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 - 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 -