• Bulletin of the Korean Chemical Society
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• 제19권12호
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• pp.1363-1368
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• 1998

Mo/γ-Al2O3 catalysts were prepared by impregnation method in various conditions to identify the states of surface Mo species. TPR (Temperature-Programmed Reduction) and Raman spectroscopy were applied to analyze the surface Mo species. TPR analysis revealed that MoO3 was reduced to Mo through MoO2, the intermediate state and the increase of Mo loading enhanced the reducibility of Mo oxide till the formation of monolayer coverage. High temperature calcination induced oxygen defects in MoO3 giving their unstable states for easier reduction. Raman spectroscopy analysis showed that the increase of Mo loading induced the polymeric Mo oxide.

• Bulletin of the Korean Chemical Society
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• 제12권5호
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• pp.544-554
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• 1991

Using the Huckel method, we obtain the analytical expressions for eigenvalues and eigenvectors of s.c., f.c.c. and b.c.c. clusters of rectangular parallelepiped shape, and of an arbitrary size. Our formula converage to those derived from the Bloch sum, in the limit of infinite extension. DOS and LDOS reveal that the major contribution of the states near Fermi level originates from the surface atoms, also symmetry of DOS curves disappears by the introduction of 2nd nearest neighbor interactions, in all the cubic lattices. An accumulation of the negative charges on surface of cluster is observed.

• 한국전기전자재료학회논문지
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• 제15권7호
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• pp.570-575
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• 2002

$SrBi_2Ta_2O_9$ thin films were etched in $Cl_2/CF_4/Ar$ inductively coupled plasma (ICP). The maximum etch rate was 1300 ${\AA}/min$ at 900 W ICP power in Cl$_2$(20%)/$CF_4$(20%)/Ar(60%). As RF source power increased, radicals (F, Cl) and ion ($Ar^+$) increased. The influence of plasma induced damage during etching process was investigated in terms of P-E hysteresis loops, chemical states on the surface, surface morphology and phase of X-ray diffraction. The chemical states on the etched surface were investigated with X-ray spectroscopy and secondary ion mass spectrometry. After annealing $700^{\circ}C$ for 1 h in $O_2$ atmosphere, the decreased P-E hysteresises of the etched SBT thin films in Ar and $Cl_2/CF_4/Ar$ plasma were recovered.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2002년도 추계학술대회 논문집 Vol.15
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• pp.236-239
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• 2002

Surface states of silicone polymer treated by plasma were investigated by the analysis by x-ray photoelectron spectroscopy (XPS) and surface voltage decay. Plasma treatment causes the silica-like oxidative layer, which is confirmed with XPS, and lowers surface resistivity with increasing the plasma treatment time. Using the decay time constant of surface voltage, the calculated surface resistivity was compared with the value directly measured by a voltage-current method. A good agreement between two methods was obtained. In addition, we estimated the thermal activation energy for surface conduction, Based on our results, we could understand the relationship between surface chemical states and surface electrical properties.

• Bulletin of the Korean Chemical Society
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• 제16권11호
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• pp.1019-1023
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• 1995

A light-emitting silicon material was prepared by electrochemical etching of n-Si single crystal wafers in a solution of hydrofluoric acid and ethanol. Visible photoluminescence from the silicon was inhomogeneous and decayed rapidly in the ambient laboratory conditions or with photoirradiation. Substantial improvements in photoluminescence which include little-dependent luminescence peak energy with excitation energy variation and longer-lasting room temperature visible photoluminescence were achieved when the surface of photoluminescent silicon material was derivatized with the surface modifier of octadecylmercaptan. Surface modification of the photoluminescent silicon was evidenced by the measurements of contact angles of static water drops, FT-IR spectra and XPS data, in addition to changed photoluminescence. Similar improvements in photoluminescence were observed with the light-emitting silicon treated with dodecylmercaptan, but not with octadecane. The present results indicate that sulfurs of octadecylmercaptans or dodecylmercaptans appear to coordinate the surface Si atoms of LESi and perturb the surface states to significantly change the luminescent characteristics of LESi.

• Bulletin of the Korean Chemical Society
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• 제25권8호
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• pp.1217-1224
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• 2004

We have calculated the probability of HBr formation and energy disposal of the reaction exothermicity in HBr produced from the reaction of gas-phase bromine with highly covered chemisorbed hydrogen atoms on a Si (001)-(2 ${\times}$1) surface. The reaction probability is about 0.20 at gas temperature 1500 K and surface temperature 300 K. Raising the initial vibrational state of the adsorbate(H)-surface(Si) bond from the ground to v = 1, 2 and 3 states causes the vibrational, translational and rotational energies of the product HBr to increase equally. However, the vibrational and translational motions of product HBr share most of the reaction energy. Vibrational population of the HBr molecules produced from the ground state adsorbate-surface bond ($v_{HSi}$ =0) follows the Boltzmann distribution, but it deviates seriously from the Boltzmann distribution when the initial vibrational energy of the adsorbate-surface bond increases. When the vibration of the adsorbate-surface bond is in the ground state, the amount of energy dissipated into the surface is negative, while it becomes positive as vHSi increases. The energy distributions among the various modes weakly depends on surface temperature in the range of 0-600 K, regardless of the initial vibrational state of H(ad)-Si(s) bond.

• Bulletin of the Korean Chemical Society
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• 제16권2호
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• pp.157-163
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• 1995

The adsorption and decomposition of NO on a stepped Pt(111) surface have been studied using thermal desorption spectroscopy and Auger electron spectroscopy. NO adsorbs molecularly in two different states of the terrace and the step, which are distinguishable in thermal desorption spectra. NO dissociates via a bent species at the step sites on the basis of vibrational spectrum data reported previously. The dissociation of NO is an activation process : the activation energy is estimated to be about 2 kcal/mol. Increase in the NO dissociation with adsorption temperature is explained by a process controlled by diffusion of the dissociated atomic nitrogen from the step to the terrace of the surface. In addition to NO and N2, the desorption peak of N2O is observed. We conclude that the formation of N2O is attributed to surface reaction of NO and N adsorbed on the surface.

• Bulletin of the Korean Chemical Society
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• 제30권12호
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• pp.2973-2978
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• 2009

The decomposition reaction mechanism of $CH_3CF_2O$ radical formed from hydroflurocarbon, $CH_3CHF_2$ (HFC-152a) in the atmosphere has been investigated using ab-initio quantum mechanical methods. The geometries of the reactant, products and transition states involved in the decomposition pathways have been optimized and characterized at DFT-B3LYP and MP2 levels of theories using 6-311++G(d,p) basis set. Calculations have been carried out to observe the effect of basis sets on the optimized geometries of species involved. Single point energy calculations have been performed at QCISD(T) and CCSD(T) level of theories. Out of the two prominent decomposition channels considered viz., C-C bond scission and F-elimination, C-C bond scission is found to be the dominant path involving a barrier height of 12.3 kcal/mol whereas the F-elimination path involves that of a 28.0 kcal/mol. Using transition-state theory, rate constant for the most dominant decomposition pathway viz., C-C bond scission is calculated at 298 K and found to be 1.3 ${\times}$ 10$^4s{-1}$. Transition states are searched on the potential energy surfaces involving both decomposition channels and each of the transition states are characterized. The existence of transition states on the corresponding potential energy surface are ascertained by performing Intrinsic Reaction Coordinate (IRC) calculation.

• Bulletin of the Korean Chemical Society
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• 제12권2호
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• pp.143-148
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• 1991

In the unhydrated and hydrated states, conformational free energies of L-ascorbic acid anion (AAA) were computed with an empirical potential function and the hydration shell model (a program CONBIO). The conformational energy was minimized from possible starting conformations expressed with five torsion angles of the molecule. The conformational entropy of each low energy conformation in both states was computed using a harmonic approximation. As found in L-ascorbic acid (AA), intramolecular hydrogen bonds (HBs) are proved to be of significant importance in stabilizing the overall conformations of AAA in both states, and give the folded conformations, which are quite different from those in crystal. There are competitions between HBs and hydration around O3 atom of the lactone ring and hydroxyls of the acyclic side chain. Especially, the whole conformation of AAA is strongly dependent on the water-accessibility of O3 atom. Though there is a significant effect of the hydration on conformational surface, the lowest energy conformation of the unhydrated AAA is conserved. The different patterns of HBs and hydration result in the conformations of AAA in both states being different from those of AA. It can be drawn by several feasible conformations obtained in the hydrated state that there exists an ensemble of several conformations in aqueous solution.

• Bulletin of the Korean Chemical Society
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• 제16권6호
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• pp.547-552
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• 1995

As an extension to the Kramers' restricted Hartree-Fock (KRHF) method [J. Comp. Chem., 13, 595 (1992)], we have implemented the Kramers' restricted configuration interaction (KRCI) program in order to calculate excited states as well as the ground state of polyatomic molecules containing heavy atoms. This KRCI is based on determinants composed of the two-component molecular spinors which are generated from KRHF calculations. The Hamiltonian employed in the KRHF and KRCI methods contains most of all the important relativistic effects including spin-orbit terms through the use of relativistic effective core potentials (REP). The present program which is limited to a small configuration space has been tested for a few atoms and molecules. Excitation energies of the group 14 and 16 elements calculated using the present KRCI program are in good accordance with the spectroscopic data. Calculated excitation energies for many Rydberg states of K and Cs indicate that spin-orbit terms in the REP, which are derived for the ground state, are also reliable for the description of highly excited states. The electronic states of the polyatomic molecule CH3I are probed from the molecular region to the dissociation limit. Test calculations demonstrate that the present KRCI is a useful method for the description of potential energy surface of polyatomic molecules containing heavy atoms.