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 - Fluorine Substitution Effects on the Photodissociation Dynamics of Iodobenzene at 304 nm JF - The Journal of Physical Chemistry Y1 - 1996 A1 - Griffiths, Jennifer A. A1 - Jung, Kwang-Woo A1 - El-Sayed, Mostafa A AB - The photodissociation dynamics of pentafluoroiodobenzene are investigated by state-selective one-dimensional translation spectroscopy at 304 nm. We have determined the one-dimensional recoil distribution and the spatial distribution in the form of the anisotropy parameter, ?, as well as the photodissociation relative yields of both ground-state I(3P3/2) and excited-state I*(2P1/2) iodine photofragments. The results are compared to those observed for iodobenzene at 304 nm. As in iodobenzene, two velocity distributions were observed for the dissociation channel which gives ground-state iodine:? a sharp, high recoil velocity peak assigned previously to n,σ* excitation and a slow recoil velocity distribution peak assigned previously to π,π* excitation. Unlike in C6H5I, the I* distribution is relatively strong and its spatial anisotropy can be measured. The fluorine perturbation has led to a number of different observations that can be summarized as follows:? (1) The high velocity distribution has a lower average value and much broader width, suggesting more rapid energy redistribution to the fluorinated phenyl ring prior to and during the dissociation process, resulting from stronger coupling between the n,σ* and π,π* states and/or a longer excited-state lifetime; (2) the slow distribution is weaker and has an almost isotropic spatial distribution (the anisotropy parameter ? ≈ 1.0), while in the iodobenzene spectrum ? is correlated with the recoil velocity; (3) the I* quantum yield for C6F5I is 14 times larger than that for iodobenzene; and (4) ? is correlated with the velocity in the I* spectrum found for C6F5I which is not observed for iodobenzene. These observed fluorine perturbations are attributed to an increased mixing between the charge-transfer state (resulting from electron transfer from the iodine nonbonding electrons to the π* orbitals of the fluorinated benzene ring) and both the n,σ* and the ring π,π* states. This leads to two effects:? (1) a decrease in the nonbonding electron density on the iodine, which decreases the spin-orbit interaction between the n,σ* states themselves, resulting in a decrease in the curve-crossing probability (thus increasing the I* yield) and (2) an increase in the coupling between the repulsive n,σ* states and the fluorinated phenyl π,π* states, leading to an increase in the rate of energy redistribution.The photodissociation dynamics of pentafluoroiodobenzene are investigated by state-selective one-dimensional translation spectroscopy at 304 nm. We have determined the one-dimensional recoil distribution and the spatial distribution in the form of the anisotropy parameter, ?, as well as the photodissociation relative yields of both ground-state I(3P3/2) and excited-state I*(2P1/2) iodine photofragments. The results are compared to those observed for iodobenzene at 304 nm. As in iodobenzene, two velocity distributions were observed for the dissociation channel which gives ground-state iodine:? a sharp, high recoil velocity peak assigned previously to n,σ* excitation and a slow recoil velocity distribution peak assigned previously to π,π* excitation. Unlike in C6H5I, the I* distribution is relatively strong and its spatial anisotropy can be measured. The fluorine perturbation has led to a number of different observations that can be summarized as follows:? (1) The high velocity distribution has a lower average value and much broader width, suggesting more rapid energy redistribution to the fluorinated phenyl ring prior to and during the dissociation process, resulting from stronger coupling between the n,σ* and π,π* states and/or a longer excited-state lifetime; (2) the slow distribution is weaker and has an almost isotropic spatial distribution (the anisotropy parameter ? ≈ 1.0), while in the iodobenzene spectrum ? is correlated with the recoil velocity; (3) the I* quantum yield for C6F5I is 14 times larger than that for iodobenzene; and (4) ? is correlated with the velocity in the I* spectrum found for C6F5I which is not observed for iodobenzene. These observed fluorine perturbations are attributed to an increased mixing between the charge-transfer state (resulting from electron transfer from the iodine nonbonding electrons to the π* orbitals of the fluorinated benzene ring) and both the n,σ* and the ring π,π* states. This leads to two effects:? (1) a decrease in the nonbonding electron density on the iodine, which decreases the spin-orbit interaction between the n,σ* states themselves, resulting in a decrease in the curve-crossing probability (thus increasing the I* yield) and (2) an increase in the coupling between the repulsive n,σ* states and the fluorinated phenyl π,π* states, leading to an increase in the rate of energy redistribution. PB - American Chemical Society VL - 100 SN - 0022-3654 UR - http://dx.doi.org/10.1021/jp952662u CP - 19 N1 - doi: 10.1021/jp952662u J1 - J. Phys. Chem. ER - TY - JOUR T1 - Photofragment translational spectroscopy of Ibr at 304 nm: Polarization dependence and dissociation dynamics JF - Journal of Chemical Physics Y1 - 1995 A1 - Jung, Kwang-Woo A1 - Griffiths, Jennifer A. A1 - El-Sayed, Mostafa A AB - The photodissociation dynamics of IBr 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 IBr at this wavelength. Two sharp velocity distributions observed for the I channel suggest the two dissociation pathways that correlate with ground-state iodine formation. Based on the expected translational energy release and the energy separation between the peaks, the two distributions have been assigned to dissociation of IBr to form I(P-2(3/2))+Br(P-2(3/2)) and I(P-2(3/2))+Br*(P-2(1/2)) with the former channel appearing at higher translational energy. The I* distribution shows one strong peak indicating that there is one dominant channel for formation of I* atoms at this wavelength which has been assigned to dissociation of IBr to form I*(P-2(1/2))+Br(P-2(3/2)) with a quantum yield of 0.1. The I* signal formed from the I*(P-2(1/2))+Br*(P-2(1/2)) dissociation channel is observed very weakly. The observed anisotropy parameter indicates that the I+Br* product (beta=-0.7) is formed mainly from the perpendicular (1) Pi(1)(2341)<--X transition while the I*+Br channel (beta=1.8) is formed predominantly from the parallel 3 Pi(0+)(2341)<--X transition followed by curve crossing to the (3) Sigma(0+)(-)(2422) State. The recoil energy dependence of the anisotropy parameter in the I atom produced in the I+Br channel shows a positive beta value above maximum of the peak recoil energy and a negative value below the peak maximum of the recoil energy distribution. These results are interpreted in terms of the presence of more than one path for the formation of I+Br photoproduct with opposite polarization for their absorbing transitions, most likely the (3) Pi(0+)(2341)<--X and the (3) Pi(1)(2341)<--X transitions. The possible excited state dynamics which give the observed results are discussed in terms of the previously proposed potential energy diagrams for IBr and ICl. (C) 1995 American Institute of Physics. VL - 103 SN - 0021-9606 N1 - Times Cited: 11 M3 - 10.1063/1.470326 ER -