• Bulletin of the Korean Chemical Society
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• 제20권8호
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• pp.943-947
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• 1999

Ligand field analyses for tris(biuret)chromium(III) chloride and hexaureachromium(III) bromide were performed and compared to understand the ligand field properties of both ligands. The optimized eσO and eπO values indicate that coordinated oxygen atom in biuret ligand is a moderate s- and strong p-donor, while that in urea ligand is a weak σ- and moderate π-donor. The electronic structures of those two complexes are quite different and they were well accounted by inclusion of an anisotropic p bonding.

• Bulletin of the Korean Chemical Society
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• 제16권11호
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• pp.1043-1045
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• 1995

The overtone of the ν2 vibrational mode in Cr(CO)6 are observed for the first time in cyclohexane and methanol at both the 266 and 213 nm excitations. The appearance of the overtones due to the displacement of the electronic excited state with respect to the ground state along the ν2 vibrational mode is interpreted in terms of wavepacket concept and molecular orbital (MO) theory. Our Raman results suggest a new interpretation for the excited state potential.

• Bulletin of the Korean Chemical Society
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• 제10권6호
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• pp.554-559
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• 1989

The electronic structure, conformational preferences, and rotational barriers have been studied for transition metal indenyl allyl complexes by means of extended Huckel calculations. After geometrical optimization the exo conformation of allyl moiety is favored over the endo. The rotational barrier of indenyl ring in (Indenyl)Mo(CO)_2(Allyl)$ is computed to be 3.8 kcal/mol. Population analysis is applied to account for the conformational preferences and rotational barriers. A series of substituted allyl complexes has been also optimized. It shows steric hindrance plays a crucial role in setting the allyl orientation.

• Bulletin of the Korean Chemical Society
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• 제19권5호
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• pp.575-579
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• 1998

The 77 K luminescence and excitation spectra, and 298 K infrared and absorption spectra of $cis-{\Alpha}-[Cr(trien)Cl_2]Cl{\cdot}H_2O$ (trien=triethylenetetramine) have been measured. Ligand field electronic transitions due to spin-allowed and spin-forbidden are assigned. The zero-phonon line in the excitation spectrum splits into two components by $198\; cm^{-1}$, and the large $^2E_g$ splitting can be reproduced by the modern ligand field theory. It is confirmed that nitrogen atoms of the trien ligand have a strong σ-donor character, but chloride ligand has weak σ- and π -donor properties toward chromium(III) ion.

• Bulletin of the Korean Chemical Society
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• 제16권7호
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• pp.574-577
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• 1995

Solvatochromic effect and hydrogen bonding interaction of NPNOH, NPNO- and NPNOR were investigated. Electronic transition energies of the dyes were plotted against empirical solvent polarity parameters, Taft's π* and Reichardt's ET(30). Good correlations were observed when the excitation energies were plotted against the energy calculated by multiple linear regression method which was developed by Taft. There is an intrinsic difference between betaine for ET(30) polarity scale and the azoderivative, which is derived from the specific hydrogen bond incurred with probe molecules and solvents. The hydrogen bonding plays a very important role for stabilization of an excited state molecule by solvents especially when a solute possesses a negative charge as with NPNO-.

• Bulletin of the Korean Chemical Society
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• 제12권2호
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• pp.211-213
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• 1991

The ground state of the oxygen molecule is calculated by various methods of coupled cluster approaches and many body perturbation theory using a double zeta plus polarization basis set and the UHF reference state. All the methods employed are capable of describing the oxygen molecule near the equilibrium bond length and the separated atom, but do not correctly depict the breaking of the multiple bond. For this basis set, including more correlations does not necessarily improve the agreement with experiment for molecular properties such as bond lengths and dissociation energies.

• Bulletin of the Korean Chemical Society
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• 제7권3호
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• pp.218-224
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• 1986

The electronic structures of silane and chlorosilanes are studied by the SCF calculations using effective core potentials (ECP's). The results obtained with ECP's are in good agreement with corresponding all electron calculations demonstrating the reliability of ECP employed. The importance of polarization functions for the second row atoms is also evident in this study. The SCF calculations of silane and chlorosilanes are useful in qualitative understanding of many chemical properties since many trends are correctly obtained with the polarization functions included in basis sets of reasonable size.

• Bulletin of the Korean Chemical Society
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• 제14권2호
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• pp.238-243
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• 1993

A self-consistent-field Green's matrix method for the calculation of electronic properties of chemisorbed system is devised and applied to the methanol on copper(110) surface. The method is based on CNDO Hartree-Fock approximation. Contour integration in the complex energy plane is used for an efficient calculation of the charge-density bond-order matrix. The information on each fragment prior to chemisorption is efficiently used and a small number of iterations are needed to reach the self-consistency. The changes of density of states and other quantities of methanol due to chemisorption are consistent with reported experimental results.

• Bulletin of the Korean Chemical Society
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• 제11권3호
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• pp.248-250
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• 1990

Dichloro and ethylenediamine rhodium(III) complexes of a flexible $N_2O_2$-type tetradentate ligand, ethylenediamine-N,N'-di- -butyric acid(eddb), have been prepared. Both s-cis- and uns-cis geometrical isomers have been yielded in the $[Rh(eddb)Cl_2]-\;and\;[Rh(eddb)(en)]^+$ complexes. Ir, pmr, and electronic absorption spectra are used to characterize the complexes obtained in this work.

• Bulletin of the Korean Chemical Society
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• 제9권5호
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• pp.311-317
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• 1988

The surface-enhanced Raman scattering(SERS) of methoxybenzonitrile in a silver sol was investigated. All of ortho-, meta-, and para-substituted benzonitriles were found to adsorb on the silver surface via the nitrogen lone pair electrons. The benzene ring of meta derivative seemed likely to stand perpendicular to the silver surface, while the benzene rings of both otho and para derivatives assumed tilted stances with respect to the surface. The SERS technique appeared to be a useful means to study the substituent electronic effects.