• Bulletin of the Korean Chemical Society
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• 제20권9호
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• pp.1045-1048
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• 1999

Electronic structures calculated based upon the extended Huckel tight-binding method for Ba1-xKxBiO3 with x = 0, 0.04, and 0.4 are reported. It is noticed that the commensurate ordering of Bi 3+ and Bi 5+ is responsible for the insulating and semiconducting behavior in BaBiO3 and Ba0.96K0.04BiO4. The band gaps of 3.2 eV and 1.4 eV for the former and the latter compounds, respectively, are consistent with the experimental results. Doping in Bi 6s-block band up to x = 0.4 causes the collapse of the ordering of Bi 3+ and Bi 5+, thereby resulting in the superconductivity in the Ba0.6K0.4BiO3 compound. Strikingly, the character of oxygen contributes to the conducting mechanism than that of the bismuth. This is quite different from the cuprate superconductors in which the character of copper dominates that of oxygen.

• Bulletin of the Korean Chemical Society
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• 제20권4호
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• pp.436-440
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• 1999

The highly resolved absorption spectra of mer-[Cr(dpt)(Gly-Gly)]ClO4·H2O [dpt = di(3-aminopropyl)amine, H2Gly-Gly = glycylglycine] have been measured between 13000 cm-1 and 50000 cm-1 temperatures down to 2 K. The vibrational intervals were extracted by recording emission and far-infrared spectra. The characteristic infrared bands in meridional isomer were discussed. The four-teen electronic origins due to spin-allowed and spin-forbidden transitions were assigned. With the use of this electronic transitions, a ligand field optimization based on the exact known ligand geometry have been performed to determine more detailed bonding properties of Gly-Gly and dpt ligands. It is confirmed that the peptide nitrogen of the Gly-Gly has a weak π-donor property toward chrornium(Ⅲ) ion.

• Bulletin of the Korean Chemical Society
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• 제22권5호
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• pp.455-462
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• 2001

The time-dependent tracking inversion method is studied to extract the potential energy surface of the electronic excited state in the photodissociation of triatomic molecules. Based on the relay of the regularized inversion procedure and time-dependent wave packet propagation, the algorithm extracts the underlying potential energy surface piece by piece by tracking the time-dependent data, which can be synthesized from Raman excitation profiles. We have demonstrated the algorithm to extract the potential energy surface of electronic excited state for NO2 molecule where the wave packet split on a saddle-shaped surface. Finally, we describe the merits of the time-dependent tracking inversion method compared with the time-independent inversion method and discussed several extensions of the algorithm.

• Bulletin of the Korean Chemical Society
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• 제17권5호
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• pp.461-463
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• 1996

The laser-induced fluorescence excitation spectrum of 7-amino-4-(trifluoromethyl)coumarin in a supersonic jet has been recorded in the 340-352 nm region. The electronic band origin was observed at 28622.8 cm-1. Vibrational assignments for the three fundamental low-frequency modes and eight combination bands have been made for the S1 electronic excited state. The out-of-plane vibrations of this molecule have been characterized from the low-frequency assignments of the spectrum. The periodic potential energy function for the CF3 torsion, which satisfactorily fits the observed data, were also determined to be V(Φ)=95X(1-cos3Φ)-32X(1-cos6Φ) where Φ is the torsional angle. The relatively low torsional barrier of 99 cm-1 in S1 state could be explained by the small steric interactions between the functional groups attached to a bicyclic ring.

• Bulletin of the Korean Chemical Society
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• 제10권6호
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• pp.495-500
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• 1989

The ionic conductivity of polycrystalline, glass, and glass-ceramic silicates was measured using two-terminal AC method with blocking electrode over a frequency range of 100 Hz to 100 KHz in the temperature range of $200^{\circ}C$ to $320^{\circ}C$. Analysing the capacitance (C), susceptance (B), impedance (Z), and conductance (G) under the given conditions, an equivalent circuit containing temperature and frequency dependent component is proposed. Higher capacitance could be observed in the low frequency region and on the improved ionic migration conditions i.e., at higher temperature in a better ionic conductor. Also the electrode polarization built up at the electrode-specimen interface could be sorted out above 10 KHz. However, grain boundary contribution couldn't be extracted from the bulk resistance over the frequency range measured here.

• Bulletin of the Korean Chemical Society
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• 제10권6호
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• pp.515-521
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• 1989

The molecular interaction of $W_2(NH_2)_4Cl_4$ fragment with chlorine ligands has been studied by means of extended Huckel calculations. We have extended the Huckel calculation to unknown edge-sharing $W_2(NH_2)_4Cl_4({\eta}-X)_2$ complexes (X = CO, H) in order to compare the stability of the complexes. The calculations showed that the size and electronic property of bridged ligand are important in determining the stability. The stabilities of the related metal-metal bonded edge-sharing complexes are discussed.

• Bulletin of the Korean Chemical Society
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• 제17권12호
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• pp.1112-1117
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• 1996

The electronic structures of twenty-seven isomers of a macrocyclic fulleropyrrolidine are investigated with semi-empirical extended Huckel (EH) molecular orbital method. The geometry of each isomer is determined by the molecular mechanics and dynamics methods based on UFF (universal force field) empirical force field. The calculated geometries, such as the carbon-carbon distances of the fullerene moiety, are in good agreement with those of related fullerene derivatives. The EH calculation shows that the formation of macrocyclic pyrrolidine ring on fullerene moiety results in the reduction of the HOMO-LUMO energy gap. From the graphical analysis of the DOS (density of states), PDOS (projected DOS), and MOOP (molecular orbital overlap population) curves, we can find that this reduction is due to splitting of the HOMO of fullerene moiety, which results from the symmetry-breaking and the distortion of the buckminsterfullerene framework from its ideal icosahedral structure.

• Bulletin of the Korean Chemical Society
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• 제17권12호
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• pp.1154-1157
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• 1996

The growth and electronic properties of ultrathin silver films deposited onto Pt(211) surface were studied using Auger electron spectroscopy (AES), low-energy electron diffraction (LEED), and x-ray photoelectron spectroscopy. The AES and LEED results indicate that the silver grows by a layer by layer growth followed by three dimensional islands growth. The XPS results show that the Ag 3d core-level binding energy of Ag overlayers on Pt(211) shifts toward lower binding energy relative to the bulk value at lower Ag coverage. This negative binding energy shift of the Ag 3d core level is explained by the reduced coordination number of the overlayer atoms and the resulting initial state band narrowing effect suggested by Wertheim and Citrin [Phys. Rev. Lett. 1978, 41, 1425].

• Bulletin of the Korean Chemical Society
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• 제21권12호
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• pp.1227-1232
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• 2000

Near the conical intersection for the 1,2 $^{2}A'$ states of $H_3$ the derivative coupling vector is calculated and analyzed on the plane of internal coordinates, (U,V) or its polar coordinates $(S{\theta})$, based on the squares of the internuclear distances. It is shown that in the vicinity of the conical intersection the derivative coupling vector behaves like ${\theta}/2S$, which is responsible for the sign changes of the real-valued electronic wave function when the nuclear configuration traverses a closed path enclosing a conical intersection. The analytic property of the wave functions is studied and especially the observation of the sign change in the configuration state function (CSF) coefficients of the real-valued electronic wave functions is demonstrated.

• Bulletin of the Korean Chemical Society
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• 제18권12호
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• pp.1296-1301
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• 1997

Polymerization of terminal alkynes (phenlacetylene and 4-ethynyltoluene) catalyzed by water soluble rhodium (Ⅰ) complex, RhCl(CO)(TPPTS)2 (TPPTS=m-P(C6H4SO3Na)3) (1) selectively produces cis-transoid polymers at room temperature in homogeneous solution of H2O and MeOH as well as in biphasic solutions of H2O and CHCl3. The rate of polymerization is higher in H2O/MeOH than in H2O/CHCl3. The iridium analog, IrCl(CO)(TPPTS)2 (2) shows catalytic activity for the polymerization of phenylacetylene only at elevated temperature to give trans-polymers. The polymerization rate increases significantly when the trimethylamine N-oxide (Me3NO) was added to the reaction mixtures. The electronic absorption spectra of the cis-transoid polymers show three absorption bands whereas the trasn-polymers show only one absorption band. It seems that the electronic absorption bands depend on the configuration of the polymers.