TY - JOUR T1 - Hot electron and phonon dynamics of gold nanoparticles embedded in a gel matrix JF - Chemical Physics Letters Y1 - 2001 A1 - Mohamed, MB A1 - Ahmadi, Temer S. A1 - Link, Stephan A1 - Braun, Markus A1 - El-Sayed, Mostafa A AB - Using pump-probe technique, the dynamics of the hot carriers in metallic nanodots induced by femtosecond laser pulses are investigated in gold nanoparticles embedded in hydrogel and in organic gel and compared to that in aqueous solution. We found that changing the surrounding matrix from aqueous solution to hydrogel and then to organic gel leads to a large increase in the relaxation time of both the electron-phonon (e-ph) and the phonon-phonon (ph-ph) coupling. Furthermore, the ph-ph relaxation time becomes sensitive to the type of the organic solvent trapped in the gel network. This indicates that the relaxation dynamics depend on the thermal conductivity, chemical structure and the molecular dynamics of the surrounding medium. (C) 2001 Elsevier Science BN. All rights reserved. VL - 343 SN - 0009-2614 N1 - Mohamed, MB Ahmadi, TS Link, S Braun, M El-Sayed, MA M3 - 10.1016/s0009-2614(01)00653-4 ER - TY - JOUR T1 - Effect of Lattice Energy Mismatch on the Relative Mass Peak Intensities of Mixed Alkali Halide Nanocrystals JF - The Journal of Physical Chemistry A Y1 - 1997 A1 - Ahmadi, Temer S. A1 - El-Sayed, Mostafa A AB - The relative mass peak intensity distribution of the [M14-nAnI13]+ mixed alkali halide nanocrystals containing a ?magic? number of 14 metal cations (M and A) and 13 iodide anions is examined. These nanocrystals were generated through sputtering of mixed solid alkali halides using fast atom bombardment and analyzed by use of a double-focusing sector field mass spectrometer. The mass peak intensities of mixed cluster ions composed of two different metals relative to the ?pure? nanocrystals (containing one or the other metal) are compared for two types of mixed cluster ions:? one with small lattice energy mismatch, i.e., [Rb14-nKnI13]+ cluster ions, and the other type with large lattice energy mismatch, i.e., [Cs14-nAnI13]+ cluster ions where A is either Na, K, or Rb. In contrast to what was previously1 found for clusters with small energy mismatch in which the rate of formation (which depends on the possible number of isomers that each mixed cluster ion can have) determines the relative intensities of mass peaks, the rate of evaporation (i.e., the cluster instability) determines the relative mass peak intensities in salts with relatively large lattice energy mismatch. These results are consistent with our previously proposed kinetic model for the formation and decay of these clusters.The relative mass peak intensity distribution of the [M14-nAnI13]+ mixed alkali halide nanocrystals containing a ?magic? number of 14 metal cations (M and A) and 13 iodide anions is examined. These nanocrystals were generated through sputtering of mixed solid alkali halides using fast atom bombardment and analyzed by use of a double-focusing sector field mass spectrometer. The mass peak intensities of mixed cluster ions composed of two different metals relative to the ?pure? nanocrystals (containing one or the other metal) are compared for two types of mixed cluster ions:? one with small lattice energy mismatch, i.e., [Rb14-nKnI13]+ cluster ions, and the other type with large lattice energy mismatch, i.e., [Cs14-nAnI13]+ cluster ions where A is either Na, K, or Rb. In contrast to what was previously1 found for clusters with small energy mismatch in which the rate of formation (which depends on the possible number of isomers that each mixed cluster ion can have) determines the relative intensities of mass peaks, the rate of evaporation (i.e., the cluster instability) determines the relative mass peak intensities in salts with relatively large lattice energy mismatch. These results are consistent with our previously proposed kinetic model for the formation and decay of these clusters. PB - American Chemical Society VL - 101 SN - 1089-5639 UR - http://dx.doi.org/10.1021/jp962045l CP - 4 N1 - doi: 10.1021/jp962045l J1 - J. Phys. Chem. A M3 - doi: 10.1021/jp962045l ER - TY - JOUR T1 - Electron Dynamics of Passivated Gold Nanocrystals Probed by Subpicosecond Transient Absorption Spectroscopy JF - The Journal of Physical Chemistry B Y1 - 1997 A1 - Logunov, Stephan L. A1 - Ahmadi, Temer S. A1 - El-Sayed, Mostafa A A1 - Khoury, J. T. A1 - Whetten, R. L. AB - The electronic dynamics of gold nanocrystals, passivated by a monolayer of alkylthiol(ate) groups, were studied by transient spectroscopy after excitation with subpicosecond laser pulses. Three solution-phase gold samples with average particle size of 1.9, 2.6, and 3.2 nm with size distribution less than 10% were used. The photoexcitation in the intraband (surface plasmon region) leads to the heating of the conduction electron gas and its subsequent thermalization through electron?electron and electron?phonon interaction. The results are analyzed in terms of the contribution of the equilibrated ?hot? electrons to the surface plasmon resonance of gold. A different spectral response was observed for different sizes of gold nanoparticles. The results were compared to the dynamics of the large (30 nm diameter) gold nanocrystals colloidal solution. The size-dependent spectral changes are attributed to the reduction of the density of states for small nanoparticles. The observed variation in the kinetics of the cooling process in gold nanoparticles with changing the laser intensity is attributed to the temperature dependence of the heat capacity of the electron gas.The electronic dynamics of gold nanocrystals, passivated by a monolayer of alkylthiol(ate) groups, were studied by transient spectroscopy after excitation with subpicosecond laser pulses. Three solution-phase gold samples with average particle size of 1.9, 2.6, and 3.2 nm with size distribution less than 10% were used. The photoexcitation in the intraband (surface plasmon region) leads to the heating of the conduction electron gas and its subsequent thermalization through electron?electron and electron?phonon interaction. The results are analyzed in terms of the contribution of the equilibrated ?hot? electrons to the surface plasmon resonance of gold. A different spectral response was observed for different sizes of gold nanoparticles. The results were compared to the dynamics of the large (30 nm diameter) gold nanocrystals colloidal solution. The size-dependent spectral changes are attributed to the reduction of the density of states for small nanoparticles. The observed variation in the kinetics of the cooling process in gold nanoparticles with changing the laser intensity is attributed to the temperature dependence of the heat capacity of the electron gas. PB - American Chemical Society VL - 101 SN - 1520-6106 UR - http://dx.doi.org/10.1021/jp962923f CP - 19 N1 - doi: 10.1021/jp962923f J1 - J. Phys. Chem. B ER - TY - JOUR T1 - Photofragment translational spectroscopy of CH2I2 at 304 nm: Polarization dependence and energy partitioning JF - Bulletin of the Korean Chemical Society Y1 - 1997 A1 - Jung, Kwang-Woo A1 - Ahmadi, Temer S. A1 - El-Sayed, Mostafa A AB - The photodissociation dynamics of CH2I2 has been studied at 304 nm by state-selective photofragment translational spectroscopy. Velocity distributions, anisotropy parameters, and relative quantum yields are obtained for the ground I(P-2(3/2)) and spin-orbit excited state I*(P-2(1/2)) iodine atoms, which are produced from photodissociation of CH2I2 at this wavelength. These processes are found to occur via B-1 <-- A(1) type electronic transitions. The quantum yield of I*(P-2(1/2)) is determined to be 0.25, indicating that the formation of ground state iodine is clearly the favored dissociation channel in the 304 nm wavelength region. From the angular distribution of dissociation products, the anisotropy parameters are determined to be beta(I)=0.4 for the I(P-2(3/2)) and beta (I*)=0.55 for the I*(P-2(1/2)) which substantially differ from the limiting value of 1.13. The positive values of anisotropy parameter, however, show that the primary processes for I and I* formation channels proceed dominantly via a transition which is parallel to I-I axis. The above results are interpreted in terms of dual path formation of iodine atoms from two different excited states, i.e., a direct and an indirect dissociation via curve crossing between these states. The translational energy distributions of recoil fragments reveal that a large fraction of the available energy goes into the internal excitation of the CH2I photofragment; /E-avl=0.80 and 0.82 for the I and I* formation channels, respectively. The quantitative analysis for the energy partitioning of available energy into the photofragments is used to compare the experimental results with the prediction of direct impulsive model for photodissociation dynamics. VL - 18 SN - 0253-2964 N1 - Jung, KW Ahmadi, TS El-Sayed, MA ER - TY - JOUR T1 - Photofragment Translational Spectroscopy of ICl at 304 nm JF - The Journal of Physical Chemistry A Y1 - 1997 A1 - Jung, Kwang-Woo A1 - Ahmadi, Temer S. A1 - El-Sayed, Mostafa A AB - The photodissociation dynamics of ICl is studied at 304 nm by state-selective photofragment translational spectroscopy. Velocity distributions, anisotropy parameters, and relative quantum yields are obtained for the ground I(2P3/2) and spin?orbit excited state I*(2P1/2) iodine atoms, which are produced from photodissociation of ICl at this wavelength. Two sharp velocity distributions are observed for the I channel, suggesting the existence of two dissociation pathways that correlate with ground state iodine formation. Based on the expected translational energy release and the energy separation between those peaks, the two distributions are assigned to dissociation of ICl to I(2P3/2) + Cl(2P3/2) and to I(2P3/2) + Cl*(2P1/2); the former channel appears at higher translational energy. The distribution of I* also shows two strong peaks, indicating that there are two dominant channels for the formation of I* atoms at this wavelength which we assign to the dissociation of ICl forming I*(2P1/2) + Cl(2P3/2) and I*(2P1/2) + Cl*(2P1/2), respectively. The quantum yield of I*(2P1/2) is determined to be 0.30, indicating that the formation of ground state iodine is clearly the favored dissociation channel at 304 nm. The observed anisotropy in the angular distribution of dissociation products (?) indicates that the I* + Cl and I* + Cl* channels are formed predominantly from the parallel transition (? = 1.7 for both channels) while the I + Cl and I + Cl* products are formed mainly from perpendicular transitions (? = ?0.5). The decrease in the anisotropy parameter of the I formation channels from their limiting value of ?1 is attributed to the presence of more than one path for the formation of I + Cl/Cl* photoproducts with opposite polarization for their absorbing transitions. The possible excited state dynamics, which give the observed results, are discussed in terms of the previously proposed energy correlation diagram for ICl.The photodissociation dynamics of ICl is studied at 304 nm by state-selective photofragment translational spectroscopy. Velocity distributions, anisotropy parameters, and relative quantum yields are obtained for the ground I(2P3/2) and spin?orbit excited state I*(2P1/2) iodine atoms, which are produced from photodissociation of ICl at this wavelength. Two sharp velocity distributions are observed for the I channel, suggesting the existence of two dissociation pathways that correlate with ground state iodine formation. Based on the expected translational energy release and the energy separation between those peaks, the two distributions are assigned to dissociation of ICl to I(2P3/2) + Cl(2P3/2) and to I(2P3/2) + Cl*(2P1/2); the former channel appears at higher translational energy. The distribution of I* also shows two strong peaks, indicating that there are two dominant channels for the formation of I* atoms at this wavelength which we assign to the dissociation of ICl forming I*(2P1/2) + Cl(2P3/2) and I*(2P1/2) + Cl*(2P1/2), respectively. The quantum yield of I*(2P1/2) is determined to be 0.30, indicating that the formation of ground state iodine is clearly the favored dissociation channel at 304 nm. The observed anisotropy in the angular distribution of dissociation products (?) indicates that the I* + Cl and I* + Cl* channels are formed predominantly from the parallel transition (? = 1.7 for both channels) while the I + Cl and I + Cl* products are formed mainly from perpendicular transitions (? = ?0.5). The decrease in the anisotropy parameter of the I formation channels from their limiting value of ?1 is attributed to the presence of more than one path for the formation of I + Cl/Cl* photoproducts with opposite polarization for their absorbing transitions. The possible excited state dynamics, which give the observed results, are discussed in terms of the previously proposed energy correlation diagram for ICl. PB - American Chemical Society VL - 101 SN - 1089-5639 UR - http://dx.doi.org/10.1021/jp970837p CP - 36 N1 - doi: 10.1021/jp970837p J1 - J. Phys. Chem. A M3 - doi: 10.1021/jp970837p ER - TY - JOUR T1 - “Cubic” Colloidal Platinum Nanoparticles JF - Chemistry of Materials Y1 - 1996 A1 - Ahmadi, Temer S. A1 - Wang, Z.L. A1 - Henglein, A. A1 - El-Sayed, Mostafa A AB - Cubic platinum nanoparticles (4-18 nm) have been synthesized for the first time in solution by the controlled reduction of K2PtCl4 with hydrogen gas in the presence of sodium polyacrylate as a capping material. The nanoparticles are found to have fee structures, similar to the bulk metal with {100} facets. PB - American Chemical Society VL - 8 SN - 0897-4756 UR - http://dx.doi.org/10.1021/cm9601190 CP - 6 N1 - doi: 10.1021/cm9601190 J1 - Chem. Mater. M3 - 10.1021/cm9601190 ER - TY - JOUR T1 - Picosecond Dynamics of Colloidal Gold Nanoparticles JF - The Journal of Physical Chemistry Y1 - 1996 A1 - Ahmadi, Temer S. A1 - Logunov, Stephan L. A1 - El-Sayed, Mostafa A AB - Colloidal gold nanoparticles with an average radius of 15 nm have a surface plasmon absorption band at 530 nm. Excitation by laser pulses of 450 fs duration, and wavelength of 600 or 380 nm ?bleached? the plasmon band and produced a transient absorption at the wings of the ?bleach? spectrum. The transient absorption was found to have a similar temporal behavior at different wavelengths. Analysis of their temporal behavior showed two time constants:? 2.5 ps, and a slower component of >50 ps. Laser excitation close to the plasmon band at 600 nm leads to the formation of ?hot? non-Fermi electronic distribution within the colloidal particles. Transient absorption from these ?hot? electrons led to different absorptions from that of the plasmon absorption of ?cold? electrons. The ?hot? electrons relax via electron?phonon coupling in 2.5 ps, and the phonon?phonon relaxation of the lattice occurs in >50 ps. At 380 nm excitation, the amplitude of the blue wing becomes smaller, and the slow component becomes longer, which could be due to possible excitation of the d-band electrons. These results are discussed in terms of Mie theory and a two-temperature model (TTM), and their consequences on the optical absorption spectrum.Colloidal gold nanoparticles with an average radius of 15 nm have a surface plasmon absorption band at 530 nm. Excitation by laser pulses of 450 fs duration, and wavelength of 600 or 380 nm ?bleached? the plasmon band and produced a transient absorption at the wings of the ?bleach? spectrum. The transient absorption was found to have a similar temporal behavior at different wavelengths. Analysis of their temporal behavior showed two time constants:? 2.5 ps, and a slower component of >50 ps. Laser excitation close to the plasmon band at 600 nm leads to the formation of ?hot? non-Fermi electronic distribution within the colloidal particles. Transient absorption from these ?hot? electrons led to different absorptions from that of the plasmon absorption of ?cold? electrons. The ?hot? electrons relax via electron?phonon coupling in 2.5 ps, and the phonon?phonon relaxation of the lattice occurs in >50 ps. At 380 nm excitation, the amplitude of the blue wing becomes smaller, and the slow component becomes longer, which could be due to possible excitation of the d-band electrons. These results are discussed in terms of Mie theory and a two-temperature model (TTM), and their consequences on the optical absorption spectrum. PB - American Chemical Society VL - 100 SN - 0022-3654 UR - http://dx.doi.org/10.1021/jp960484e CP - 20 N1 - doi: 10.1021/jp960484e J1 - J. Phys. Chem. ER - TY - JOUR T1 - Shape-Controlled Synthesis of Colloidal Platinum Nanoparticles JF - Science (New York, N.Y.) Y1 - 1996 A1 - Ahmadi, Temer S. A1 - Wang, Z.L. A1 - Green, T.C. A1 - Henglein, A. A1 - El-Sayed, Mostafa A AB - The shapes and sizes of platinum nanoparticles were controlled by changes in the ratio of the concentration of the capping polymer material to the concentration of the platinum cations used in the reductive synthesis of colloidal particles in solution at room temperature. Tetrahedral, cubic, irregular-prismatic, icosahedral, and cubo-octahedral particle shapes were observed, whose distribution was dependent on the concentration ratio of the capping polymer material to the platinum cation. Controlling the shape of platinum nanoparticles is potentially important in the field of catalysis. VL - 272 CP - 5270 U1 - http://www.ncbi.nlm.nih.gov/pubmed/8662492?dopt=Abstract M3 - 10.1126/science.272.5270.1924 ER - TY - JOUR T1 - Dynamics of Formation and Evaporation of Mixed Alkali Halide Nanocrystals: A Case of Comparable Lattice Energies JF - The Journal of Physical Chemistry Y1 - 1994 A1 - Ahmadi, Temer S. A1 - El-Sayed, Mostafa A AB - View http://dx.doi.org/10.1021/j100095a013 for article's front page in lieu of an abstract PB - American Chemical Society VL - 98 SN - 0022-3654 UR - http://dx.doi.org/10.1021/j100095a013 CP - 44 N1 - doi: 10.1021/j100095a013 J1 - J. Phys. Chem. M3 - doi: 10.1021/j100095a013 ER -