In the Classroom

edited by
Advanced Chemistry Classroom and Laboratory Joseph J. BelBruno
Dartmouth College
Hanover, NH 03755

Plasmons: Why Should We Care?

Dean J. Campbell*
Department of Chemistry and Biochemistry, Bradley University, Peoria, IL 61625; *campbell@bradley.edu

Younan Xia
Department of Chemistry, University of Washington, Seattle, WA 98195

The physical phenomenon of plasmons has helped to at least three types of SPs:
enhance methods of chemical analysis in recent decades, even • Propagating SPs, which occur on extended metal sur-
to the point where it is possible to detect a single molecule. faces
Though many of these methods have not yet found their way
• Localized SPs, which occur in small volumes such as
into traditional chemistry classes and labs, it is likely that
metal particles
many of today’s chemistry and biochemistry majors will en-
counter plasmon-based techniques in their future. Some tech- • Acoustic SPs, which are predicted to exist for some
niques, such as surface plasmon resonance, staining for structures and metal surfaces and are the subject of
microscopy, and colorimetry have already been commercial- continued study (3). These plasmons have not yet seen
ized. Other applications for plasmons are still being explored, extensive use in chemistry and will not be discussed
for example, plasmon-based alternatives to traditional elec- further in this article.
tronic circuits. This review will provide a brief overview of The combination of photons and SPs produce electro-
plasmons and the techniques that build upon them. magnetic excitations on extended surfaces known as surface
Strictly speaking, plasmons are quantized waves in a col- plasmon polaritons (SPPs) or propagating surface plasmons
lection of mobile electrons that are produced when large num- (PSPs) (1, 5). PSPs have lower frequencies and energies than
bers of these electrons are disturbed from their equilibrium bulk plasmons; metal surfaces in contact with a vacuum have
positions (1, 2). Electrons present in classic gaseous plasmas PSPs with a theoretical frequency of ωp兾√2 (1, 3). Figure
can support plasmons, hence the name of these waves. The 1A shows a representation of PSPs. As the waves of electron
collection of mobile electrons in metals is referred to as a density travel along the surface, alternating regions of posi-
quantum plasma (2). This is composed of delocalized elec-
trons that bathe the metal nuclei and their localized core elec-
trons, as described by the free-electron theory of metals (1).
This description of metallic bonding has been used to ex-
plain many metallic properties.
Metals that best exhibit this free-electron plasma be-
havior include the alkali metals, Mg, Al, and noble metals
such as Cu, Ag, and Au (1). Plasmons can exist within the
bulk of metals, and their existence was used to explain en-
ergy losses associated with electrons beamed into bulk metals
(3). For a bulk metal of infinite size, the frequency of oscil-
lation, ωp, of the plasmons can be described by the follow-
ing equation (1):

ωp = (Ne2兾ε0me)1兾2 (1)

where N is the number density of mobile electrons, ε0 is the

dielectric constant of a vacuum, e is the charge of an elec-
tron, and me is the effective mass of an electron.
Surface plasmons (SPs) are a type of plasmon associated
with the surfaces of metals. They are significantly lower in
frequency (and energy) than bulk plasmons and can inter-
act, under certain conditions, with visible light in a phenom-
enon called surface plasmon resonance (SPR). SPs have been Figure 1. (A) Depiction of propagating surface plasmons (1). (B)
the most useful to chemists. For example, the electric fields Depiction of localized surface plasmons (1). Regions of greater elec-
of SPs amplify optical phenomena such as Raman scattering tron density are represented by lighter shading. Electric fields are
(1, 4), which will be discussed later in the article. There are represented by arrows.

www.JCE.DivCHED.org • Vol. 84 No. 1 January 2007 • Journal of Chemical Education 91

 In the Classroom
Figure 2. Extinction spectra of 10 nm, 50 nm, and 100 nm Au
particles. The spectra are scaled to the same maximum absorbance.
Note the red shift of the plasmons as particle size increases. The
colloids were obtained from British Biocell International, Cardiff,
Britain.
tive and negative charges are produced. The electric fields pro-
duced by these regions of differing charge decay exponen-
tially away from the metal surface (5). A macroscopic physical
analogy that has been used to describe surface plasmons is
that of seaweed floating in water near a shoreline. The waves
of water lapping along the shoreline represent the electric
fields and the seaweed sloshed back and forth by these waves
represent electrons (6).
Though PSPs can be produced with light, simply shin-
ing light on a smooth metal surface in air is not sufficient
because the momentum of the light does not match that of
the SPs (3). Neither will the smooth metal surface emit light
from plasmons.1 Various methods are employed to enable
light to produce and to be produced by PSPs. Some meth-
ods involve passing the light through a medium with a higher
refractive index than air, such as glass, before it comes near
to the metal surface (3, 5). To better explain the role of re-
fractive index, consider what happens when a beam of light
passes from a medium with a higher index into a medium
with a lower index. In many cases, part of the incident beam
is reflected from the interface and part of the incident beam
passes into the medium with the lower refractive index (and
is refracted in the process). However, when the angle of the
incident light exceeds a critical angle, no portion of the light
leaves the medium with higher refractive index and is com-
pletely reflected. This is the condition of total internal re-
flectance (7). Many fiber optic cables utilize the same
principle to transmit light down curved strands: the refrac-
tive index of the core of the fiber optic is higher than that of
its cladding layer, and the condition of total internal reflec-
tance keeps the light in the fiber (8). Under the conditions
of total internal reflectance, light waves that strike the inter-
face between two materials with differing refractive indices
produce new light waves that propagate from the interface a
very short distance into the medium with the lower refrac-
tive index. These evanescent waves decay exponentially as the
distance from the interface increases. At a particular angle of
incident light beyond the critical angle, evanescent waves can
92 Journal of Chemical Education • Vol. 84 No. 1 January 2007
propagate PSPs along a thin layer of metal placed at the in-
terface between the media with differing refractive indices
(5, 6, 9). This SP resonance angle is susceptible to the re-
fractive index of the media near the metal film, making it
sensitive to chemical changes that involve changes in refrac-
tive index (or its square, the dielectric constant).
Other methods to enable light to access a metal surface
and produce PSPs involve roughening the surface, thereby
changing its momentum. If light shines on a metal diffrac-
tion grating with parallel, linear features, it can be diffracted
by that grating. At the same time, however, PSPs will be
propagated along the surface of the grating in the direction
perpendicular to the linear features (5, 10, 11). SPs can also
be enhanced by randomly roughened metal surfaces. The
rough surfaces can be considered as a superposition of many
gratings (11).
Localized surface plasmons (LSPs), are the collective elec-
tron oscillations in small volumes, Figure 1B. LSPs also have
lower frequencies and energies than bulk plasmons; metal
particles in contact with a vacuum have LSPs with a theo-
retical frequency of ωp兾√3 (1, 3). LSP resonances are pro-
duced in a somewhat different fashion from PSPs. An example
of this interaction between light and the electrons of a metal
particle is illustrated in Figure 1B (1, 12). For this phenom-
enon to occur, the particle must be much smaller than the
wavelength of incident light. The electric field of the inci-
dent light can induce an electric dipole in the metal particle
by displacing many of the delocalized electrons in one direc-
tion away from the rest of the metal particle and thus pro-
ducing a net negative charge on one side. Since the rest of
the metal particle is effectively a cationic lattice of nuclei and
localized core electrons, the side opposite the negative charge
has a net positive charge. LSPs have also been referred to as
dipole plasmons, but the oscillating field of the incident light
can induce quadrupole as well as dipole resonances, especially
for particles greater than 30 nm in diameter (12, 13). If a
particle with a dipole can be considered to have a positively
charged pole and a negatively charged pole, then a particle
with a quadrupole can be considered to have two positively
charged poles and two negatively charged poles.
The energy of light required to produce LSP resonance
depends on a number of factors, including the size, shape,
and composition of the particles, as well as the composition
of the surrounding media. The interactions of light with
spherical metal particles can be described by Mie theory,
which is based upon an exact solution to Maxwell’s equa-
tions (1). This theory also predicts what fraction of light im-
pinging upon colloidal metal particles will be absorbed and
what fraction will be scattered. The sum of absorption and
scattering is the extinction of light due to the particles. This
is actually what is measured when one places a colloidal metal
suspension into a UV–vis spectrometer. Figure 2 shows the
extinction spectra for spherical Au colloids with differing di-
ameters. Generally speaking, as the particle size increases, the
plasmon resonant frequency decreases (shifts to longer wave-
lengths) (1). Small Au particles (with diameters less than 20
nm) exhibit extinction that is primarily due to absorption;
larger particles tend to exhibit much stronger scattering (1).
Though solid spherical Au and Ag particles are easy to
synthesize, their plasmon energies do not cover much of the
electromagnetic spectrum. Particles with other shapes are ca-
• www.JCE.DivCHED.org

+
adsorbates
−
+
−
+
−
+
−
plasmons
+ − + − metal
+ −
+
−
+ −
−
+ −
+
+ −
+
+
−
−
incident
plasmon +
+
−
−
light
of sphere +
+ −
−
plasmon
hybridized of cavity
plasmons
Figure 3. A hybridization model for the plasmon behavior of Au
nanoshells (15). The plasmons of a spherical shell can be consid-
ered a hybribization of the plasmon from a solid sphere and the
plasmon of a spherical void.
pable of covering much wider energy ranges (14). Moving
beyond spherical particles requires more advanced method-
ology, both synthetically and theoretically. Many of these plas-
mon resonant structures feature dimensions between 1 and
100 nm, making them “nanostructures” (1). Technology that
deals with such nanostructures is called “nanotechnology”.
Non-spherically symmetric particles can be synthesized by
directionally dependent growth rate control with polymers
or surfactants (15, 16). Another method for controlling par-
ticle shapes uses other particles or surfactant assemblies as
templates (15, 16). Other template-directed patterning meth-
ods have been used to produce structures on surfaces that
exhibit LSPs (17).
Plasmons and their associated electric fields can be cal-
culated for a variety of different particle shapes. The
plasmonic behavior of these particles has been successfully
described by the discrete dipole approximation (DDA)
method, which subdivides a particle of interest into an array
of polarizable cubes (1, 17). It seems that the most intense
plasmon electric fields tend to be located near areas of the
particles with the sharpest curvature (15).
Particles of different shapes have different plasmon
properties. For example, rod-shaped Ag or Au particles ex-
hibit two plasmons: a longitudinal plasmon, corresponding
to the long axis of the rod, and a transverse plasmon, corre-
sponding to the short axis of the rod. Keeping the diameters
of the rods constant while increasing their lengths result in
the transverse plasmon remaining essentially constant in fre-
quency (or energy) while the longitudinal plasmon decreases
in frequency (1, 15). Hollow metal particles tend to have
lower plasmon resonant frequencies than solid metal particles
(18). The plasmon behavior of small hollow spherical metal
particles, or shells, has recently been described by using a hy-
bridization model that resembles, at first glance, the hybrid-
ization of molecular orbitals, Figure 3. In this model, the
plasmons associated with a shell can be thought of as a com-
bination of the plasmon from a solid sphere of the same di-
ameter as the exterior of the shell and a plasmon from a
spherical cavity in extended metal with the same diameter as
the interior of the shell. The plasmons hybridize to produce
a new higher energy plasmon and a new lower energy plas-
mon (the lower energy plasmon is more likely to interact with
light). As the diameter of the solid sphere approaches that of
www.JCE.DivCHED.org • Vol. 84 No. 1 January 2007
In the Classroom
surface
θ
reflected
light
glass prism
Figure 4. Schematic of the surface plasmon resonance technique (4,
9). Light passing through a prism onto a metal film at the proper inci-
dent angle θ will amplify propagating surface plasmons in the metal
film. The nature of the adsorbates helps determine the actual SPR angle.
the spherical cavity (that is, as the thickness of the metal shell
decreases) their plasmons interact more strongly and increase
the energy separation of the hybridized plasmons and ulti-
mately decrease the energy of the lower-energy hybridized
plasmon. The net result is that the shells with thinner metal
layers have plasmons that are shifted to lower frequencies (18).
Aggregation of colloidal metal particles can also lower their
plasmon frequencies (1, 19). Finally, the refractive index of
the medium surrounding the metal particles can influence
the frequency of their LSPs (1, 18, 20). Typically, a higher
refractive index (or dielectric constant) of the medium pro-
duces a lower plasmon frequency. A macroscale physical anal-
ogy one might make to this phenomenon is using an
oscillating weighted spring to represent the electric field of
the LSP. A high dielectric medium can be represented by a
viscous, higher-friction medium like oil. A spring in a vacuum
will oscillate with a higher frequency than the spring in the
oil.
Applications Using PSPs
One of the major applications of the phenomenon of
PSP is surface plasmon resonance analysis. The specific ge-
ometry of this technique varies. The Kretchmann–Raether
arrangement is described in Figure 4 (10). This involves shin-
ing a monochromatic light source through a prism onto a
thin metal film deposited along one of its flat faces. A detec-
tor senses the light reflected from the film. As the angle be-
tween the incident light and the normal to the film is
increased through the critical angle, the intensity of light
reaching the detector increases. However, when the angle is
increased even further through the SPR angle, the intensity
of light reaching the detector decreases to a minimum. The
specific SPR angle of the system varies as the refractive index
of the medium adjacent to the metal film changes. Molecules
can be attached to the metal film, and the changes in inter-
actions of these molecules under different conditions can be
monitored as changes to their collective refractive index.
These SPR systems are commercially available and have been
used to study the binding interactions of biomolecules (6,
9). These systems can be integrated with other analytical sys-
tems, for example, mass spectrometry may be performed on
the species adsorbed to the metal film (9).
• Journal of Chemical Education 93
 In the Classroom
Another application of PSPs is based on a phenomenon
called extraordinary transmission (21). Ordinarily one would
expect a screen placed in front of a light beam to block a
significant fraction of the light being transmitted through the
screen. However, if a metal film containing a two dimensional
array of holes of the proper size and periodicity is placed in
the light beam, more light is transmitted through the screen
at certain wavelengths than is expected. It is postulated that
the light resonates with PSPs at the incident side of the metal
film. The PSPs propagate to the other side of the film, where
they produce light that transmits away from the other side.
This phenomenon is being explored as a method for study-
ing species adsorbed to the metal films, for example, the in-
frared absorbance of some alkanethiols on Cu are enhanced
by a factor of 102 (22).
The technique of scanning near-field optical microscopy
(SNOM) can access PSPs on a metal surface. In this tech-
nique, light is shone down a glass fiber that has been reduced
to a diameter less than the wavelength of light. When the
tip of this fiber is brought very close to the metal surface,
circular PSPs will radiate from the tip to the metal (5). This
process, which has been explained by both evanescent waves
from the high refractive index glass fiber and diffraction from
the fiber tip itself (5), enables PSPs to be initiated at specific
locations on a surface with great precision.
Finally, PSPs are being explored as an alternative means
of transmitting information (23, 24). Plasmons travel through
metals with optical frequencies, about 105 times faster than
the frequency of today’s microprocessors. At the same time,
there is not as much need for light transmitting materials as
would be necessary for entirely light-based (photonic) com-
puters; many plasmonic components would use the same
materials as electronic components. One challenge to over-
come is that the distance plasmons can travel is currently less
than that the dimensions of a computer chip (24).
Applications Using LSPs
One of the most recognizable results of LSP resonance
is the dramatic absorption of light by some small metal par-
ticles. Solid Au and Ag particles can have extinction coeffi-
cients 106 times greater than molecular chromophores (1).
The deep red and purple colors associated with colloidal Au
have been known since antiquity, for example, in tinted glass
such as the Lycurgus cup from the 4th century C.E. (25).
“Purple of Cassius” was used as a coloring agent for glass and
enamel and is thought to be a colloidal mixture of Au and
hydrated SnO2 (26). Michael Faraday first reported the pro-
duction of aqueous colloidal Au suspensions (using phospho-
rus as a reducing agent) in 1857. Some of these colorful
suspensions are still preserved today at the Faraday Museum
in London (1, 27). Au and Ag colloids can be produced and
used conveniently in the student laboratory, and some of these
educational preparations and applications have been pub-
lished in this Journal and elsewhere (28–34).
The high light-absorbing properties of Au colloids en-
able them to serve as structural and chemical labels for light
microscopy (35). For example, Au colloids can be placed into
biological tissue for use as optical contrast agents to enhance
imaging of these tissues. The colloid particle surfaces can be
derivatized with molecules such as antibodies to enhance their
94 Journal of Chemical Education • Vol. 84 No. 1 January 2007
selective binding to tissue surfaces (16). Visibility of the
bound Au colloids can be enhanced by depositing Ag onto
the metal particles (36). Most colloidal particles of Au can-
not be easily made to produce light like many colloidal semi-
conductor particles. Very small (< 5 nm) Au clusters can
produce light by photoluminescence. Though the photolu-
minescence phenomenon itself is attributed to electronic tran-
sitions within the Au clusters, it is believed that plasmons
associated with these very small particles amplify the inten-
sity of the incoming light and therefore enhance their pho-
toluminescence (37). Recently Au colloids have also been
induced to produce light by a phenomenon called third har-
monic generation (38). This may enable these Au particles
to be used as light-producing labels in the future. Fluores-
cence of chemical species near a metal surface can also be
enhanced by plasmons, but the challenge in using this method
of enhancement is that if the species get too close (less than
about 5 nm) to the metal the fluorescence is actually dimin-
ished (quenched) (11, 15).
One application based on the intense light absorbance
of Au colloids is photothermal therapy. Au colloids them-
selves are fairly chemically and biologically inert, but Au par-
ticles bound to living tissue can absorb light energy and
convert it to thermal energy, destroying the tissue. Hollow
Au particles can now be produced with plasmon resonances
in the near infrared region of the electromagnetic spectrum.
Since water and most biomolecules do not absorb in this re-
gion of the electromagnetic spectrum, it is possible to beam
this energy some distance into tissue to heat the Au particles
(15, 18). One way to illustrate this principle to a class would
be to place Au colloid (e.g., by evaporating a drop of sus-
pension) onto a polystyrene Petri dish and to place the dish
near the Fresnel lens focal point of a high intensity overhead
projector. We used a 7800 lumen projector with the mirror
and the focusing lens removed. A ring stand and clamp were
used to hold the assemblage about 40 cm above the glass top
surface of the projector. (CAUTION: The focused light from
an overhead projector can be dazzlingly bright and can heat
some objects dramatically.) The transparent Petri dishes them-
selves are not melted by the focused light, but light-absorb-
ing materials such as Au colloids, carbon nanotubes, and even
dark permanent marker ink can absorb sufficient energy to
damage the polystyrene dish at the location of these light ab-
sorbing materials (39). The surrounding transparent polysty-
rene is not affected. Some hollow colloidal metal cages
synthesized by the Xia group absorb light energy so well that
the light of a camera flash can melt the cages (40). These
flash-induced shape changes have been verified by transmis-
sion electron microscopy (Figure 5) and scanning electron
microscopy. These colloidal cages can also melt transparent
polystyrene when irradiated by intense projector light.
Au colloids and their LSPs can also be used as colori-
metric chemical sensors. The pink test stripe of a positive
pregnancy test can be composed of Au colloids coated with
antibodies that have bound to hormone human chorionic
gonadotropin (hCG) in urine. These complexes are then cap-
tured by more antibodies in the test band region (41). The
pink control stripe can also be composed of colloidal Au. Au
colloids coated with other biologically interacting molecules
have shown aggregation-induced changes to their plasmon
frequencies (1, 13, 35). For example, the surfaces of some
• www.JCE.DivCHED.org
 In the Classroom

Au particles have been derivatized with strands of DNA.

When these fixed strands match complementary strands of
free-floating DNA, the strands all link together by hydrogen
bonding and the colloidal particles aggregate together. The
Au colloid plasmons shift in frequency during aggregation,
and the suspension changes color, indicating a positive test
for that particular sequence of free-floating DNA (42). An-
other biochemical detection method that is somewhat remi-
niscent of the SPR analysis method mentioned previously uses
LSP-active features patterned onto an Au surface. Binding
of molecules of interest to other molecules already attached
to these Au features produces a change in the refractive in-
dex near these features, resulting in a change in their plas-
mon energy. This energy change can be monitored by UV–vis
spectroscopy. This method has recently been shown to be ca-
pable of detecting amyloid-β derived diffusible ligands
(ADDLs), which are believed to play a role in Alzheimer’s
disease (43).
Resonance of LSPs amplifies electric fields, E, near the
particle surfaces. The |E|2 of the plasmon electric field can
be 102 to 104 of the |E|2 of the incident light (17). The elec-
tric fields of plasmons can amplify the Raman signals of
chemical species near the metal surface, thus enabling the
technique of surface-enhanced Raman spectroscopy (SERS).2
Weaver and Norrod have already described SERS in this Jour-
nal and experiments suitable for the undergraduate labora-
tory are available (28, 33, 44). Briefly, Raman spectroscopy
is a type of vibrational spectroscopy that is sensitive to po-
Figure 5. Flash melting of Au cages (35). (A) Transmission electron
larizable bonds within molecules (typically different than microscope (TEM) image of unmelted Au cages formed by reduc-
bonds that are already polarized—the domain of infrared tion around polyhedral Ag templates (the Ag is oxidized away in
spectroscopy) (45). The electric field interacts with polariz- the process). (B) TEM image of Au droplets formed by melting Au
able molecules to produce dipoles, described by the equa- cages with a camera flash.
tion (28):
p = αE
where α is polarizability of the molecule, E is the applied elec- ticles that are very close (on the order of one nanometer) to
tric field, and p is the electric dipole induced in the molecule one another have enabled the detection of SERS signals from
As the equation shows, p can be made larger by increas- single molecules located between these particles (48).
ing either α or E, but plasmons tend to enhance E. As the
intensity of the induced dipoles increases, the intensity of the Conclusion
Raman signals from those molecules increase. This surface
enhancement of Raman signals was first observed from pyri- This brief survey has merely scratched the surface, so to
dine adsorbed onto a roughened Ag substrate (46). Repro- speak, of many of the chemical applications of plasmons. Plas-
ducible control of the degree of enhancement has been mon-enhanced applications have begun to make inroads into
problematic. It appears that many of the roughened substrates chemistry education and are well-suited for introduction in
have “hot spots” with exceptionally good signal enhancement physical chemistry and instrumental analysis classes. Some
(18). Precise control of the nature of the surface roughness methods of fabrication and analysis of plasmon-producing
(e.g., by patterning techniques) allows for better control of structures are sufficiently simple for use in labs in general,
the degree of Raman enhancement and of the wavelength physical, and inorganic chemistry. Readers who are interested
required to access the surface plasmons (17). Recently, a pat- in knowing more about research and educational aspects of
terned Ag substrate was used to detect calcium dipicinolate, plasmons and plasmon-producing structures are encouraged
a compound present in anthrax spores, by SERS (47). It is to peruse the references provided, especially the May, 2005
estimated that this method can detect as little as 2600 spores, issue of the MRS Bulletin (1,15–18, 23, 42).
which is less than the infectious dose of approximately 10,000
spores. The Raman signal of the adsorbed species can be dra- Acknowledgments
matically enhanced with colloids as well. Enhancement of
the electric fields of both the incident and Raman scattered DJC would like to acknowledge Bradley University for
light by 104 produces an overall theoretical enhancement of sabbatical support. DJC would like to thank Benjamin Wiley
108 (17). The regions where colloidal particles come into close and Jingyi Chen for helpful discussions, supplying the Au
proximity appear to be the location of intense plasmon elec- cages, and assistance with transmission electron microscopy.
tric fields (15). The fields that can arise between two par- YX has been supported in part by a grant from the NSF

www.JCE.DivCHED.org • Vol. 84 No. 1 January 2007 • Journal of Chemical Education 95

 In the Classroom
(DMR-0451788) and a fellowship from the David and Lucile
Packard Foundation. YX is a Camille Dreyfus Teacher
Scholar. Work was performed in part at the University of
Washington Nanotech User Facility (NTUF), a member of
the National Nanotechnology Infrastructure Network
(NNIN), which is supported by the NSF.
Note
1. The blackbody glow of a light bulb filament is based on a
completely different mechanism from plasmons.
2. The signal enhancement for SERS may also be due in part to
at least one other non-plasmon mechanism, referred to as chemical
enhancement. In this situation, some adsorbed molecules may inter-
act with surface atoms, shifting or creating new electronic states in the
visible light region in a manner similar to charge-transfer complexes
(4, 11). These light-absorbing new species would have enhanced
Raman signals due to a resonance Raman mechanism (4, 11).
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