (46).
When these surfaces are heated, the surface restructures from
a reconstructed ordered structure (exhibiting the so-called
“missing row” reconstruction) in the presence of hydrogen,
Figure 8. Top and side view of the Ir(100)-(1×5) surface reconstruc-
tion. The more open square (100) lattice is reconstructed into a
close-packed hexagonal overlayer, with a slight buckling as shown
in the side view.
JChemEd.chem.wisc.edu • Vol. 75 No. 2 February 1998 • Journal of Chemical Education
The Flexible Surface
to large (111) orientation facets in the presence of oxygen,
and then again to smooth (110) unreconstructed surfaces in
the presence of carbon monoxide (Fig. 11).
Low-energy electron diffraction surface crystallography
studies indicate the detailed atomic level nature of such re-
constructions (42). When carbon is adsorbed on the Ni(100)
surface, it occupies fourfold hollow sites (Fig. 12). As a re-
sult of the formation of the carbon–metal chemisorption
bonds, the surface metal atoms move away from the adsorption
site, presumably to give more space to the carbon atom so it
can sink deeper into the surface, thereby forming bonds with
second-layer nickel atoms underneath (47). This expansion
around the chemisorption site induces strain, which is relieved
by rotation of the surface unit cell as shown in Figure 12.
When sulfur is chemisorbed on the Fe(110) crystal face
(48), the S atom pulls the neighboring Fe atoms into equal
distances from the chemisorption site to form four equal Fe–S
bonds. The strength of these bonds pays for the weakening of
the metal–metal bonds as a result of the restructuring. When
NO is adsorbed on the Ni(111) surface, the molecule occupies
a threefold hollow site, a so-called hcp (hexagonal close-packed)
hollow site. This means there is a metal atom directly under-
neath the chemisorption site in the second metal layer.
Chemisorption induces an upward movement of this metal
atom in the second layer, and rumpling of the metal surface.
When ethylene adsorbs on the Rh(111) surface (49), it re-
arranges and occupies a hollow site (in this case, again, an
hcp hollow site). The rearranged ethylene (which has lost a
hydrogen) is called ethylidyne. This is shown in Figure 13.
The metal atoms move away from the carbon atom bound
to the hollow site to allow the carbon to bond to the Rh atom
directly underneath the carbon in the second layer. On the
Pt(111) surface (50, 51), ethylene also forms an ethylidyne
molecule—again in a threefold hollow site, but in this case
it is an fcc hollow site. That is, there is no metal atom di-
rectly underneath the carbon in the second metal layer. In
this circumstance, the surface metal atoms move inward to
presumably provide as strong a bond as possible to the carbon,
and metal–metal distances are altered on the surface as well.
The second metal atom next to the chemisorption bond
moves downward to produce a corrugated surface. It appears
that surface bonding is clusterlike, where nearest-neighbor
metal atoms that surround the adsorbate move to optimize
the surface chemical bond. The heat of adsorption, which is
always exothermic, pays for the weakening of the next nearest
neighbor metal–metal bonds, which are altered as a result of
the movement of the metal atoms nearest to the chemisorp-
tion site.
Figure 9. The normal alcohols show substantial ordering at the liq-
uid–vapor interface. The OH groups of the alcohols extend into
the liquid forming a hydrogen-bonded network, while the alkyl
chains are oriented away from the liquid.
169
 Viewpoints

When two molecules are coadsorbed on the surface,
adsorbate-induced reconstruction may be very different from
when only one or the other molecule is chemisorbed. This is
shown for benzene and CO coadsorption on the Rh(111)
surface (Fig. 14). When these molecules form a mixed unit
cell, under the benzene the metal atoms are closer to their
bulklike configuration than under the CO molecule (52).
There is rumpling of the surface that occurs because of the
differences in chemical bonding of the coadsorbed species to
the substrate metal atoms. When benzene adsorbs alone it is
bent. Four of the C atoms are in one type of surface site while
two of the others are in different types of surface sites. When
coadsorption occurs, the benzene molecule is flattened out.
Rough Surfaces Do Chemistry
Surface irregularities, steps, and kinks are very effective
for breaking adsorbate chemical bonds and in catalysis as well.
This is best known by the temperature-programmed desorption
(TPD) of H2 from flat, stepped, and kinked surfaces of Pt
(Fig. 15). H2 desorbs at maximum rates at the highest tempera-
ture from kink sites, then at somewhat lower temperatures from
step sites, and at even lower temperatures from flat (111) ter-
races (53). This indicates higher heats of adsorption of the H
Table 2. Structure Sensitivity of H2/D2 Exchange at Low
Pressures (~10 ᎑ 6 torr)
Surface Reaction Probability
Stepped Pt(332) 0.9
Flat Pt(111) ~10 ᎑1
Defect-free Pt(111) ⱕ10 ᎑3
atom at these defect sites. Thus, the thermodynamic driving
force for dissociation is certainly greater at these sites, which
can explain their enhanced bond-breaking activity.
It is difficult to understand, however, that these same
strongly adsorbing sites are also very active sites for catalysis.
This is shown in Table 2. The reaction probability of H2/D2
exchange on stepped surfaces is near unity at low pressures
on a single scattering event, whereas it is below the detection
limit (< 10᎑3) on the flat (111) crystal face, as shown by mo-
lecular beam surface scattering studies (54). How is it possible
that the strongly adsorbing step sites, where H has a long
residence time because of its high binding energy, are also
the sites of rapid reaction turnover?
One possible explanation is that the strongly adsorbed
hydrogen restructures the surface near the step, thereby creat-

Figure 10. Field ion micro-

graphs (image gas: Ne; T
= 85 K) of a (001)-oriented
Rh tip (top left ) before and
(bottom left ) after reaction
with 10᎑4 Pa CO for 30 min
at 420 K . The stereo-
graphic projections at the
right demonstrate the
change in morphology from
nearly hemispherical to po-
lygonal. The scheme at the
bottom right indicates the
coarsening of the crystal
and the dissolution of a
number of crystallographic
planes due to the reaction
with CO.

170 Journal of Chemical Education • Vol. 75 No. 2 February 1998 • JChemEd.chem.wisc.edu


Figure 11. In situ high-pressure STM
pictures showing adsorbate-induced
surface reconstructions of Pt(110) un-
der atmospheric pressures: Top: Topo-
graphic image of the surface in hydro-
gen after heating to 425 K for 5
hours, showing (n×1) missing-row re-
construction randomly nested. Vertical
range: ∆ z = 10 Å . Center: Topo-
graphic image of the surface in oxy-
gen after heating to 425 K for 5
hours; ∆ z = 25 Å . Bottom: Topo-
graphic image of the surface in car-
bon monoxide after heating to 425 K
for 4 hours; ∆z = 42 Å.
ing the active site for the catalytic exchange process. At the
low pressures of these molecular beam scattering experiments,
the low coverages keep the structure of the flat part of the
surface unaltered.
Similarly, stepped Ni surfaces dehydrogenate C2H4 at
much lower temperatures (< 150 K) than the (111) face of
Ni (~230 K). The more open (111) and (211) crystal faces
of Fe (Fig. 16) are several orders of magnitude more active
for NH3 synthesis than the close-packed Fe (110) crystal face,
which showed no detectable reaction rate ( 55).
Clusterlike Bonding of Adsorbed Molecules
When ethylene chemisorbs at ~ 300 K on the (111) crystal
faces of various transition metals (Pt, Rh, Pd), it chemically
rearranges to form the molecule-surface compound shown
in Figure 13. Its structure as determined by LEED-surface
crystallography is very similar to multinuclear organometal-
lic complexes such as Os3 CCH3 or Co3 (CO)9 CCH3. The
rearranged ethylene, which has also lost a hydrogen, is called
ethylidyne and belongs to the alkylidyne group (species of the
formula CnH2n᎑1), a common substituent in surface chemistry
Figure 12. Carbon-chemisorption-induced restructuring of the
Ni(100) surface.
JChemEd.chem.wisc.edu • Vol. 75 No. 2 February 1998 • Journal of Chemical Education
The Flexible Surface
and organometallic chemistry. The vibrational spectrum of
chemisorbed ethylidyne is nearly identical to that of the organo-
metallic cluster Os3 CCH3 , which contains three metal atoms.
The C–C bond distance (1.45 Å) is slightly less than the
single carbon–carbon bond length of 1.54 Å (0.154 nm), as
in cluster compounds. Thus, the surface chemical bond of
chemisorbed ethylene can, as a first approximation, be viewed
as a clusterlike bond that contains at least three metal atoms
(56). The C–C bond order present in gaseous ethylene is
reduced from two to nearly one upon chemisorption. This
reduction in bond order of alkenes and alkynes upon chemi-
sorption on metal surfaces is commonly observed, indicating
charge transfer from the molecules into the metal.
Benzene usually chemisorbs on metals with its ring parallel
to the surface (although it may adsorb in a different configura-
tion when it loses hydrogen). Because of charge transfer to the
metal, C–C bond elongations occur with respect to the sym-
metry of the adsorption site. The ring may even bend, with
two of the opposing carbon atoms closer to the metal surface
than the other four carbon atoms. Distortions and elonga-
tions of C–C bonds are also found when benzene is bound
to clusters of metal atoms in organometallic complexes. Thus
the clusterlike bonding model appears to be valid for chemi-
sorbed benzene as well.
The bonding picture of adsorbed molecules becomes
more complicated if there are more bonding sites available
on the same molecule. For example, pyridine (C5H5N) may
bind through the lone electron pair of its nitrogen or through
the π-electrons of the carbon ring. Thus, depending on the
metal, the binding geometry of the substrate, the temperature,
or the adsorbate coverage, the molecule may be tilted with
respect to the substrate surface, its ring may be parallel with it,
or it may be upright with bonding solely through the nitrogen.
It is too simplistic to consider that only the nearest-
neighbor metal atoms of the substrate participate in the bond-
ing. There is evidence that the atoms at next-nearest-neigh-
bor sites change their location when chemisorption occurs,
moving either closer or further away from the chemisorp-
tion bonds.
171
 Viewpoints
The Flexible Surface
As a result of all these studies that indicate adsorbate-
induced restructuring and clusterlike bonding, the new model
of the surface which has been adopted is the so-called “flex-
ible surface” (53). In the past it was assumed that the metal
atoms at the surface are rigid and occupy equilibrium sites
dictated by the bulk unit cell. On adsorption, their location
would not be altered. Instead, the flexible surface is one where
the metal atoms move into new sites, dictated by the chemi-
sorption bond so as to optimize that bond: upon adsorption
the surface restructures, thereby creating the active sites for
surface chemical processes.
Figure 14. The coadsorbed surface structure of benzene and car-
bon monoxide on the Rh(111) crystal face as obtained by low-
energy electron diffraction surface crystallography.
172 Journal of Chemical Education • Vol. 75 No. 2 February 1998 • JChemEd.chem.wisc.edu
Figure 13. The structure of
ethylidyne on Rh(111). Ethylidyne
is bonded on the hcp 3-fold hollow
site. This site has a metal atom right
underneath the carbon bonding site
in the second layer. The adsorption-
induced distortion in the top metal
layers pulls the nearest neighbor
metal atoms up out of the surface
plane.
The flexible-surface model explains why rough surfaces
or defect sites at surfaces are so active in surface chemistry.
Bond breaking and catalysis most frequently occur at low
coordination sites such as steps and kinks or at defect sites
such as oxygen vacancies in oxide surfaces. The lower the co-
ordination of metal atoms (the fewer nearest neighbors), the
more easily they restructure to optimize the surface adsorp-
tion bond. Thus, rough surfaces or atoms at steps move more
readily, and of course small clusters of atoms where the co-
ordination is much reduced are the most flexible. It is not
surprising therefore that we use nanoclusters in the field of
catalysis (and in many instances chemisorption) to optimize
chemical effects, such as chemical reactions or adsorption.
The extraordinary diversity of surface chemistry is due
to the chameleon-like change of surface structure and bond-
ing as the chemical environment of the surface is altered.
Platinum is an excellent combustion catalyst operating in an
oxidizing atmosphere and is a primary ingredient of the auto-
mobile catalytic converter. Platinum is also an excellent catalyst
for hydrocarbon conversion under reducing conditions to
produce high-octane gasoline (aromatic molecules and
branched isomers) from straight chain alkanes (for example
from n-hexane and n-heptane, which have octane numbers
near zero). The platinum surface structure and thus its bonding
behavior is completely different under the different reaction
conditions, thereby mediating dramatically different catalytic
surface chemistry.
Technological Impact of Molecular Surface Chemistry:
Selected Examples
Molecular surface chemistry contributed to the devel-
opment and improvement of a wide range of technologies
(57). A complete description is far beyond the limits of this
article. In this section we will discuss only its present and
future impact on catalysis and semiconductor devices.
Since the early 1970s, molecular surface chemistry has
made significant contributions to our understanding of catalyst-
 The Flexible Surface

based chemical and petroleum technologies. The hydrogenation

of carbon monoxide yields methane or methanol exclusively,
oxygenated molecules containing several carbon atoms or liquid,
and high-molecular-weight hydrocarbon products (depending
on the type of catalyst employed) (40). The dissociation of
CO was found to be the dominant reaction step in producing
methane, followed by stepwise hydrogenation of the surface
carbon over several transition metal surfaces. Potassium was
found to be an outstanding “promoter” of CO dissociation
through weakening of the C–O bond by charge transfer.
Methanol production was found to occur through the hydro-
genation of undissociated CO2 or CO (which reaction domi-
nates depends on catalyst formulation). Higher-molecular-weight
hydrocarbons are produced by secondary polymerization
reactions.
The reforming of naphtha over platinum was found to
be a structure-sensitive reaction. By altering the surface struc-
ture of platinum particles [(111) or (100) orientation] the
product distribution could be altered. Bimetallic platinum-
based catalysts (Pt–Re, Pt–Ir, and Pt–Sn) have also been in-
vestigated by surface-science studies. These studies have con-
tributed greatly to their optimization in this important high-
octane fuel producing technology.
The same is true for the iron-based catalyst that produces
ammonia from N2 and H2. The structure sensitivity of this
reaction was uncovered, implicating the (111) and (211) crys-
tal faces of iron as the most active (58, 59) (Fig. 16). The
surface structures that are more open and contain sites that
are surrounded by seven iron neighbor atoms (C7 sites) are
the most active. These are the (111) and (211) crystal faces.
The structure of the (110) crystal face does not allow the
adsorbed nitrogen species to bind with second- and third-layer
atoms (55), and probably for this reason the rate for the syn-
thesis of ammonia is some 500 times lower than on the (111)

Figure 16. Schematic representations of the idealized surface struc-

tures of the (111), (211), (100), (210), and (110) orientation of
Figure 15. Thermal desorption spectra of hydrogen from a flat iron single crystals (the coordination of each surface atom is indi-
(111), a stepped (557), and a kinked (12,9,8) surface of plati- cated). The bar diagram shows the corresponding activity of the
num. single crystal surfaces in ammonia synthesis.

JChemEd.chem.wisc.edu • Vol. 75 No. 2 February 1998 • Journal of Chemical Education 173

 Viewpoints
surface structure. The role of potassium promoters as bond-
ing modifiers in aiding the dissociation of N2, as well as weak-
ening the bonding of ammonia to the iron surface to inhibit
product poisoning, has been uncovered. The role of alumina
as a structure modifier, aiding the restructuring of iron par-
ticles to possess crystal faces most active for ammonia synthe-
sis [(111) and (211)], has been proven by surface-science stud-
ies. As a result, a new generation of catalysts with superior ac-
tivity could be prepared for this important industrial process.
Environmentally important catalytic processes have be-
come the focus of rapid development in recent years. None
of them is more important than the 3-way catalytic converter
utilized to clean automobile exhaust. It utilizes Pt, Pd, Rh,
and cerium oxide as an important promoter (60). The chal-
lenge is to fully oxidize unburned hydrocarbons and CO to
CO2 while reducing NOx to N2 under all conditions of en-
gine use: cold start, steady-state operation, and using a broad
range of air and fuel mixtures. This is achieved with the help
of one of the most successful chemical sensors, the oxygen
detector ( λ-probe) on automobiles. It helps to adjust the air-
to-fuel ratio of the mixture entering the internal combustion
engine and to optimize the efficiency of the 3-way catalytic
converter. This technology works well on the present-day
automobile. The development of lean-burning, more fuel-
efficient cars presents new challenges to surface chemistry and
the technology used to clean automobile exhaust.
Semiconductor-based technologies are at the heart of com-
puter manufacturing. The fabrication of microelectronic circuits
often involves layer-by-layer deposition of semiconductor (Si,
GaAs, etc.), metal (Al, Cu, etc.), and insulator (SiO2, polymer)
thin films, in various configurations. The film thickness of
each of these materials is presently in the 103–104-Å range,
and these layers alternate in both two and three dimensions.
Fabrication of these layers is carried out by surface processes
using chemical vapor deposition, sublimation, or sputter
deposition from a radio-frequency plasma. Nucleation and
growth mechanisms are monitored by surface-science techniques
such as reflection high-energy electron diffraction (RHEED)
and electron microscopy. We shall look at two problems of
semiconductor device technology that are currently the fo-
cus of intense surface-science studies.
The first is that insulating gate oxides for “metal oxide
semiconductor field effect transistors” (MOSFET) are produced
by oxidizing silicon to SiOx. Both the oxygen-to-silicon ratio
and the thickness of the oxide are important process vari-
ables, as they control the device’s performance. The gate oxides
must become thinner, their surfaces or interfaces must be
atomically smooth, and their impurity concentrations must
be minimized in order to increase the speed of electron trans-
port and device reliability.
The second problem is that the chemical and mechanical
integrity of the metal-insulator interfaces can be compromised
by water vapor or by the chemical attack of impurities segre-
gating at the interface (e.g., alkali atoms, carbon, oxygen).
When this happens, the adhesion of the insulator oxide to
the metal is altered and delamination occurs. “Trap” states
that arise at the Si–SiO2 interface from Si atoms with coordina-
tion numbers other than 4 are another problem because they
can trap charge at the interface. All these changes of chemical
and mechanical properties at the interface can have very del-
eterious effects on the electrical properties. It is essential that
we learn how to fabricate chemically stable insulator–metal
174 Journal of Chemical Education • Vol. 75 No. 2 February 1998 • JChemEd.chem.wisc.edu
interfaces that maintain adhesion under changing ambient
conditions (temperature, humidity, etc.). As the insulating
oxide is replaced by a polymer with a smaller dielectric con-
stant, the study of metal–polymer interfaces becomes a fron-
tier area of the science of semiconductor surface technology.
Other important surface technologies developed in recent
years with the help of molecular surface chemistry should
also be mentioned. Air separation to oxygen and nitrogen was
accomplished with the help of molecular sieves because of
their higher heat of adsorption for N2 (~ 7 kcal/mol) than
for O2 (~ 3 kcal/mol), thereby preferentially releasing oxygen.
Conversely, microporous carbon engineered to have bimodal
distribution of pores adsorbs the smaller O2 (3.46 Å) in its
small pores in preference to N2 (3.64 Å) and preferentially
releases nitrogen. The magnetic disc drive provides information
storage in computers by nanoscale tracking of a magnetic thin
film that is coated by an atomically smooth carbon deposit
and lubricated by a drop of fluoro-ether lubricant. The optical
fiber operates on total internal reflection in glass by the
cladding that is made by another glass of different composition
and with a smaller refractive index. Such glass structures are
produced using chemical vapor deposition of oxides in an
appropriate sequence. Diamond films are produced by appli-
cation of a high-energy plasma of methane and hydrogen or
by chemical vapor deposition to provide a chemically inert,
extremely hard coating with high thermal conductivity, that
withstands chemical and mechanical attacks superbly (61).
Adhesives and the contact lens are important surface technolo-
gies using polymers that provide controlled adhesion and
some degree of biocompatibility, respectively.
Future Directions in Surface Chemistry
Coadsorption on Surfaces
Most studies of modern surface chemistry focus on single
adsorbate systems, atoms, or molecules and investigate structure
and bonding, adsorption, diffusion, and desorption dynamics
as a function of temperature. In most chemical reactions, how-
ever, two or more reactants are utilized. Oxygen, hydrogen,
and water are the coadsorbates present most frequently, although
mixtures of organic molecules are adsorbed during hydro-
carbon conversion reactions. Catalytic systems always use
additives that accelerate the reaction rate or improve selec-
tivity. Potassium, which is an electron donor to iron, weakens
the bonding of the product molecule, ammonia (NH3 ),
thereby accelerating its desorption from the surface. Con-
versely, potassium increases the bonding of carbon monoxide
(an electron acceptor) to iron and other transition metals,
leading to the dissociation of the molecule (62). As a result,
the rate of production of hydrocarbons by the hydrogenation
of CO is greatly accelerated. In the future, more studies involv-
ing coadsorbed atoms and molecules must be pursued to un-
cover their influence on surface chemistry as a consequence of
their interactions, adsorbate–adsorbate and adsorbate-substrate.
High-Pressure Surface Science
Increasing the coverage of adsorbates often enhances restruc-
turing of the substrate and changes the surface chemistry. The
easiest way to increase coverage is to increase the reactant pres-
sure, since pressure is proportional to coverage (adsorption iso-
therm). When CO adsorbs on platinum surfaces it occupies
mostly top and bridge sites, with its C=O bond perpendicular

to the metal surface (63). As the pressure is increased to above
10 torr a high coverage incommensurate overlayer forms, and
at even higher pressures (≥ 100 torr) the formation of platinum
carbonyl clusters with CO-to-Pt-ratio greater than one can be
detected. This pressure-dependent change in surface chemistry
is driven by the formation of strong CO–Pt bonds that in-
duce the weakening and then the breaking of metal–metal
bonds to produce a thermodynamically more stable surface
structure. Newly available techniques permit atomic and mo-
lecular studies of external surfaces in the presence of high-
pressure gas or a liquid at the interface. These include the
scanning tunneling and atomic force microscopes (STM and
AFM) and sum frequency generation (SFG)–surface vibra-
tional spectroscopy (10, 46). In the future these techniques
and others will be used to carry out in situ studies of mo-
lecular surface chemistry at high reactant pressures and at high
temperatures.
Monitoring Surface Chemistry at Ever-Improving
Spatial Resolution and Time Resolution
STM and AFM provide spatial resolution of surfaces and
surface species on the nanometer scale. There is a continuing
need to develop spectroscopic techniques that have the same
resolution because they will provide means to study and ma-
nipulate surfaces on that spatial scale. Increased time resolu-
tion will permit us to monitor the motion of surface atoms and
molecules, their diffusion, rotation, vibrational and electronic
excitation, and their reaction dynamics.
Studies of the Buried Interfaces, Solid–Liquid and
Solid–Solid
Techniques that open up high-pressure surface chemis-
try also permit molecular studies of the buried interfaces. This
will result in rapid developments in molecular phenomena
at solid–liquid (64) and solid–solid interfaces, including elec-
trochemistry, biology, and tribology (friction, lubrication,
wear) (65).
Achieving 100% Selectivity in Surface Reactions—
the Environmental Imperative
In most surface catalyzed reactions we desire to obtain
only one product, although the formation of other chemicals is
also thermodynamically allowed. We need to understand cata-
lytic selectivity, how to obtain 100% selectivity to avoid the
formation of undesirable molecules that often lead to sepa-
ration problems, pollution, or catalytic deactivation.
Nanoparticles: Surfaces in Three Dimensions
Particles with dispersions between 1 and 0.1 represent
transition between single atoms and molecules and the bulk
solid. They have many surprising properties as their electronic
structure, atomic structure, and phase diagram—and as a con-
sequence, their surface chemistry—change with particle size.
The fabrication of nanoparticles of uniform size (66, 67) and
their study is one of the intellectual frontiers of modern sur-
face chemistry.
Molecular surface chemistry is one of the most rapidly
developing branches of chemistry. It is an intellectual frontier
of the discipline with enormous potential to develop surface
technologies that improve our quality of life, create employ-
ment, and create wealth. It will remain a rapidly advancing
frontier area for many years to come.
JChemEd.chem.wisc.edu • Vol. 75 No. 2 February 1998 • Journal of Chemical Education
The Flexible Surface
Acknowledgment
This work was supported by the Director, Office of En-
ergy Research, Office of Basic Energy Sciences, Materials Sci-
ences Division, of the U.S. Department of Energy under
Contract No. DE-AC03-76SF00098.
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Gabor A. Somorjai
University of California at Berkeley
Department of Chemistry and
Material Sciences Division of
Berkeley National Laboratory
Ph.D., Chemistry, 1960, University
of California at Berkeley
B.S., Chemical Engineering,
1956, Technical University,
Budapest, Hungary
Gabor A. Somorjai is one of the most influential scientists
in the area of surface chemistry today. He has received nu-
merous awards, including the 1997 Von Hippel Award which
he was awarded on December 3, 1997. His influence on sur-
face chemistry can be seen in more than 750 papers pub-
lished on surface science, heterogeneous catalysis, and solid
state chemistry. Somorjai has educated more than 90 Ph.D.
students and collaborated more than 110 postdoctoral sci-
entist of whom Günther Rupprechter is one. The research
interests of his group include molecular studies of the struc-
ture and bonding of surfaces, surface science of heterogenous
catalysis, and molecular studies of polymer surfaces and po-
lymerization. During the past 30 years Somorjai has made
significant contributions in surface science, new surface in-
strumentation, and catalysis.
176 Journal of Chemical Education • Vol. 75 No. 2 February 1998 • JChemEd.chem.wisc.edu
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74, 129.
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89, 1598.
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1996, 77, 3858.
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1995, 1, 233.
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1997, 372, L249.
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B 1997, 101, 9973–9977.
Günther Rupprechter
University of California at Berkeley
Department of Chemistry and
Material Sciences Division of
Berkeley National Laboratory
Ph.D., Chemistry, 1996, Leopold
Franzens University, Innsbruck
B.S., Chemistry, 1992, Leopold
Franzens University, Innsbruck
Günther Rupprechter received his Ph.D. in 1996 under the
supervision of Konrad Hayek on “Microstructural and mor-
phological changes on epitaxially grown noble metal catalyst
particles upon oxidation and reductive activation.” At present
he is a postdoctoral fellow at the University of California at
Berkeley working with Gabor A. Somorjai. Rupprechter’s
current research interests include structure–activity correla-
tions in heterogeneous catalysis, fabrication of well-faceted
polyhedral nanocrystals on oxidic supports by epitaxial
growth and electron beam lithography, and analysis of sur-
face structure and surface composition. He also has received
a number of awards and fellowships.