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Potential Energy Curves and Geometrical Structure Variations for [MX4]2- : M=Ni(II), Pd(II), Pt(II); X=Cl-, Br-) Dissociating into ([MX3]- + X-) : Ab Initio Study
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  • Potential Energy Curves and Geometrical Structure Variations for [MX4]2- : M=Ni(II), Pd(II), Pt(II); X=Cl-, Br-) Dissociating into ([MX3]- + X-) : Ab Initio Study
  • Potential Energy Curves and Geometrical Structure Variations for [MX4]2- : M=Ni(II), Pd(II), Pt(II); X=Cl-, Br-) Dissociating into ([MX3]- + X-) : Ab Initio Study
저자명
Park. Jong-Keun,Kim. Bong-Gon,Koo. In-Sun
간행물명
Bulletin of the Korean Chemical Society
권/호정보
2005년|26권 11호|pp.1795-1802 (8 pages)
발행정보
대한화학회
파일정보
정기간행물|ENG|
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이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
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기타언어초록

Potential energy curves and internuclear (M-X) distance variations for dissociation reactions of $[MX_4]^{2-}$ into ($[MX_3]^-$ + $X^-$) have been calculated using ab initio Hartree-Fock (HF), second order M$ddot{o}$ller-Plesset perturbation (MP2), and Density Functional Theory (DFT) methods with a triple zeta plus polarization (TZP) basis set. The equilibrium geometrical structures of $[MX_4]^{2-}$ are optimized to tetrahedral geometry for $[NiX_4]^{2-}$ and square planar geometry for ($[PdX_4]^{2-}$ and $[PtX_4]^{2-}$). The bond (M-X) distances of $[NiCl_4]^{2-}$, $[NiBr_4]^{2-}$, $[PdCl_4]^{2-}$, $[PdBr_4]^{2-}$, $[PtCl_4]^{2-}$, and $[PtBr_4]^{2-}$ at the DFT level are 2.258, 2.332, 2.351, 2.476, 2.367, and 2.493 $AA$, respectively. The dissociation energies for the bond dissociation of ($[MX_3]^-$${cdot}{cdot}{cdot}$$X^-$) at the DFT level are found to be 4.73 eV for $[NiCl_4]^{2-}$, 4.89 eV for $[NiBr_4]^{2-}$, 4.93 eV for $[PdCl_4]^{2-}$, 5.57 eV for $[PdBr_4]^{2-}$, 5.44 eV for $[PtCl_4]^{2-}$, and 5.87 eV for $[PtBr_4]^{2-}$. As the (M${cdot}{cdot}{cdot}$X) distance of ($[MX_3]^-$${cdot}{cdot}{cdot}$$X^-$) increases, the distance variation (Rt) of trans (M-X) bond at the trans-position is shorter than those (Rc) of two cis (M-X) bonds at the cisposition. Simultaneously the atomic charge variation of trans-X atom is more positive than those of equilibrium $[MX_4]^{2-}$ structures, while the variation of leaving X group is more positive.