• Title/Summary/Keyword: Laser Photolysis

Search Result 33, Processing Time 0.026 seconds

Reaction of Cr Atoms with O2 at Low Pressures: Observation of New Chemiluminescence Bands from CrO2*

  • Son, Hyung-Su;Ku, Ja-Kang
    • Bulletin of the Korean Chemical Society
    • /
    • v.25 no.2
    • /
    • pp.226-232
    • /
    • 2004
  • Ground and low-lying electronic states of Cr atoms in the gas phase were generated from photolysis of $Cr(CO)_6$ vapor in He or Ar using an unfocussed weak UV laser pulse and their reactions with $O_2$ and $N_2O$ were studied. When 0.5-1.0 Torr of $Cr(CO)_6$ /$O_2$ /He or Ar mixtures were photolyzed using 295-300 nm laser pulses, broadband chemiluminescence peaked at ~420 and ~500 nm, respectively, was observed in addition to the atomic emissions from $z^7P^{\circ}$, $z^5P^{\circ}$, and $y^7P^{\circ}$ states of Cr atoms. When $N_2O$ was used instead of $O_2$, no chemiluminescence was observed. The chemiluminescence intensities as well as the LIF intensities for those three low-lying electronic states ($a^7S_3,\;a^5S_2\;and\;a^5D_J$) showed second-order dependence on the photolysis laser power. Also, the chemiluminescence intensities were first-order in $O_2$ pressure, but the presence of excess Ar showed a strong inhibition effect on them. Based on the experimental results, the chemiluminecent species in this work is attributed to $CrO_2^*$ generated from hot ground state Cr atoms with $O_2$. The apparent radiative lifetimes of the chemiluminescent species and collisional quenching rate constants by $O_2$ and Ar also were investigated.

Matrix Infrared Spectra and DFT Computations of 2H-Azirine Produced from Acetonitrile by Laser-Ablation Plume Radiation

  • Cho, Han-Gook
    • Bulletin of the Korean Chemical Society
    • /
    • v.35 no.7
    • /
    • pp.2093-2096
    • /
    • 2014
  • 2H-azirine, a less known acetonitrile isomer, is observed in matrix IR spectra from the precursor exposed to radiation from laser ablation of transition-metals. Its vibrational characteristics confirm the previous results, and those for the deuterated and $^{13}C$ substituted isotopomers are also newly reported. The weak absorptions are traced to the low production yield due to its high energy and low extinction constants. IRC computations reveal smooth inter-conversion between 2H-azirine and $CH_2NCH$, providing a rationale for the observed variation of their relative contents during photolysis.

Time Resolved ESR Studies on Short-Lived Reaction Intermediates Produced by Laser Photolysis of Anthraquinone in Organic Solvents (유기용매에서 Anthraquinone의 광반응에서 생성하는 짧은 수명의 반응중간체에 관한 시간분해 ESR 연구)

  • Hong, Daeil;Yun, Young Hyoun;Sohn, Moo-Jeong;Kim, Kyung-Chan;Kuwata, Keiji
    • Journal of the Korean Chemical Society
    • /
    • v.39 no.4
    • /
    • pp.237-243
    • /
    • 1995
  • The measurments of neutral semiquinone radicals, which were formed from the laser flash photolysis of anthraquinone (AQ) in the mixed solvents were carried out by the time resolved electron spin resonance (trESR) spectroscopy. The chemically induced dynamic electron polarization (CIDEP) spectra of the neutral semiquinone radical (AQH${\cdot}$) and semiquinone radical anion (AQ${\cdot}$-) were successively detected in the laser flash photolysis of AQ in the mixtures of 2-propanol (PrOH) and triethylamine (TEA). The neutral semiquinone radical was short-lived with the half-life of 0.8 ${\mu}sec$, whereas the semiquinone radical anion was relatively stable and then its cwESR could be observed. The rate constant of the spin-depolarization of semiquinone radical anion was $2.6{\times}10^5 sec^{-1}$ and the decay of the radical anion was the first order reaction with the rate constant of $3.0{\times}10^2\; sec^{-1}$. No CIDEP of semiquinone radical anion was observed in the mixture of PrOH and the lower concentration of TEA than 2 percent. The CIDEP spectrum of the neutral semiquinone radical was detected in the mixture of benzene and TEA with the half-life of 3.0 ${\mu}sec$. The neutral semiquinone radical could not be detected by cwESR. Neither CIDEP nor ESR absorption could be observed in PrOH, TEA or benzene only.

  • PDF

PHOTOINDUCED ELECTRON TRANSFER REACTIONS OF 1,4-DIPHENYL-1,3-BUTADIYNE

  • Kim, Bang-Duk;Shim, Sang-Chul
    • Journal of Photoscience
    • /
    • v.5 no.1
    • /
    • pp.23-26
    • /
    • 1998
  • Irradiation of diphenylbutadiyne (DPB) in methanol with 9,10-dicyanoanthracene (DCA) yields four methanol adducts, two more than the products obtained in the absence of DCA. Laser flash photolysis studies indicate the reaction to proceed through a photoinduced electron transfer mechanism involving DPB cation radical and DCA anion radical.

  • PDF

Photodecomposition Mechanism of 2-Methoxy-1,2-diphenyl Diazoethane

  • Seong, Dae Dong;Im, Gwi Taek;Kim, Min Sik;Park, Dong Gyu
    • Bulletin of the Korean Chemical Society
    • /
    • v.16 no.1
    • /
    • pp.47-52
    • /
    • 1995
  • The mechanism of the photodecomposition of 2-methoxy-1,2-diphenyl diazoethane has been investigated in methanol and isoprene using time-resolved laser flash photolysis techniques. The reaction of triplet carbene which is generated from 2-methoxy-1,2-diphenyl diazoethane with methanol is believed to proceed via thermal excitation to the singlet state. The activation energy and enthalpy are consistent with a mechanism involving thermal equilibrium between the triplet and singlet state followed by the reaction of the singlet with methanol to give ether.

Time Resolved Electron Spin Resonance Spectroscopy of Anthrasemiquinone Radical Produced by Pulse Laser Photolysis. A Study on Chemically Induced Dynamic Electron Polarization (광화학 반응에서 생성된 Anthrasemiquinone Radical의 시간분해 ESR ; CIDEP에 관한 연구)

  • Hong Daeil;Kuwata Keiji
    • Journal of the Korean Chemical Society
    • /
    • v.34 no.5
    • /
    • pp.404-412
    • /
    • 1990
  • The time resolved electron spin resonance spectroscopy are used to two measurement methods of chemically induced dynamic electron polarization (CIDEP) and absorption ESR. The spectra of the semiquinone radical anion were successively detected in the laser flash photolysis of anthraquinone in the mixtures of 2-propanol and triethylamine. The semiquinone radical anion was fairly stable and its cw ESR could be observed. The rate constant (T1$^{-1}$) of the spin-depolarization of polarized semiquinone radical anion was 2.6 ${\times}\;1-^5$ sec$^{-1}$ and the decay of the radical anion was the first order with the rate constant (K$_1}$) of 300.0 sec$^{-1}$. The intensity of CIDEP spectra increased with the increasing the microwave power, but the Torrey wiggles appeared following with decay curves.

  • PDF

Tin Germanium Sulfide Nanoparticles for Enhanced Performance Lithium Secondary Batteries (고성능 리튬 이차 전지를 위한 황화 주석 저마늄 (SnxGe1-xS) 나노입자 연구)

  • Cha, E.H.;Kim, Y.W.;Lim, S.A.;Lim, J.W.
    • Journal of the Korean Electrochemical Society
    • /
    • v.18 no.1
    • /
    • pp.31-37
    • /
    • 2015
  • Composition-controlled ternary components chalcogenides germanium tin sulfide ($Sn_xGe_{1-x}S$) nanoparticles were synthesized by a novel gas-phase laser photolysis reaction of tetramethyl germanium, tetramethyl tin, and hydrogen sulfide mixture. Subsequent thermal annealing of as-grown amorphous nanoparticles produced the crystalline orthorhombic phase nanoparticles. All these composition-tuned nanoparticles showed excellent cycling performance of the lithium ion battery. The germanium sulfide nanoparticles exhibit a maximum capacity of 1200 mAh/g after 70 cycles. As the tin composition (x) increases, the capacity maintains better at the higher discharge/charge rate. This novel synthesis method of tin germanium sulfide nanoparticles is expected to contribute to expand their applications in high-performance energy conversion systems.

Observation of Elusive CF2Cl…Cl in Matrix Infrared Spectra and Density Functional Calculations

  • Cho, Han-Gook
    • Bulletin of the Korean Chemical Society
    • /
    • v.34 no.11
    • /
    • pp.3274-3278
    • /
    • 2013
  • $CF_2Cl{\cdots}Cl$, an elusive photo-isomer of $CF_2Cl_2$, has been observed in matrix IR spectra from the precursors exposed to radiation from laser ablation of transition-metals. Other plausible products, $CFCl_2{\cdots}F$ and $FClC{\cdots}F-Cl$ are not detected due to their considerably higher energies. Parallel to its previously reported analogues, the C-X bonds are considerably stronger than those of the reactant, and particularly the Cl atom that is weakly bound to the residual Cl atom forms an unusually strong carbon-halogen bond. NBO analysis reveals that the C-Cl bond is a true double bond, and the weak $Cl{\cdots}Cl$ bond is largely ionic, $F_2C=Cl^{\delta+}{\cdots}Cl^{\delta-}$. IRC computation reproduces smooth inter-conversion between the reactant and product, and the transition state is energetically close to the product, consistent with its prompt disappearance in the early stage of photolysis.

Matrix Infrared Spectra and DFT Computations of CH2CNH and CH2NCH Produced from CH3CN by Laser-Ablation Plume Radiation

  • Cho, Han-Gook
    • Bulletin of the Korean Chemical Society
    • /
    • v.34 no.5
    • /
    • pp.1361-1365
    • /
    • 2013
  • The smallest ketenimine and hydrogen cyanide N-methylide ($CH_2CNH$ and $CH_2NCH$) are provided from the argon/acetonitrile matrix samples exposed to radiation from laser ablation of transition-metals. New infrared bands are observed in addition to better determination of the vibrational characteristics for the previously reported bands, and the $^{13}C$ substituted isotopomers ($^{13}{CH_2}^{13}CNH$ and $^{13}CH_2N^{13}CH$) are also generated. Density functional frequency calculations and the D and $^{13}C$ isotopic shifts substantiate the vibrational assignments. $CH_2CNH$ is probably produced through single-step conversion of $CH_3CN$, whereas $CH_2NCH$ through two-step conversion via 2H-azirine. Inter-conversions between these two products evidently do not occur during photolysis and annealing.

Electrical Properties of Laser CVD Silicon Nitride Film (Laser CVD SiN막의 전기적 특성)

  • Kim, Yong-Woo;Kim, Sang-Wook;Park, Jong-Wook;Kim, Chun-Sub;Sung, Yung-Kwon
    • Proceedings of the KIEE Conference
    • /
    • 1990.11a
    • /
    • pp.85-87
    • /
    • 1990
  • Silicon nitride film was deposited on a silicon wafer using a laser CVD(LCVD) technique, which is based on direct photolysis of $SiH_4/NH_3$ gas mixture by ArF laser beam(${\lambda}=193\;nm$). The refractive index of deposited SiN film is 1.9 at the temperature of $300^{\circ}C$, pressure of 5 torr. The breakdown field strength of LCVD SiN film was 10MV/cm. In IR spectrum, the absorption peak of Si-H, N-H, and Si-N is detected and it is shown that hydrogen is included in SiN film. From analysis of absorption band. it is calculated that density of Si-H, N-H bond is higher than $5{\times}10^{22}cm^{-3}$. LCVD MIS capacitor and PECVD MIS capacitor have injection-type hysteresis but it is known that hysteresis loss of LCVD MIS capacitor is smaller than that of PECVD MIS capacitor. It means that Interface state density of LCVD capacitor is smaller than that of PECVD capacitor. In addition, the flatband voltage($V_{FB}$) of LCVD is smaller than that of PECVD capacitor. And it means that fixed charged density($Q_{FIX}$) of LCVD capacitor is smaller than that of PECVD MIS capacitor.

  • PDF