%0 Journal Article %J Journal of Applied Physics %D 2006 %T Determination of the aspect ratio statistical distribution of gold nanorods in solution from a theoretical fit of the observed inhomogeneously broadened longitudinal plasmon resonance absorption spectrum %A Eustis, Susie %A El-Sayed, Mostafa A %X The determination of the statistical distribution of aspect ratios of a nanorod solution is desirable for experimentally synthesized solutions. The traditional method of using transmission electron microscopy (TEM) images for size determination gives statistically incorrect values due to distortions introduced by TEM sample preparation and by difficulties in counting a sufficiently large number of rods. In the present work, we propose a method to obtain the aspect ratio distribution using the observed longitudinal surface plasmon resonance absorption spectrum of gold nanorods in solution. The observed inhomogeneously broadened spectrum is fitted with a collection of homogeneously broadened spectra of nanorods each with a specific aspect ratio and population contribution using Gans extension [Ann. Phys. 47, 270 (1915)] of Mie theory. The fit generates an aspect ratio distribution for the rods in solution from which the median value and the statistical distribution are determined. This method is statistically more accurate, more convenient, and less expensive than the traditional method of TEM analysis on a solid substrate. (c) 2006 American Institute of Physics. %B Journal of Applied Physics %V 100 %8 Aug %@ 0021-8979 %G eng %M WOS:000240236800122 %] 044324 %R 10.1063/1.2244520 %0 Journal Article %J Journal of Physical Chemistry B %D 2006 %T Molecular mechanism of the photochemical generation of gold nanoparticles in ethylene glycol: Support for the disproportionation mechanism %A Eustis, Susie %A El-Sayed, Mostafa A %X It is found that replacement of the chloride ions in tetrachloroauric acid with bulky bromide ions inhibits the formation of gold nanoparticles in the photochemical reduction in ethylene glycol. However, the addition of silver ions to either the bromide or the chloride auric acid solution is found to enhance the rate of gold nano-particle formation. These results are found to be accounted for by the previously proposed mechanism (Eustis, S.; Hsu, H.-Y.; El-Sayed, M. A. J. Phys. Chem. B 2005, 109, 4811) which involves disproportionation of the chloroauric complexes to generate free gold atoms and chloride ions. The steric effects of the bulky bromide ions inhibit the formation of the Au-Au bond needed in the electron transfer process of the disproportionation reaction. The addition of Ag(+) ions results in the formation of insoluble silver halide, which shifts the disproportionation reaction toward the formation of gold atoms and thus the formation of gold nanoparticles. %B Journal of Physical Chemistry B %V 110 %P 14014-14019 %8 Jul %@ 1520-6106 %G eng %M WOS:000239141800003 %R 10.1021/jp062972k %0 Journal Article %J Journal of Physical Chemistry B %D 2006 %T Plasmon coupling in nanorod assemblies: Optical absorption, discrete dipole approximation simulation, and exciton-coupling model %A Jain, Prashant K %A Eustis, Susie %A El-Sayed, Mostafa A %X The shape anisotropy of nanorods gives rise to two distinct orientational modes by which nanorods can be assembled, i.e., end-to-end and side-by-side, analogous to the well-known H and J aggregation in organic chromophores. Optical absorption spectra of gold nanorods have earlier been observed to show a red-shift of the longitudinal plasmon band for the end-to-end linkage of nanorods, resulting from the plasmon coupling between neighboring nanoparticles, similar to the assembly of gold nanospheres. We observe, however, that side-by-side linkage of nanorods in solution shows a blue-shift of the longitudinal plasmon band and a red-shift of the transverse plasmon band. Optical spectra calculated using the discrete dipole approximation method were used to simulate plasmon coupling in assembled nanorod dimers. The longitudinal plasmon band is found to shift to lower energies for end-to-end assembly, but a shift to higher energies is found for the side-by-side orientation, in agreement with the optical absorption experiments. The strength of plasmon coupling was seen to increase with decreasing internanorod distance and an increase in the number of interacting nanorods. For both side-by-side and end-to-end assemblies, the strength of the longitudinal plasmon coupling increases with increasing nanorod aspect ratio as a result of the increasing dipole moment of the longitudinal plasmon. For both the side-by-side and end-to-end orientation, the simulation of a dimer of nanorods having dissimilar aspect ratios showed a longitudinal plasmon resonance with both a blue-shifted and a red-shifted component, as a result of symmetry breaking. A similar result is observed for a pair of similar aspect ratio nanorods assembled in a nonparallel orientation. The internanorod plasmon coupling scheme concluded from the experimental results and simulations is found to be qualitatively consistent with the molecular exciton coupling theory, which has been used to describe the optical spectra of H and J aggregates of organic molecules. The coupled nanorod plasmons are also suggested to be electromagnetic analogues of molecular orbitals. Investigation of the plasmon coupling in assembled nanorods is important for the characterization of optical excitations and plasmon propagation in these nanostructures. The surface plasmon resonance shift resulting from nanorod assembly also offers a promising alternative for analyte-sensing assays. %B Journal of Physical Chemistry B %V 110 %P 18243-18253 %8 Sep %@ 1520-6106 %G eng %M WOS:000240496500031 %R 10.1021/jp063879z %0 Journal Article %J Journal of Photochemistry and Photobiology a-Chemistry %D 2006 %T Using silica films and powders modified with benzophenone to photoreduce silver nanoparticles %A Eustis, Susie %A Krylova, G. %A Smirnova, N. %A Eremenko, A. %A Tabor, C. E. %A Huang, Wenyu %A El-Sayed, Mostafa A %X Porous silica (SiO2 films and powders), modified with benzophenone (BP), facilitates the formation of stable sliver nanoparticles by taking advantage of the solid supported photosensitizer. The silica serves as a carrier for the BP into an aqueous solution and its subsequent removal. Benzophenone, bound to a silica film, was able to reduce silver ions to generate nanoparticles in solution, while silica powder with bound BP generates silver nanoparticles that are attracted to the silica. Silver nanoparticles are also fabricated in porous silica films by incorporating silver ions into the films before casting and then irradiating the film in a solution containing BP. From pH studies, it is concluded that the ketyl-radicals and anion-radicals of BP and IPA both take part in the reduction of silver ions. These synthetic studies provide a new photochemical reduction method by immobilizing the reactant on a silica surface allowing generation of silver nanoparticles in solution attached to powders or inside a film for catalytic applications or increased conductivity of silica films. (c) 2006 Elsevier B.V. All rights reserved. %B Journal of Photochemistry and Photobiology a-Chemistry %V 181 %P 385-393 %8 Jul %@ 1010-6030 %G eng %M WOS:000238963700034 %R 10.1016/j.jphotochem.2005.12.024 %0 Journal Article %J The Journal of Physical Chemistry B %D 2005 %T Aspect Ratio Dependence of the Enhanced Fluorescence Intensity of Gold Nanorods:  Experimental and Simulation Study %A Eustis, Susie %A El-Sayed, Mostafa A %X Experimental observations and theoretical treatments are carried out for the band shape and relative intensity of the emission from gold nanorods of various aspect ratios in the range between 2.25 (1.5 theory) and 6.0 (9 theory). The calculation of the fluorescence spectra requires knowledge of the nanorod size distribution, the enhancement factors, and the shape of the unenhanced fluorescence spectrum. The size distribution is determined from the fit of the observed absorption spectrum for each value of aspect ratio studied to the theoretical model of Gans. The theory by Boyd and Shen is used for calculating the enhancement of the fluorescence spectrum of the previously observed weak emission of bulk gold, which originates from the interband transition. This is carried out for nanorods of different aspect ratios. To compare theory to the observed nanorod fluorescence spectra, which suffer from self-absorption, the calculated nanorod fluorescence spectra are corrected for this effect using the observed absorption spectra. The comparison between the observed and the calculated fluorescence band shapes is found to be good. The calculated changes in the relative intensities upon changing the aspect ratios are found to be much greater than that observed. This is due to the fact that for the observed emission of all the nanorods studied nonradiative processes dominate the relaxation mechanism of the excited state, a fact that was not included in the theoretical treatments.Experimental observations and theoretical treatments are carried out for the band shape and relative intensity of the emission from gold nanorods of various aspect ratios in the range between 2.25 (1.5 theory) and 6.0 (9 theory). The calculation of the fluorescence spectra requires knowledge of the nanorod size distribution, the enhancement factors, and the shape of the unenhanced fluorescence spectrum. The size distribution is determined from the fit of the observed absorption spectrum for each value of aspect ratio studied to the theoretical model of Gans. The theory by Boyd and Shen is used for calculating the enhancement of the fluorescence spectrum of the previously observed weak emission of bulk gold, which originates from the interband transition. This is carried out for nanorods of different aspect ratios. To compare theory to the observed nanorod fluorescence spectra, which suffer from self-absorption, the calculated nanorod fluorescence spectra are corrected for this effect using the observed absorption spectra. The comparison between the observed and the calculated fluorescence band shapes is found to be good. The calculated changes in the relative intensities upon changing the aspect ratios are found to be much greater than that observed. This is due to the fact that for the observed emission of all the nanorods studied nonradiative processes dominate the relaxation mechanism of the excited state, a fact that was not included in the theoretical treatments. %B The Journal of Physical Chemistry B %I American Chemical Society %V 109 %P 16350 - 16356 %8 2005 %@ 1520-6106 %G eng %U http://dx.doi.org/10.1021/jp052951a %N 34 %! J. Phys. Chem. B %R 10.1021/jp052951a %0 Journal Article %J Journal of Physical Chemistry B %D 2005 %T Gold nanoparticle formation from photochemical reduction of Au3+ by continuous excitation in colloidal solutions. A proposed molecular mechanism %A Eustis, Susie %A Hsu, H. Y. %A El-Sayed, Mostafa A %X A photochemical reduction of Au3+ with continuous 250-400 nm excitation is studied in ethylene Zalycol, and poly (vinylpyrrolidone) (PVP) is used as a capping material. After the absorption of Au3+ disappears, excitation is stopped. The surface plasmon absorption of gold as well as the thermal reappearance of the Au3+ absorption are found to increase as a function of time. The rates of these changes are studied as a function of the mole fraction of ethylene glycol in water. Experimental results show that a small amount of ethylene glycol increases the formation of gold nanoparticles and decreases the reformation of the Au3+ absorption after irradiation. Increasing the glycol concentration first increases the rate of formation of gold nanoparticles to a maximum at a mole fraction 0.40. As the glycol concentration is further increased, the rate of formation of the gold nanoparticles and the rate of re-formation of Au3+ decrease. A mechanism is proposed that involves the reduction of the excited Au3+ to Au2+ by ethylene glycol. This is followed by the disproportionation of Au2+ to Au3+ and Au1+. Both the reduction of Au1+ by ethylene glycol and its disproportionation lead to the formation of Au-0, which upon nucleation and growth form An nanoparticles. %B Journal of Physical Chemistry B %V 109 %P 4811-4815 %8 Mar %@ 1520-6106 %G eng %M WOS:000227734500003 %R 10.1021/jp0441588 %0 Journal Article %J Photochemical & Photobiological Sciences %D 2005 %T Growth and fragmentation of silver nanoparticles in their synthesis with a fs laser and CW light by photo-sensitization with benzophenone %A Eustis, Susie %A Krylova, G. %A Eremenko, A. %A Smirnova, N. %A Schill, A. W. %A El-Sayed, Mostafa A %X The photo-sensitization synthetic technique of making silver nanoparticles using benzophenone is studied using both a laser and a mercury lamp as light sources. The power and irradiation time dependence of the synthesized nanoparticle absorption spectra and their size distribution [as determined by transmission electron microscopy (TEM)] are studied in each method and compared. In the laser synthesis, as either the laser power or the irradiation time increases, the intensity of the surface plasmon resonance absorption at 400 nm is found to increase linearly first, followed by a reduction of the red edge of the plasmon resonance absorption band. The TEM results showed that in the laser synthesis low powers and short irradiation times produce nanoparticles around 20 nm in diameter. Increasing the power or irradiation time produces a second population of nanoparticles with average size of 5 nm in diameter. These small particles are believed to be formed from the surface ablation of the large particles. The surface plasmon absorption band is found to be narrower when the nanoparticles are produced with laser irradiation. Throughout the exposure time with the CW lamp, the plasmon resonance absorption band of the particles formed first grows in intensity, then blue shifts and narrows, and finally red shifts while decreasing in intensity. The TEM results for lamp samples showed particle formation and growth, followed by small nanoparticle formation. The above results are discussed in terms of a mechanism in which, the excited benzophenone forms the ketal radical, which reduces Ag+ in solution and on the Ag nanoparticle surface. As the time of irradiation or the light energy increases the benzophenone is consumed, which is found to be the limiting reagent. This stops the formation of the normal large nanoparticles while their photo-ablation continues to make the small particles. %B Photochemical & Photobiological Sciences %I Royal Society of Chemistry %V 4 %P 154-159 %G eng %N 1 %R 10.1039/B411488D %0 Journal Article %J Chem. Soc. Rev. %D 2005 %T Why gold nanoparticles are more precious than pretty gold: Noble metal surface plasmon resonance and its enhancement of the radiative and nonradiative properties of nanocrystals of different shapes %A Eustis, Susie %A El-Sayed, Mostafa A. %K display %X This tutorial review presents an introduction to the field of noble metal nanoparticles and their current applications. The origin of the surface plasmon resonance and synthesis procedures are described. A number of applications are presented that take advantage of the electromagnetic field enhancement of the radiative properties of noble metal nanoparticles resulting from the surface plasmon oscillations. %B Chem. Soc. Rev. %I The Royal Society of Chemistry %V 35 %P 209-217 %G eng %N 3 %R 10.1039/B514191E