• Bulletin of the Korean Chemical Society
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• v.31 no.1
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• pp.92-99
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• 2010

Photoexcitation of a precursor ion inside a cell floated at high voltage installed in a tandem time-of-flight (TOF) mass spectrometer provides triple tandem mass spectrometric information and allows kinetic and mechanistic studies. In this work, the factors affecting, or downgrading, the performance of the technique were identified. Ion-optical and computational analyses showed that an optimum instrument could be designed by utilizing a reflectron with linear-plus-quadratic potential inside. Theoretical predictions were confirmed by tests with instruments built with different ion-optical layout. With optimized instruments, masses of intermediate ions in the consecutive dissociation of a precursor ion could be determined with the maximum error of $\pm5$ Da. We also observed excellent agreement in dynamical parameters (critical energy and entropy) for the dissociation of a model peptide ion determined by instruments with different ion-optical layout operated under optimum conditions. This suggests that these parameters can be determined reliably by the kinetic method developed previously when properly designed and operated tandem TOF instruments are used.

• Mass Spectrometry Letters
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• v.12 no.4
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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.

• Mass Spectrometry Letters
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• v.12 no.2
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• pp.41-46
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• 2021

Collision-induced dissociation (CID) and higher-energy collisional dissociation (HCD) are the widely used fragmentation technique in mass spectrometry-based proteomics studies. Understanding the fragmentation pattern from the tandem mass spectra using statistical methods helps to implement efficient spectrum analysis algorithms. The study characterizes the frequency of occurrence of multi-charged fragment ions and their neutral loss events of doubly and triply charged peptides in the CID and HCD spectrum. The dependency of the length of the fragment ion on the occurrence of multi-charged fragment ion is characterized here. Study shows that the singly charged fragment ions are generally dominated in the doubly charged peptide spectrum. However, as the length of the product ion increases, the frequency of occurrence of charge 2 fragment ions increases. The y- ions have more tendencies to generate charge 2 fragment ions than b- ions, both in CID and HCD spectrum. The frequency of occurrence of charge 2 fragment ion peaks is prominent upon the dissociation of the triply charged peptides. For triply charged peptides, product ion of higher length occurred in multiple charge states in CID spectrum. The neutral loss peaks mostly exist in charge 2 states in the triply charged peptide spectrum. The b-ions peaks are observed in much less frequency than y-ions in HCD spectrum as the length of the fragment increases. Isotopic peaks are occurred in charge 2 state both in doubly and triply charged peptide's HCD spectrum.

• Bulletin of the Korean Chemical Society
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• v.35 no.3
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• pp.833-838
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• 2014

The energy- and time-dependent branching to the competing dissociation paths are studied by theory for coupled unimolecular dissociations of the o-, m-, and p-chlorotoluene radical cations to $C_7{H_7}^+$ (benzylium and tropylium). There are four different paths to $C_7{H_7}^+$, three to the benzylium ion and one to the tropylium ion, and all of them are coupled together. The branching to the multiple paths leads to the multiexponential decay of reactant with the branching ratio depending on both internal energy and time. To gain insights into the multipath branching, we study the detailed kinetics as a function of time and internal energy on the basis of ab inito/RRKM calculations. The number of reaction steps to $C_7{H_7}^+$ is counted for each path. Of the three isomers, the meta mostly goes through the coupling, whereas the para proceeds with little or no coupling. In the beginning, some reactants with high internal energy decay fast to the benzylium ion without any coupling and others rearrange to the other isomers. Later on all three isomers dissociate to the products via long-lived intermediates. Thus, the reactant shows a multiexponential decay and the branching ratio varies with time as the average internal energy decreases with time. The reciprocal of the effective lifetime is taken as the rate constant. The resulting rate-energy curves are in line with experiments. The present results suggest that the coupling between the stable isomers is thermodynamically controlled, whereas the branching to the product is kinetically controlled.

• Bulletin of the Korean Chemical Society
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• v.26 no.11
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• pp.1795-1802
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• 2005

Potential energy curves and internuclear (M-X) distance variations for dissociation reactions of $[MX_4]^{2-}$ into ($[MX_3]^-$ + $X^-$) have been calculated using ab initio Hartree-Fock (HF), second order M$\ddot{o}$ller-Plesset perturbation (MP2), and Density Functional Theory (DFT) methods with a triple zeta plus polarization (TZP) basis set. The equilibrium geometrical structures of $[MX_4]^{2-}$ are optimized to tetrahedral geometry for $[NiX_4]^{2-}$ and square planar geometry for ($[PdX_4]^{2-}$ and $[PtX_4]^{2-}$). The bond (M-X) distances of $[NiCl_4]^{2-}$, $[NiBr_4]^{2-}$, $[PdCl_4]^{2-}$, $[PdBr_4]^{2-}$, $[PtCl_4]^{2-}$, and $[PtBr_4]^{2-}$ at the DFT level are 2.258, 2.332, 2.351, 2.476, 2.367, and 2.493 $\AA$, respectively. The dissociation energies for the bond dissociation of ($[MX_3]^-$${\cdot}{\cdot}{\cdot}$$X^-$) at the DFT level are found to be 4.73 eV for $[NiCl_4]^{2-}$, 4.89 eV for $[NiBr_4]^{2-}$, 4.93 eV for $[PdCl_4]^{2-}$, 5.57 eV for $[PdBr_4]^{2-}$, 5.44 eV for $[PtCl_4]^{2-}$, and 5.87 eV for $[PtBr_4]^{2-}$. As the (M${\cdot}{\cdot}{\cdot}$X) distance of ($[MX_3]^-$${\cdot}{\cdot}{\cdot}$$X^-$) increases, the distance variation (Rt) of trans (M-X) bond at the trans-position is shorter than those (Rc) of two cis (M-X) bonds at the cisposition. Simultaneously the atomic charge variation of trans-X atom is more positive than those of equilibrium $[MX_4]^{2-}$ structures, while the variation of leaving X group is more positive.

• Journal of The Korean Astronomical Society
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• v.29 no.spc1
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• pp.345-346
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• 1996

The contrasting values of the oscillator strengths for the (0,0) band of SiH+ molecules for the $A\;^1II-X\;^1{\sum}+$ transition reported in literature, motivated us to reinvestigate the same with the help of a new set of well accepted solar photospheric models, elemental abundances and dissociation energy.

• Journal of the Korean Institute of Gas
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• v.19 no.3
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• pp.54-59
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• 2015

The gas hydrate of 10 trillion tons are buried under continental slope in the world(permafrost : 2%, marine continental slope: 98%), but technology for the the commercial gas recovery has not developed yet. There are normally four representative recovery methods: depressurization method, thermal stimulation method, inhibition injection method, and displacement method. This study focuses on change of dissociation time and gas production according to gas hydrate saturation rate and depressurization rate. It was found that the correlation between depressrization rate and dissociation time was like as $Y=0.0004X^2-0.499X+176.86$. It was also found that the bigger depressurization rate is, the better production is(methane gas is produced over 46.2% at depressurization rate 50% compared with 40%). However, on the contrary to this, it is presumed that gas production is decreased at 60% due to gas hydrate reformation.

• Korean Journal of Materials Research
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• v.20 no.9
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• pp.457-462
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• 2010

Adsorption of a water molecule on a Si (001) surface and its dissociation were studied using density functional theory to study the distribution of -OH fragments on the Si surface. The Si (001) surface was composed of Si dimers, which buckle in a zigzag pattern below the order-disorder transition temperature to reduce the surface energy. When a water molecule approached the Si surface, the O atom of the water molecule favored the down-buckled Si atom, and the H atom of the water molecule favored the up-buckled Si atom. This is explained by the attractions between the negatively charged O of the water and the positively charged down-buckled Si atom and between the positively charged H of the water and the negatively charged up-buckled Si atom. Following the adsorption of the first water molecule on the surface, a second water molecule adsorbed on either the inter-dimer or intra-dimer site of the Si dimer. The dipole-dipole interaction of the two adsorbed water molecules led to the formation of the water dimer, and the dissociation of the water molecules occurred easily below the order-disorder transition temperature. Therefore, the 1/2 monolayer of -OH on the water-terminated Si (001) surface shows a regular distribution. The results shed light on the atomic layer deposition process of alternate gate dielectric materials, such as $HfO_2$.

• Bulletin of the Korean Chemical Society
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• v.8 no.2
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• pp.88-96
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• 1987

The effects of initial vibrational energy on VV energy transfer in the collinear collision of two diatomic molecules, either homonuclear or heteronuclear, has been studied over a range of collision energies in classical mechanics. When initial vibrational energy is very large, only a small fraction of vibrational energy in the excited molecule is transferred to the colliding partner. In this case, the VV step is found to be strongly coupled with VT during the collision. At low collision energies, energy transfer in the homonuclear case of $O_2$+ $O_2$ with small initial vibrational energy is found to be very inefficient. In the heteronuclear case of CH + HC with the initial energy equivalent to one vibrational quantum, VV energy exchange is found to be very efficient at such energies. Between 0.3 and 0.5 ev, nearly all of vibrational energy of the excited molecule with one to about three vibrational quanta in CH + HC is efficiently transferred to the colliding partner through pure VV process in a sequence of down steps during the collision. The occurrence of multiple impacts during the collision of two heteronuclear molecules and the collisional bond dissociation of homonuclear molecules are also discussed.

• Journal of the Korean Chemical Society
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• v.41 no.9
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• pp.449-459
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• 1997

The bonded state polarizabilities of ions in the alkali halides are estimated by using the Seitz and Ruffa (SR) energy level analysis relation. The effective number of electrons $(N_{eff})$ in the Slater-Kirkwood formula are used for all members of an isoelectronic sequence. The effective dispersion coefficients $(C_6^{eff})$ are calculated by the use of the empirical formula (J. Chem. Phys. 1991, 95, 1852) estimating $(N_{eff})$ values to reproduce the experimental $(C_6^{eff})$ for atom-atom (or molecule) interactions. In the framework of the T-Rittner model the model potential is constructed and used to calculate the values of dissociation energy and dipole moment. The results obtained in the present study are in good agreement with the experiment one.