• Title/Summary/Keyword: photodissociation

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Photodissociation Dynamics of Allyl Alcohol in UV: The Exit Channel Barrier for OH Production

  • Lee, Ji-Hye;Kang, Tae-Yeon;Kwon, Chan-Ho;Hwang, Hyon-Seok;Kim, Hong-Lae
    • Bulletin of the Korean Chemical Society
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    • v.32 no.2
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    • pp.510-514
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    • 2011
  • Photodissociation dynamics of allyl alcohol ($H_2C$=CH-$CH_2OH$) has been investigated at 205 - 213 nm along the UV absorption band by measuring rotationally-resolved laser-induced fluorescence spectra of OH radicals. Observed energy partitioning of the available energy among products at all photon energies investigated was similar and the barrier energy for OH production is about 574.7 kJ/mol from the OH yield measurements. The potential energy surfaces for the $S_0$, $T_1$, and $S_1$ excited states along the dissociation coordinate were obtained by ab initio quantum chemical calculations. The observed energy partitioning was successfully modeled by the "barrier-impulsive model" with the reverse barrier and the geometry obtained by the calculated potential energy surfaces. The dissociation takes place on the $T_1$ excited state potential energy surface with an energy barrier in the exit channel and a large portion of the photon energy is distributed in the internal degrees of freedom of the polyatomic products.

Photodissociation of C3H5Br and C4H7Br at 234 nm

  • Kim, Hyun-Kook;Paul, Dababrata;Hong, Ki-Ryong;Cho, Ha-Na;Lee, Kyoung-Seok;Kim, Tae-Kyu
    • Bulletin of the Korean Chemical Society
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    • v.33 no.1
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    • pp.143-148
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    • 2012
  • The photodissociation dynamics of cyclopropyl bromide ($C_3H_5Br$) and cyclobutyl bromide ($C_4H_7Br$) at 234 nm was investigated. A two-dimensional photofragment ion-imaging technique coupled with a [2+1] resonanceenhanced multiphoton ionization scheme was utilized to obtain speed and angular distributions of the nascent $Br(^2P_{3/2})$ and $Br^*(^2P_{1/2})$ atoms. The recoil anisotropies for the Br and $Br^*$ channels were measured to be ${\beta}_{Br}=0.92{\pm}0.03$ and ${\beta}_{Br^*}=1.52{\pm}0.04$ for $C_3H_5Br$ and ${\beta}_{Br}=1.10{\pm}0.03$ and ${\beta}_{Br^*}=1.49{\pm}0.05$ for $C_4H_7Br$. The relative quantum yield for Br was found to be ${\Phi}_{Br}=0.13{\pm}0.03$ and for $C_3H_5Br$ and $C_4H_7Br$, respectively. The soft radical limit of the impulsive model adequately modeled the related energy partitioning. The nonadiabatic transition probability from the 3A' and 4A' potential energy surfaces was estimated and discussed.

Observation of Methyl Radical Recombination Following Photodissociation of CH3I at 266 nm by Time-Resolved Photothermal Spectroscopy

  • Suh, Myung-Koo;Sung, Woo-Kyung;Li, Guo-Sheng;Heo, Seong-Ung;Hwang, Hyun-Jin
    • Bulletin of the Korean Chemical Society
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    • v.24 no.3
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    • pp.318-324
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    • 2003
  • A time-resolved probe beam deflection (PBD) technique was employed to study the energy relaxation dynamics of photofragments produced by photodissociation of $CH_3I$ at 266 nm. Under 500 torr argon environment, experimental PBD transients revealed two energy relaxation processes; a fast relaxation process occurring within an acoustic transit time (less than 0.2 ㎲ in this study) and a slow relaxation process with the relaxation time in several tens of ㎲. The fast energy relaxation of which signal intensity depended linearly on the excitation laser power was assigned to translational-to-translational energy transfer from the photofragments to the medium. As for the slow process, the signal intensity depended on square of the excitation laser power, and the relaxation time decreased as the photofragment concentration increased. Based on experimental findings and reaction rate constants reported previously, the slow process was assigned to methyl radical recombination reaction. In order to determine the rate constant for methyl radical recombination reaction, a theoretical equation of the PBD transient for a radical recombination reaction was derived and used to fit the experimental results. By comparing the experimental PBD curves with the calculated ones, the rate constant for methyl recombination is determined to be $3.3({\pm}1.0)\;{\times}\;10^6\;s^{-1}torr^{-1}$ at 295 ± 2 K in 500 torr Ar.

Photodissociation Dynamics of C2H4BrCl: Nonadiabatic Dynamics with Intrinsic Cs Symmetry

  • Lee, Kyoung-Seok;Paul, Dababrata;Hong, Ki-Ryong;Cho, Ha-Na;Jung, Kwang-Woo;Kim, Tae-Kyu
    • Bulletin of the Korean Chemical Society
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    • v.30 no.12
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    • pp.2962-2968
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    • 2009
  • The photodissociation dynamics of 1,2-bromochloroethane ($C_2H_4BrCl$) was investigated near 234 nm. A two-dimensional photofragment ion-imaging technique coupled with a [2+1] resonance-enhanced multiphoton ionization scheme was utilized to obtain speed and angular distributions of the nascent Br($^2P_{3/2}$) and Br${\ast}($^2P_{1/2}$) atoms. The total translational energy distributions for the Br and Br${\ast}$ channels were well characterized by Gaussian functions with average translational energies of 100 and 84 kJ/mol, respectively. The recoil anisotropies for the Br and Br${\ast}$ channels were measured to be ${\beta}$ = 0.49 ${\pm}$ 0.05 for Br and 1.55 ${\pm}$ 0.05 for Br${\ast}$. The relative quantum yield for Br${\ast}$ was found to be ${\Phi}_{Br{\ast}}$ = 0.33 ${\pm}$ 0.03. The probability of nonadiabatic transition between A' states was estimated to be 0.46. The relevant nonadiabatic dynamics is discussed in terms of interaction between potential energy surfaces in Cs symmetry.

A Study on Effect of $NO_2$ Photodissociation rate on Ozone concentration from Rural and Urban Area in the Winter (청정지역과 도시지역에서 $NO_2$ 광분해율이 오존농도에 미치는 영향에 관한 연구)

  • 이정주;이동범;윤중섭
    • Journal of Environmental Health Sciences
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    • v.26 no.4
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    • pp.141-147
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    • 2000
  • Due to a rapid in automobiles since the 1980’s, the concentration of NO, and HC has also increased along with cases of VOCs. These air pollutants have created $O_3$ concentration, which cause a harmful effect to the human health. This issue has become a subject of great public interest. For this paper, to compare the concentration of $O_3$, NO, N $O_2$ between the rural and urban area in the winter, the concentrations of each have been measuredevery hour during Jan.~Feb. 2000, 1998, respectively. To calculate the Photochemical Steady State, $\Phi$= $J_{N O_2}$[N $O_2$]/ $k_1$[NO][ $O_3$], temperature and $J_{ N O_2}$ has been determined. The NO concentration in the rural are showed at below 10 ppb while the NO concentration in the urban area showed maximum value of 90~120 ppb. But the $O_3$ concentration in both areas showed less than 30 ppb. The reason is that the N $O_2$ photodissiciation rate is low due to the temperature being below 2$^{\circ}C$ and less than 60 degrees in the solar zenith angle during the winter time, which makes the $O_3$ concentration in both areas, similar in the concentration level. N $O_2$ photodissociation rate in both ares showed maximum value of 3.0mW/$\textrm{cm}^2$. Values of $\Phi$ determined from the rural area was consistently the unity, approaching 1. But values of $\Phi$ determined from the urban was roughly higher than unity, approaching above 1or 2 for clear sky-high sun(10:00~16:00).

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Photofragment Translational Spectroscopy of CH₂I₂ at 304 nm: Polarization Dependence and Energy Partitioning

  • 정광우;Temer S. Ahmadi;Mostafa A. El-Sayed
    • Bulletin of the Korean Chemical Society
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    • v.18 no.12
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    • pp.1274-1280
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    • 1997
  • 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(2P3/2) and spin-orbit excited state I*(2P1/2) iodine atoms, which are produced from photodissociation of CH2I2 at this wavelength. These processes are found to occur via B1 ← A1 type electronic transitions. The quantum yield of I*(2P1/2) 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 β(I)=0.4 for the I(2P3/2) and β(I*)=0.55 for the I*(2P1/2) 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; < Eint > /Eavl=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.

Non-Lorentzian Resonance Due to the Detuning in One-Color Two-Photon Photodissociation

  • Lee, Seong Yul
    • Bulletin of the Korean Chemical Society
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    • v.21 no.7
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    • pp.712-714
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    • 2000
  • Non-Lorentyian resonance is predicted to occur in two-photon photoabsorption processes due to the detuning off the intermediate levels. This type of non-Lorentzian resonance is distinct from the asymmetric resonance resulting from the effects of q uantum interference between competing indistinguishable dynamic pathways. The product distributions are shown to be constant near this type of resonance.