• Title/Summary/Keyword: $d_{z^2}$-orbital

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전이금속 불순물(W)에 의한 GaSe의 전자구조 및 자성 변화

  • Park, Eun-Won
    • Proceeding of EDISON Challenge
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    • 2017.03a
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    • pp.433-436
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    • 2017
  • SIESTA를 이용하여 GaSe 단일층에서 금속 원자(Ga)를 전이금속 원자(W)로 치환하였을 때($W_{Ga}$)의 구조 deformation, 에너지 안정성, 전자구조와 자성을 확인하였다. 그 결과, 구조가 바뀌면서 평면에 수직한 방향으로 구조 변형이 나타났고, $W_{Ga}$에서 W의 NN는 Se이 되었다. Clean surface만큼 $W_{Ga}$도 안정된 구조임을 알 수 있었다. $W_{Ga}$에서 W에 의한 defect states가 up, down 6개씩 split되어 나타났으며, ${\Gamma}$ point에서 degenerated 경향을 보였다. 또한 W에 의한 magnetic moment는 $1{\mu}_B$인 것을 확인하였다. Defect states는 degenerated $d_{yz}$, $d_{zx}$ orbital character, degenerated $d_{xy}$, $dx^2-y^2$ orbital character, defect states는 $d_z{^2}$ orbital character을 띠는 것으로 나뉘었고, 이에 따라 에너지가 함께 높아졌다.

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Study on Electronic Structures and Properties in High $T_c\;YBa_2Cu_O_{7-x}\;and\;YBa_2Cu_4O_8$ Superconductors (고온 초전도체 YBa$_2 Cu_3O_{7-x}$와 YBa$_2Cu_4O_8$의 전자구조와 성질에 관한 연구)

  • Son Man-Shick;Ha Hyun-Shick;Paek U-Hyon;Lee Kee-Hag
    • Journal of the Korean Chemical Society
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    • v.35 no.4
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    • pp.316-323
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    • 1991
  • We calculated a difference between the YBa$_2Cu _3O_{7-x}$ superconductor (123 system) of critical temperature, 95 K and the YBa$_2Cu_4 O_8$ superconductors (124 system) of critical temperature, 80 K in Y-system superconductors using Extended Huckel Theory (EHT). The valence electron population (VEP), reduced overlap population (ROP) and net charge for the charged cluster models relating to the layer and the chain in 123 and 124 systems were compared. The VEPs of Cu atom in the layer of 123 and 124 systems populated d$_{z^2}$ orbital more than d$_{x^2-y^2}$ orbital, and in the chain of 123 and 124 systems populated d$_{y^2-z^2}$ orbital more than d$_{z^2}$ orbital. The ROP of the Cu(1)-O(1) in the layer of 123 system was larger than the value of the Cu(1)-O(2), but the ROP of the Cu(1)-O(2) in the layer of 124 system was larger than the value of the Cu(1)-O(1). The ROP of Cu(2)-O(4) in the chain of 123 and 124 systems were larger than the value of the Cu(2)-O(3). In 123 system the net charge values of the Cu in the layer was larger than the value of the Cu in the chain. However, in 124 system the net charge value of the Cu in the chain was larger than the value in the layer.

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Molecular Orbital Anaysis of Water Activation on TiO2(110) Surface (TiO2(110) 표면에 흡착된 물분자의 결합 활성화에 관한 MO 연구)

  • Kang, Dae-Bok;
    • Journal of the Korean Chemical Society
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    • v.46 no.3
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    • pp.179-186
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    • 2002
  • A molecular orbital analysis based on the extended Huckel calculations has been carried out to study the OH bond activation of water on the $TiO_2$(110) surface. $H_2O$ binds with its axis perpendicular to the surfac on top of the five-coordinate $Ti^{4+}$ atom via its $3a_1$ orbital. In this bonding situation, the two-coordinated bridging $O^{2-}$ atom ($O_b$, basic site) on $TiO_2$(110) is too distant from an H atom of water to form hydrogen-bondig interactions with water that facilitate O-H bond cleavage. It has been elucidated that the O-H bond is appreciably weakened when the water molecule is tilted to give a hydrogen bond with the $O_b$ atom. This mechanism includes mutual transfer of electron density from the $3a_1$ orbital of the water molecule to the $Ti^{4+} 3d_{z2}$ orbital and from the $O_b$ P orbitals to the $2b_1$ of the adsorbed water molecule This should result in lengthening of the O-H bond in the surface complex and the subsequent dissociation into the fragments OH and H.

Electronic Structure and Properties of High-Tc Superconductor Y-Ba-Cu-O. 1. Oxygen-deficiency in the $YBa_2Cu_3O_x $Superconductor ($6{\leq}{\times}{\leq}7$)

  • U-Hyon Paek;U-Sung Choi;Kee-Hag Lee;Chang-Hong Kim
    • Bulletin of the Korean Chemical Society
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    • v.10 no.6
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    • pp.504-509
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    • 1989
  • The effect of oxygen-deficiency on the charge distributions and orbital energies for small copper oxide clusters representing the superconducting materials $YBa_2Cu_3O_x (6{\leq}x{\leq}7)$ were investigated by the extended Huckel molecular orbital (EHMO) method with the tight-binding model. Our calculations show +3 oxidation state of Cu(1) in the $CuO_3$ chain and +2 or +1 of Cu(2) in the $CuO_2$ layers for $YBa_2Cu_3O_7$ with the nominal charge of $Cu_3$ = +7 (or +5), while for $YBa_2Cu_3O_6$ +1 oxidation state of Cu(1) and +3 (or +2) of Cu(2) in the $CuO_2$ layers with the nominal charge of $Cu_3$ = +7 (or +5). For $Cu_3O_{12}$ cluster representing $YBa_2Cu_3O_7$ with the nominal charge of $Cu_3$ = +7 the Cu(2) $d_{{x^2}-{y^2}}$ orbitals in the $CuO_2$ layers is a typical Jahn-Teller $d^9$ system with the partial hole and the Cu(1) $d_{{_z2}-{_y2}}$ orbital in the $CuO_3$ chain contains hole occupancy. For $Cu_3O_{10}$ cluster representing $YBa_2Cu_3O_6$ with the nominal charge of Cu = +5 the orbital character of the highest partially occupied MO (HPOMO) and the lowest completely unoccupied MO (LCUMO) of $Cu_3O_{12}$ representing $YBa_2Cu_3O_7$ with the nominal charge of $Cu_3$ = +7 is reversed, and the character of Cu(1) $d{{x^2}-{y^2}}$ orbital of LCUMO of the $Cu_3O_{12} $cluster is vanished. It is suggested that the local crystal field environment of Cu(1) by the oxygens in the Cu(1) chain may play a vital role in conductivity and superconductivity, either alone or through cooperative electronic coupling with the Cu(2) layers in $YBa_2Cu_3O_7.$.

Synthesis and Characterization of 1,4-Diimine Complexes of 1,2,3,4,5-Pentamethylcyclopentadienylrhodium and iridium

  • Paek, Cheol-Ki;Ko, Jae-Jung;Uhm, Jae-Kook
    • Bulletin of the Korean Chemical Society
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    • v.15 no.11
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    • pp.980-984
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    • 1994
  • Monomeric rhodium and iridium diimine complexes $Cp^*M(HNRNH)(Cp^*$ = 1,2,3,4,5-pentamethylcyclopentadienyl : (M=lr; R=o-$C_6H_4 (1a), 4,5-(CH_3)_2-C_6H_2-1,2 (1b), 4,5-(Cl)_2-C_6H_2-1,2$ (1c), NCC=CCN-1,2 (1d): M=Rh; R=NCC=CCN-1,2 (1e)) have been synthesized from $[CP^*MCl_2]_2$ and 2 equiv. of diamine in the presence of $NEt_3$. The Crystal structure of 1a was determined by X-ray diffraction method : 1a was crystallized in the monoclinic system, space group $P2_{1/c}$, with lattice constants a=9.543 (1) ${\AA}$, b=16.286 (1) ${\AA}$, c=10.068 (1) ${\AA}$ and ${\beta}$=99.25 (1), with Z= 4. Least-squares refinement of the structure led to R factor of 0.049. The coordination sphere of rhodium and iridium can be described as a 2-legged piano-stool. All complexes are highly colored. Electrochemical studies show that 1d and 1e display quasi-reversible reduction and 1a-1c display irreversible reductions, suggesting that the acceptor orbital might be localized on the diimine ring.

Determination of Absolute Coordinates of Cadastral Satellite Station using Gipsy-Oasis II (Gipsy-Oasis II를 이용한 지적위성기준점의 절대 좌표 결정)

  • Song, Dong Seob;Yun, Hong Sic
    • KSCE Journal of Civil and Environmental Engineering Research
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    • v.26 no.2D
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    • pp.317-324
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    • 2006
  • This study deals with the precise GPS data processing refer to ITRF2000 through the calculation of absolute coordinates of cadastral satellite station which were established by purpose of cadastral surveying. We used the Gipsy-Oasis II software developed Jet Propulsion Laboratory to estimate daily position of GPS stations with orbital and atmospheric parameters. Especially, we carried out ionospheric delay, tropospheric delay, data existence whether or not and quality control check of observation data during pre-processing. The standard deviation of absolute coordinates was determined better than ${\pm}4mm$ from GPS precise analysis. The RMSE of difference between the result of this study and existing result by using Bernese s/w shows ${\Delta}X={\pm}0.079m$, ${\Delta}Y={\pm}0.019m$ and ${\Delta}Z={\pm}0.031m$.

Synthesis and Spectroscopic Characterization of Manganese(II), Iron(III) and Cobalt(III) Complexes of Macrocyclic Ligand. Potential of Cobalt(III) Complex in Biological Activity

  • El-Tabl, Abdou S.;Shakdofa, Mohamad M.E.;El-Seidy, Ahmed M.A.
    • Journal of the Korean Chemical Society
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    • v.55 no.6
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    • pp.919-925
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    • 2011
  • A new series of manganese(II), iron(III) and cobalt(III) complexes of 14-membered macrocyclic ligand, (3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane-1,8-diamine) have been prepared and characterized by elemental analyses, IR, UV-VIS, $^1H$- and $^{13}C$- NMR spectra, magnetic susceptibilities, conductivities, and ESR measurements. Molar conductance measurements in DMF solution indicate that the complexes are electrolytes. The ESR spectrum for cobalt(III) complex in $CD_3OD+10%D_2O$ after exposure to $^{60}Co-{\gamma}$-rays at 77 K using a 0.2217 M rad $h^{-1}$ vicrad source showed $g_{\perp}$ > $g_{\parallel}$ > $g_e$, indicating that, the unpaired electron site is mainly present in the $d_z2$ orbital with covalent bond character. In this case, the ligand hyperfine tensors are nearly collinear with ${\gamma}$-tensors, so there is no major tendency to bend. Therefore, little extra delocalization via the ring lobe of the $dz^2$ orbital occurs. However, the ESR spectrum in solid state after exposure to $^{60}Co-{\gamma}$-rays at 77 K showed $g_{\parallel}$ > $g_{\perp}$ > $g_e$, indicating that, the unpaired electron site is mainly present in the $d_x2_{-y}2$ ground state as the resulting spectrum contains a large number of randomly oriented molecules provided that, the principle directions of g and A tensors. Manganese (II) complex 2, $[H_{12}LMn]Cl_4.2H_2O$, showed six isotropic lines characteristic to an unpaired electron interacting with a nucleus of spin 5/2, however, iron(III) complex 3, $[H_{12}LFe]Cl_5.H_2O$, showed spectrum of a high spin $^{57}Fe$ (I=1/2), $d^5$ configuration. The geometry of these complexes was supported by elemental analyses, IR, electronic and ESR spectral studies. Complex 1 showed exploitation in reducing the amount of electron adducts formed in DNA during irradiation with low radiation products.

THE BIMA PROJECT: O-C DIAGRAMS OF ECLIPSING BINARY SYSTEMS

  • HAANS, G.K.;RAMADHAN, D.G.;AKHYAR, S.;AZALIAH, R.;SUHERLI, J.;IRAWATI, P.;SAROTSAKULCHAI, T.;ARIFIN, Z.M.;RICHICHI, A.;MALASAN, H.L.;SOONTHORNTHUM, B.
    • Publications of The Korean Astronomical Society
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    • v.30 no.2
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    • pp.205-209
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    • 2015
  • The Eclipsing Binaries Minima (BIMA) Monitoring Project is a CCD-based photometric observational program initiated by Bosscha Observatory - Lembang, Indonesia in June 2012. Since December 2012 the National Astronomical Research Institute of Thailand (NARIT) has joined the BIMA Project as the main partner. This project aims to build an open-database of eclipsing binary minima and to establish the orbital period of each system and its variations. The project is conducted on the basis of multisite monitoring observations of eclipsing binaries with magnitudes less than 19 mag. Differential photometry methods have been applied throughout the observations. Data reduction was performed using IRAF. The observations were carried out in BVRI bands using three different small telescopes situated in Indonesia, Thailand, and Chile. Computer programs have been developed for calculating the time of minima. To date, more than 140 eclipsing binaries have been observed. From them 71 minima have been determined. We present and discuss the O-C diagrams for some eclipsing binary systems.