• Bulletin of the Korean Chemical Society
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• 제12권6호
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• pp.652-658
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• 1991

The effect of intermolecular collisions in the infrared multiphoton dissociation (IRMPD) of difluorochloromethane was investigated using He, Ar, and $N_2$ as buffer gases. The reaction probability for IRMPD of difluorochloromethane was measured as a function of laser fluence and the buffer gas pressure under unfocused beam geometry. It was observed that the reaction probability was initially enhanced with the increase of buffer gas pressure up to about 20 torr, but showed a decline at higher pressures. The reaction probability increases monotonically with the laser fluence, but the rate of increase diminishes at higher fluences. An attempt was made to simulate the experimental results by the method of energy grained master equation (EGME). From the parameters that fit the experimental data, the average energy loss per collision, $<{\Delta}E>_d$, was estimated for the He, Ar, and $N_2$ buffer gases.

• Bulletin of the Korean Chemical Society
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• 제11권3호
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• pp.214-220
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• 1990

We have studied the Infrared Multiphoton Dissociation (IRMPD) of 1-bromo-3-chloropropane by using the pulsed $CO_2$ laser. The product yields and the HCl/HBr branching ratios in IRMPD of $BrCH_2CH_2CH_2Cl$ are studied under the focused beam geometry as a function of buffer gas (He) pressure, laser energy, and photolysing wavelength. It is observed that the total dissociation yield has a laser energy dependence of 1.8-2.0 power order and the branching ratio is very slightly dependent on the pulse energy for the laser lines employed. The dependences of total dissociation yield and branching ratio on the buffer gas pressures show that the dissociation yield monotonically decreases and the branching ratio slightly decreases with the increase of the buffer gas pressure. The Energy-Grained Master Equation (EGME) was applied to explain the laser pulse energy and the buffer gas pressure(He) dependence of the dissociation yield and the branching ratio.

• Bulletin of the Korean Chemical Society
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• 제34권11호
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• pp.3327-3334
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• 2013

Infrared multiphoton dissociation (IRMPD) spectra of various protonated 1,2-diaminoethane-water clusters DAE-$H^+-(H_2O)_n$ (n = 1-6) were measured in the wavelength range of 3000-3800 $cm^{-1}$. The IRMPD spectra of the well separated ionic clusters were simulated by the MP2 method employing various basis sets. Comparison of the IRMPD spectra with the theory indicates that each cluster may exist as several low-lying conformers, and the sum spectra of the various conformers reveal almost one to one correspondence between theory and experiment. Free N-H and O-H stretches are observed in the ranges of 3400-3500 and 3600-3800 $cm^{-1}$, respectively. The $O-H{\cdots}N$ and $N-H{\cdots}O$ stretches are, however, observed in the broad region of 3000-3600 $cm^{-1}$. The theoretical calculations on DAE-$H^+-(H_2O)_n$ (n = 1-4) show gradual decrease of the average binding energy between DAE-$H^+$ and $H_2O$ as the cluster size increases, attaining the lowest value of 55 kJ/mol when n = 4. We found a low energy barrier of 21 kJ/mol to the isomerization converting the lowest energy cluster of DAE-$H^+-(H_2O)_n$ to the second lowest one.

• Bulletin of the Korean Chemical Society
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• 제10권1호
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• pp.96-101
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• 1989

The infrared multiphoton decomposition of trichloroethylene-H(TCE-H) and trichloroehtylene-D(TCE-D) was studied by using the high power $CO_2$ laser. The pressure dependence of TCE-H decomposition showed that the HCl elimination channel to form ClC ≡ CCl was the major step at high pressures, while the HC ≡ CCl formation step became important at low pressures. $Cl_2C$ = CHCl ${\rightarrow}$ (high pressure) ClC ${\equiv}$ CCl + HCl ${\rightarrow}$ (low pressure) HC ${\equiv}$ CCl + 2Cl${\cdot}$($Cl_2$) The IRMPD of TCE-H and TCE-D mixtures with 10P(20) laser line showed that optimum conditions of large isotope selectivity were the low system pressures and high laser powers. The experimentally observed dependence of the branching ratios on the pressure and laser fluence, and the isotope selectivity coefficients were quantitatively explained by using the modified energy grained master equations (EGME) model.

• Bulletin of the Korean Chemical Society
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• 제9권3호
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• pp.161-164
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• 1988

Infrared multiphoton decompositions (IRMPD) of $BrCH_2CH_2CH_2CH_2Cl$ were studied by using the pulsed $CO_2$laser. At 0.3 J laser energy the experimentally observed product ratios could be reasonably explained by the RRKM calculation with initial excitation energy of ca. 80 Kcal/mol. The pressure dependence of product yields led us to conclude that the collisional deactivation by the inert gas decreased the yield of low energy dissociation channel more significantly.

• Mass Spectrometry Letters
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• 제12권4호
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• pp.126-130
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• 2021

The mass spectrometry (MS) provides the mass-to-charge ratios of atoms, molecules, stable/metastable complexes, and their fragments. I have taken a long journey with MS to address outstanding issues and problems by experiments and theory and gain insights into underlying principles in chemistry. By looking through the mass-to-charge ratio, I have studied thermochemical problems in silicon chemistry, the infrared multiphoton dissociation spectroscopy of organometallic intermediates, unimolecular dissociations of halotoluene radical cations, and the kinetics of association/dissociation of alkali halide triple ions with Lewis bases. Various MS platforms have been used to characterize non-covalent interactions between porphyrins and fullerenes and those between the group IIB ions and trioctylchalcogenides, and to examine the binding of the group IA, IIA and porphyrin ions to G-quadruplex DNA. Recently, I have focused on mass-balanced H/D isotope dipeptide tags for MS-based quantitative proteomics, a simple chemical modification method for MS-based lipase assay, and the kinetics and dynamics of energy-variable collision-induced dissociation of chemically modified peptides. Now, I see an important role of MS in global issues in the post-COVID era, as the society demands high standards for indoor air quality to contain the airborne-pathogen transmission as well as in-situ monitoring and tracking of carbon emissions to reduce global warming.

• Journal of Photoscience
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• 제12권2호
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• pp.101-107
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• 2005

Infrared multiphoton dissociation of $CHCl_2F$ was studied using $CO_2$ laser excitation. Three products, $C_2Cl_2F_2$, $C_2ClF_3$, and $C_2HClF_2$, were identified by the analysis of the gas mixture from the photoreaction of $CHCl_2F$. The dependence of the reaction probability on added Ar gas pressure and excitation laser pulse energy was investigated. At low pressure (< 10 torr), the reaction probability increased as Ar pressure increased due to the rotational hole-filling effect, while it diminished with the increase of Ar pressure at high pressure (> > 20 torr) due to the collisional deactivation. The ratio of two products $(C_2ClF_3/C_2Cl_2F_2)$ decreased at low pressure (< 10 torr) and increased at high pressure (> 20 torr) with the increase of Ar pressure. The log-log plot of the reaction probability vs. laser pulse energy (${\\phi}$) was found to have a linear relationship, and its slope decreased as the added Ar pressure was increased. The reaction mechanisms for product formation have been suggested and validated by experimental evidences and considering the energetics. Fluorine-chlorine exchange reaction in the intermediate complex has been suggested to explain the formation of $C_2ClF_3$.