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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Frontier Orbital Consistent Quantum Gapping Potential (FOC-QCP) for Bulky Ligand of Transition Metal Complexes
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Frontier Orbital Consistent Quantum Gapping Potential (FOC-QCP) for Bulky Ligand of Transition Metal Complexes

机译：过渡金属配合物的大配体的前沿轨道一致量子缺口势（FOC-QCP）

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Chemically reasonable models of PR3 (R = Me,Et,~iPr,and ~iBu) were constructed to apply the post Hartree-Fock method to large transition metal complexes.In this model,R is replaced by the H atom including the frontier orbital consistent quantum capping potential (FOC-QCP) which reproduces the frontier orbital energy of PR3.The steric effect is incorporated by the new procedure named steric repulsion correction (SRC).To examine the performance of this FOC-QCP method with the SRC,the activation barriers and reaction energies of the reductive elimination reactions of C2H6 and H2 from M(R~1)2(PR~23)2 (M = Ni,Pd,or Pt;R~1 = Me for R~2 = Me,Et,or ~iPr,or R~1 = H for R2 = (Bu) were evaluated with the DFT[B3PW91],MP4(SDQ),and CCSD(T) methods.The FOC-QCP method reproduced well the DFT[B3PW91]- and MP4(SDQ)-calculated energy changes of the real complexes with PMe3.For more bulky phosphine,the SRC is important to present correct energy change,in which the MP2 method presents reliable steric repulsion correction like the CCSD-(T) method because the systems calculated in the SRC do not include a transition metal element.The monomerization energy of [RhCl(P'Pr3)2]2 and the coordination energies of CO,H2,N2,and C2H4 with [RhCl(P~t-Pr3)2]2 were theoretically calculated by the CCSD(T) method combined with the FOC-QCP and the SRC.The CCSD(T)-calculated energies agree well with the experimental ones,indicating the excellent performance of the combination of the FOC-QCP with the SRC.On the other hand,the DFT[B3PW9l]-calculated energies of the real complexes considerably deviate from the experimental ones.
机译：构建化学上合理的PR3模型（R = Me，Et，〜iPr和〜iBu），以将后Hartree-Fock方法应用于大型过渡金属配合物。在该模型中，R被包括原子轨道在内的H原子取代一致的量子封盖电势（FOC-QCP）可以再现PR3的前沿轨道能量。通过名为“空间排斥校正”（SRC）的新程序，可以合并空间效应。从M（R〜1）2（PR〜23）2（M = Ni，Pd或Pt; R〜1 = Me表示R〜2 = Me，C（H〜1）2（PR〜23）2）对C2H6和H2的还原消除反应的活化能垒和反应能用DFT [B3PW91]，MP4（SDQ）和CCSD（T）方法对R2 =（Bu）的Et或〜iPr或R〜1 = H进行了评估。FOC-QCP方法很好地再现了DFT [B3PW91] ]-和MP4（SDQ）计算的与PMe3的实际配合物的能量变化。对于更庞大的膦，SRC对于呈现正确的能量变化很重要，其中MP2方法可提供可靠的空间位阻由于SRC中计算的系统不包含过渡金属元素，因此像CCSD-（T）方法那样进行离子校正。[RhCl（P'Pr3）2] 2的单体化能和CO，H2，N2的配位能理论上通过CCSD（T）方法结合FOC-QCP和SRC计算出具有[RhCl（P〜t-Pr3）2] 2的C2H4。CCSD（T）计算的能量与实验值吻合得很好，另一方面，DFT [B3PW91]计算出的实际配合物的能量与实验值有很大的出入。

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