• Bulletin of the Korean Chemical Society
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• v.35 no.4
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• pp.1225-1228
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• 2014

• Journal of the Korean Ceramic Society
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• v.38 no.7
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• pp.678-682
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• 2001

복합 페롭스카이트(P $b_{1-x}$C $a_{x}$)(C $a_{1}$3/N $b_{2}$3/) $O_3$(0.6$\leq$x$\leq$0.8) 세라믹스의 마이크로파 유전특성과 결합원자가사이의 관계에 대하여 고찰하였다. 유전상수(K)는 Ca 치환량이 증가함에 따라 A-자리의 이온반경 세제곱에 비례하여 감소하며, Qf 값은 증가하였다. Ca 치환량이 증가함에 따라 관찰된 이온분극률($\alpha$$_{obs}$)과 이론적인 이온분극률($\alpha$$_{theo}$) 사이의 편차는 3.47%에서 6.37%로 증가하였다. 이는 A-자리 결합원자가의 감소에 따른 결합강도의 감소로 해석하였다. 소결시편의 공진주파수의 온도계수(TCF)는 AB $O_3$페롭스카이트 화합물의 A-자리 결합원자가에 의존하였다.

• The Journal of Natural Sciences
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• v.15 no.1
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• pp.47-56
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• 2005

The substituent dependence of geometric distortion through the two independent electronic substituent effects is analyzed for mono-substituted benzene derivatives of $C_{2v}$. Based on resonance structures, quantitative relationships expressing the resonance and field/inductive contribution terms in bond distortions are derived. The calculated field-effect parts of $C_{ipso}$_$C_{ortho}$ ring bonds increase and decrease compared to benzene for electropositive and electronegative substituents respectively. The nonbonded axial distance, $C_{ipso}$....$C_{para'}$ decreases for electronegative substituents and increases for electropositive substituents. As the electronegativity increases, the distance $C_{ortho}$....$C_{ortho'}$ increases. With the $\pi$-donors, $C_{meta}$....$C_{meta'}$ nonbonded distances are shorter compared to the ones of benzene, and for $\pi$-acceptors, the are longer. Our model based on valence bond approach predicts that the average bond length determined the area of ring, and the sum of the angles <$C_{ortho}$_$C_{ispo}$_$C_{ortho}$ and <$C_{meta}$_$C_{para}$_$C_{meta}$ determines the axial distance.

• Bulletin of the Korean Chemical Society
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• v.23 no.2
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• pp.253-261
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• 2002

Vibrational properties of ferrocyanide complex ion, $[Fe(CN)_6]^{4-}$ , have been studied based on the force constants obtained from the density functional calculations at B3LYP/$6-31G^{\ast\ast}$ level by means of the normal mode analysis using new bond angle and linear angle internal coordinates recently developed. Vibrations of ferrocyanide were manipulated by twenty-three symmetry force constants. The angled bending deformations of C-Fe-C, the linear bending deformations of Fe-C${\equiv}$N and the stretching vibrations of Fe-C have been quantitatively assigned to the calculated frequencies. The force constants in the internal coordinates employed in the modified Urey-Bradley type potential were evaluated on the density functional force field applied, and better interaction force constants in the internal coordinates have been proposed. The valence force constants in the general quadratic valence force field were also given. The stretch-stretch interaction and stretch-bending interaction constants are not sensitive to the geometrical displacement in the valence force field.

• YAKHAK HOEJI
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• v.38 no.1
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• pp.91-96
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• 1994

Irradiation of the berberinephenolbetaine [1] effected valence tautamerization to five 8,14-cycloberbine[21, which was converted to the spirobenzylisoquinolines by regioselective C-N bond cleavage A variety of ring systems such as compounds [4], [5] and [6] were introduced by the structural modification of berberinephenolbetaine.

• Bulletin of the Korean Chemical Society
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• v.14 no.1
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• pp.55-58
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• 1993

In order to determine the cobalt substituting site in $AlPO_4-5$ framework, ASED-MO theory has been used. The substitution of cobalt for aluminum is energetically more favorable than that for phasphorous. The stabilized energy of the former is 51 eV lower than that of the latter. The calculated net charge was +1.27 for Al, +0.85 for P, and +1.56 for Co, respectively. The valence electron population (VEP), reduced overlap population (ROP) and net charge for the charged cluster models were compared for $AlPO_4-5$ and $CoAlPO_4-5$ systems. Then, twe find that the covalency of P-O bond was greater than that of Al-O bond.

• Bulletin of the Korean Chemical Society
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• v.15 no.10
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• pp.857-860
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• 1994

We have calculated the ${\pi}$-electron density, atom self-polarizability, and free valence on each atom of N-(2-chlorobenzyl)-pyridinium, N-(benzyl)-2-chloropyridinium, and N-(2-chlorobenzyl)-2-chloropyridinium salts using a simple Huckel method in order to discuss their intramolecular photocyclization reaction in a qualitative method. Our calculation qualitatively predicts that photocyclization occurs through forming radicals as a reaction intermediate by breaking a C-Cl bond after photoexcitation into a triplet state via intersystem crossing from an initially excited singlet state. We noticed that this C-Cl bond breaking is aided by ${\pi}$-complex formation between a chlorine atom and the ${\pi}$ -electrons of the neighboring ring in the triplet state and a stronger ${\pi}$-complex bond makes C-Cl bond breaking, i.e., radical formation, much easier. A chlorine atom will form a stronger ${\pi}$ -complex bond to a benzyl ring of N-(benzyl)-2-chloropyridinium than a pyridinium ring of N-(2-chlorobenzyl)-pyridinium because the former can donate its ${\pi}$-electron more easily than the latter. The chlorine at position 15 of N-(2-chlorobenzyl)-2-chloropyridinium salt in the excited state also provides its ${\pi}$-electron to the benzyl ring. So this ${\pi}$-electron can increase the bond strength of the $\pi-complex.$ Therefore, the strength of ${\pi}$-complex follows the order of N-(2-chlorobenzyl)-2-chloropyridinium, N-(benzyl)-2-chloropyridinium, and N-(2-chlorobenzyl)-pyridinium salts and thus the radical formation rate. This provides us with an intramolecular photocyclization reaction rate of the same order as given above.

• Bulletin of the Korean Chemical Society
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• v.19 no.6
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• pp.654-660
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• 1998

$[Fe^{II}Fe^{III}BPLMP(OAc)_2](BPh_4)_2$ (1), a new model for the reduced form of the purple acid phosphatases, has been synthesized by using a dinucleating ligand, 2,6-bis[((2-pyridylmethyl)(6-methyl-2-pyridylmethyl)amino) methyl]-4-methylphenol (HBPLMP). Complex I has been characterized by X-ray diffraction method as having (μ-phenoxo)bis(acetato)diiron core. Complex 1 was crystallized in the monoclinic space group C2/c with the following cell parameters: a=41.620(6) Å, b=14.020(3) Å, c=27.007(4) Å, β=90.60(2)°, and Z=8. The iron centers in the complex 1 are ordered as indicated by the difference in the Fe-O bond lengths which match well with typical $Fe^{III}-O\; and\; Fe^{II}-O$ bond lengths. Complex 1 has been studied by electronic spectral, NMR, EPR, SQUID, and electochemical methods. Complex 1 exhibits strong bands at 592 nm, 1380 nm in $CH_3CN$ (ε = 1.0 × 103 , 3.0 × 102). These are assigned to $phenolate-to-Fe^{III}$ and intervalence charge-transfer transitions, respectively. Its NMR spectrum exhibits sharp isotropically shifted resonances, which number half of those expected for a valence-trapped species, indicating that electron transfer between $Fe^{II}\;and\;Fe^{III}$ centers is faster than NMR time scale. This complex undergoes quasireversible one-electron redox processes. The $Fe^{III}_2/Fe^{II}Fe^{III}\;and\;Fe^{II}Fe^{III}/Fe^{II}_2$ redox couples are at 0.655 and -0.085 V vs SCE, respectively. It has $K_{comp}=3.3{\times}10^{12}$ representing that BPLMP/bis(acetate) ligand combination stabilizes a mixed-valence $Fe^{II}Fe^{III}$ complex in the air. Complex 1 exhibits a broad EPR signal centered near g=1.55 which is a characteristic feature of the antiferromagnetically coupled high-spin $Fe^{II}Fe^{III}$ system $(S_{total}=1/2)$. This is consistent with the magnetic susceptibility study showing the weak antiferromagnetic coupling $(J= - 4.6\;cm^{-1},\; H= - 2JS_1{\cdot}S2)$ between $Fe^{II}\; and \;Fe^{III}$center.

• Journal of the Korean Chemical Society
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• v.23 no.4
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• pp.206-209
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• 1979

Empirical force-field calculations have been applied to eight 1,6-anhydropyra-noses, the crystal structures$^{13{\sim}21}$ of which have been studied by single crystal X-ray or neutron diffraction analysis. The theoretical calculations reproduce closely the variations in conformation between $^1C_4$ and $E_0$, which are observed in the pyranose rings. The smaller conformational differences in the five-membered anhydro ring are not so well predicted. The calculated C-C bond lengths agree with those observed within 0.012${\AA}$ with one exception. The C-O bond lengths show a larger deviation, 0.027${\AA}$. The non-hydrogen atom valence angles agree within 1.9$^{\circ}$.

• Proceedings of the Korean Vacuum Society Conference
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• 2000.02a
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• pp.144-144
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• 2000

이전에 수행된 연구에서 표면에 수직하게 dangling bond를 가지는 adatom으로 장식된 6H-SiC(0001) {{{{ SQRT { 3} }}}}$\times${{{{ SQRT { 3} }}}} 표면은 단일 전자 모형으로는 설명되어지지 않는 반도체적 성질을 가지는 것으로 보고되어졌다. 최근의 많은 이론적, 실험적 결과는 이 표면이 Mott-Hubbard 모형으로 설명되어질 수 있음이 보고되어졌다. 이 표면에서 Si이 좀 더 풍부한 3$\times$3 표면의 여러 모형들에 대해 이론적, 실험적 연구는 Energy적으로 E-J 모형이 가장 안정하다고 보고하였다. E-J모형은 표면에 수직인 dagling bond를 가지며 6H-SiC(0001) {{{{ SQRT { 3} }}}}$\times${{{{ SQRT { 3} }}}} 표면에 비해 1/3배의 밀도를 지닌다. 또한 최근의 연구에서 3$\times$3 표면 또한 단일 전자모형은 이 표면의 반도체적 성질에 위배되며 Mott-Hubbard 모형으로 설명되어질수 있음이 보고되어졌다. 이러한 표면 위에 알칼리금속인 Na을 흡착시키면서 일함수의 변화와 Valence Band의 변화를 측정하였다. XPS를 이용하여 Na이 흡착되면서 발생되는 Si과 C의 내각준위의 변화를 측정하였다. 6-SiC(0001) {{{{ SQRT { 3} }}}}$\times${{{{ SQRT { 3} }}}} 과 3$\times$3 표면 구조 모델을 Na을 흡착한 6H-SiC(0001) {{{{ SQRT { 3} }}}}$\times${{{{ SQRT { 3} }}}} 과 3$\times$3 표면으로부터 측정한 UPS, XPS data들로부터 지금까지 제기되어 있는 각 재배열 구조 모형들을 비교 검토하였다.