TORSIONAL POTENTIAL OF BIPHENYL : AB INITIO CALCULATIONS WITH THE DUNNING CORRELATION CONSISTED BASIS SETS
TORSIONAL POTENTIAL OF BIPHENYL : AB INITIO CALCULATIONS WITH THE DUNNING CORRELATION CONSISTED BASIS SETS
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联苯的扭转势：使用 Dunning 相关性组成的基组从头开始计算
DOI：
10.1063/1.477928
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发表时间：
1999
影响因子：
4.4
通讯作者：
K. Tanabe
中科院分区：
文献类型：
--
作者：
S. Tsuzuki;T. Uchimaru;K. Matsumura;M. Mikami;K. Tanabe
采用Dunning相关组成基集（最多可达cc-pVQZ， 960个基函数）和二阶Mo/ller-Plesset方法（MP2）进行电子相关校正，计算了联苯的内部旋转势垒高度。虽然先前的Hartree-Fock （HF）和MP2计算表明，内部旋转势阱高度在0°（ΔE0）处明显大于90°（ΔE90）处，但我们的MP2/cc-pVQZ//MP2/6- 31g *计算表明，ΔE0 （2.28 kcal/mol）接近ΔE90 (2.13 kcal/mol)，这与实验测量的估计一致。苯二聚体的计算表明，色散相互作用增加了共面构象的相对稳定性。以前计算中使用的基集不足以评价吸引色散相互作用。色散相互作用对共面构象稳定化作用的低估可能是上文中对ΔE0估计过高的原因之一。
The internal rotational barrier heights of biphenyl were calculated with the Dunning correlation consisted basis sets (up to cc-pVQZ, 960 basis functions) and the electron correlation correction by the second order Mo/ller-Plesset method (MP2). Although previous Hartree–Fock (HF) and MP2 calculations showed that the internal rotational barrier height at 0° (ΔE0) was substantially larger than that at 90° (ΔE90), our MP2/cc-pVQZ//MP2/6-31G* calculations showed that ΔE0 (2.28 kcal/mol) was close to ΔE90 (2.13 kcal/mol), which agreed with the estimation from experimental measurements. The calculations of benzene dimers suggested that the dispersion interaction increased the relative stability of the coplanar conformer. The basis sets employed in the previous calculations were not large enough to evaluate the attractive dispersion interaction. The underestimation of the stabilization of the coplanar conformer by the dispersion interaction would be one of the reasons for the overestimation of ΔE0 in the previou...