Since a large range of particle sizes were analyzed, multipole terms
have also been taken into account throughout.
For the numerical calculation of the extinction efficiency Qext
(Qext ) óext/ðR2) the original FORTRAN code of Bohren and
Huffman was used, which can be found in the appendix of ref 10,
together with computational details. The complex refractive index
n(ì) for bulk gold was taken from the experimental work of
Johnson and Christy,16 where the original data were fitted with a
spline-fit to enable the calculation of Qext over a continuous range
of ì. All calculations were performed with water at 20 °C as the
surrounding medium where a wavelength-independent refractive
index was assumed (nmed ) 1.333). The calculated value for the
extinction efficiency can be related to the experimentally observed
absorption (A) by eq 4 via the number density of particles per
unit volume N and the path length of the spectrometer (d0), which
is usually 1 cm.Since the optical functions of gold are dependent on the particle
size for particle sizes smaller than the mean free path in bulk
gold, we have corrected n for the influence of a reduced mean
free path of the conduction electrons. This was done in the
framework of the extended Drude model following the arguments
brought forward in ref 17. In brief, the complex dielectric constant
( ) n2) is split into contributions from the bound electrons (B1
and B2) and contributions from the free electrons (A1(R) and A2-
(R)) according to eq 5. These contributions are shown in Figure 2.The mean
free path of the conduction electrons in the bulk (l¥ 42 nm for
gold) is simply the product of ôs and the Fermi velocity (vF). In
small particles the mean free path is reduced due to collisions of
electrons with the particle surface, which is represented by an
additional contribution ôc to the collision time, where ôc ) R/vF,19
and hence the dependence of the mean free path on R for a small
spherical particle is given by
To take this effect into account, ö0(R)(ö0(R) ) ö0 + vF/R) is
calculated and the contributions of the free electrons to the
dielectric constants are recalculated according to eqs 5a and 5b
using ö0(R) instead of ö0. If not stated otherwise, all results for
Qext(R, ì) shown in this paper were calculated using optical
functions corrected for the mean free path effect by this procedure,
and typical results for 1(R) and 2(R) are shown in Figure 3.