• Bulletin of the Korean Chemical Society
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• v.34 no.8
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• pp.2281-2285
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• 2013

The electronic structure, optical spectra, and thermodynamic properties of the three FOX-7 polymorphs (${\alpha}$, ${\beta}$, and ${\gamma}$) have been studied systematically using density functional theory. The LDA (CA-PZ) and generalized gradient approximation (GGA) (PW91) functions were used to relax the three FOX-7 phases without any constraint. Their density of states and partial density of states were calculated and analyzed. The band gaps for the three phases were calculated and the sequence of their sensitivity was presented. Their absorption coefficients were computed and compared. The thermodynamic functions including enthalpy (H), entropy (S), free energy (G), and heat capacity ($C_p$) for the three phases were evaluated.

• Bulletin of the Korean Chemical Society
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• v.18 no.1
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• pp.23-27
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• 1997

The luminescence and excitation spectra of [Cr(trans-diammac)](ClO4)3 (trans-diammac=trans-6, 3-dimethyl-l, 4, 8, 11-tetraazacyclotetradecane-6, 13-diamine) taken at 77 K are reported. The mid and far-infrared spectra at room-temperature are also measured between 4000 cm-1and 50 cm-1. In the excitation spectrum the 2Eg components are splitted by 102 cm-1. Using the observed electronic transitions, a ligand field analysis was performed to determine more detailed bonding properties of the coordinated atoms toward chromium(Ⅲ). According to the results, we can confirm that the six nitrogen atoms have a strong σ-donor character, and the trans-diammac secondary amine has a greater value of eσ than does the primary amine.

• Bulletin of the Korean Chemical Society
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• v.14 no.1
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• pp.118-122
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• 1993

The 77 K luminescence and excitation spectra, room-temperature FT-infrared and visible absorption spectra of a newly prepared complex cis-[Cr(cyclam)(pn)]$(ClO_4)_3$, where cyclam and pn represent 1,4,8,11-tetraazacyclotetradecane and 1,2-propanediamine respectively, have been measured. Absorption maximum of the first spin-allowed transition in the electronic absorption spectra of cis-[Cr(cyclam)(pn)]$^{3+}$ and cis-[Cr(cyclam)(en)]$^{3+}$ appears at nearly the same position. The two spin-allowed and six spin-forbidden electronic transitions are assigned from the visible absorption and excitation spectra. It is also shown that the zero phonon line in the excitation spectrum splits into two components by 50 cm$^{-1}$.

• Bulletin of the Korean Chemical Society
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• v.14 no.1
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• pp.132-137
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• 1993

The electronic structure of two dimensional layered compound, FeOCl, is studied with the band model and the cluster model approximation employing Extended-Huckel (EH) method. We examine the effects of intercalation (e.g., localization of transferred electron, conductivity increase). FeOCl has the electronic structure typical for layered compounds as expected. For FeOCl-$Li_{1/2}$ system, the charge transfer from Li to the FeOCl lattice occurs, and electrons are built up almost exclusively on Fe atoms. The partially filled band of FeOCl-$Li_{1/2}$ complex is responsible for the increase in conductivity.

• Bulletin of the Korean Chemical Society
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• v.19 no.1
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• pp.5-21
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• 1998

The purpose of this paper is to show that X-ray absorption spectroscopy (XANES and EXAFS) is a powerful technique for characterizing both crystalline and amorphous solids from structural (local order) and electronic point of view. The principle of this technique is briefly described by showing the main factors which must be considered for recording and fitting the experimental results. Some non-trivial examples have been selected for demonstrating that XAS spectroscopy is the only technique for bringing a definitive answer as for example: the determination of the local distortion of the $NiO_6$ octahedra in the $Li_{1-z}Ni_{1+z}O_2$ layered oxides and the evidence of the presence of copper pairs in the NASICON-type phosphate $CuZr_2 (PO_4)_3$. Are also reported some significant examples for which XAS spectroscopy is decisive with other characterization methods as (i) Raman spectroscopy for glasses (ii) Mossbauer spectroscopy for $LiNi_{1+z-t}Fe_To_2$ oxides (iii) magnetic measurements for Ce-based intermetallic compounds.

• Bulletin of the Korean Chemical Society
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• v.21 no.1
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• pp.9-22
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• 2000

Optical-optical double resonance experiments have been used to identify and characterize five ion-pair states and several of the bound and repulsive valence states of ClF. This report provides a description of these experiments for $^{35}CIF$ and $^{37}CIF$, and a summary of the current knowledge of the valence and ion-pair states. The important role of perturbations among the rovibronic levels of the bound valence states and their utilization in the double resonance technique is discussed. The ion-pair states of the same symmetry, ${\Omega}$=$0^+$ (E and f) and 1( $\beta$ and G) interact very strongly and the spectroscopy of these states is anomalous and, hence, interesting. Comparison is made to some recent ab initio calculations for ClF. One possible explanation of the irregular vibrational energy levels and rotational constants of the ion-pair states of $O^+$ and 1 symmetry is a crossing of the diabatic potentials of these states. Some currently unresolved questions about ClF spectroscopy are posed for future work. Where appropriate, analogy is made between the electronic states of ClF and the corresponding valence and ion-pair states of $Cl_2.$.

• Bulletin of the Korean Chemical Society
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• v.20 no.1
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• pp.81-84
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• 1999

The emission and excitation spectra of [Cr(NH3)5(imH)](ClO4)3·H2O (imH=imidazole) taken at 77 K are reported. The 298 K visible and far-infrared spectra are also measured. The vibrational intervals of the electronic ground state are extracted from the far-infrared and emission spectra. The ten electronic bands due to spin-allowed and spin-forbidden transitions are assigned. Using the observed transitions, a ligand field analysis has been performed to determine the bonding properties of coordinated imidazole in the title chromium(Ⅲ) complex. It is confirmed that nitrogen atom of the imidazole ligand has a medium it-acceptor property toward chromium(Ⅲ) ion. The zero-phonon line in the excitation spectrum splits into two components by 181 cm-1, and the large 2Eg splitting can be reproduced by the ligand field theory.

• Bulletin of the Korean Chemical Society
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• v.14 no.6
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• pp.740-743
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• 1993

By considering both electron-electron and electron-lattice interactions, the effect of charge transfer on the bond structure and electronic states of $C_{60}$ is studied without configuration limitation. The results show that the electron-electron interaction does not eliminate the layer structure of the bond distortion and the self-trapping of transferred electrons. For charged ${C_{60}}^{2-}$, there exist two localized electronic states, which possess laminar wave functions, and four nonequivalent groups of carbon atoms, which induce a fine-structure in the NMR spectrum line.

• Bulletin of the Korean Chemical Society
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• v.15 no.9
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• pp.762-765
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• 1994

Picosecond time-resolved resonance Raman spectroscopy has been used to study the photochemistry of Cr(CO$)_6$ in cyclohexane following photoexcitation at 266 nm. Photodissociative loss of CO is found to occur within our pulse width of ${\leq}$5 ps by probing the 533 c$m^{-1}$ vibrational mode of ground state Cr(CO$)_6$. The subsequent dynamics after photodissociation are interpreted in terms of solvation, vibrational and electronic relaxations. The vibrational relaxation time of 100 ps and 83 ps are observed by monitoring v=O and v=l of the 381 c$m^{-1}$ transient mode, respectively. No evidence was found for solvation and electronic relaxation occurring on a time scale of ${\leq}$5 ps.

• Bulletin of the Korean Chemical Society
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• v.16 no.11
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• pp.1015-1019
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• 1995

The electronic structures and properties of the neutral and multiply charged C60n ions (n=2+ to 6-) with spin states have been investigated by semi-empirical MNDO calculations. In the ground state, C601- has the lowest total energy and the highest binding energy. The neutral C60 ion is supposed to have a high ionization potential and a high electron affinity. The HOMO and LUMO positions are lower in the cationic C60 than in the anionic C60. The LUMO energy becomes increasingly positive from C601- to C606- and the HOMO energy becomes increasingly negative from C602+ to C60. The HOMO-LUMO gap of the neutral C60 ion is higher than that of the multiply charged C60 ions. From the HOMO-LUMO gap, it seems reasonable to expect that electrons of the multiply charged C60 ions will be more polarizable than those of the neutral C60 ion. The HOMO and LUMO energies increase as the negative charge increases.