Bond length alternation in cyclic polyenes. I. Restricted Hartree–Fock method
Bond length alternation in cyclic polyenes. I. Restricted Hartree–Fock method
复制标题
环状多烯中的键长交替 I. 受限 Hartree-Fock 方法。
DOI：
10.1002/qua.560240405
复制
发表时间：
1983
影响因子：
2.2
通讯作者：
E. Chin
中科院分区：
文献类型：
--
作者：
J. Paldus;E. Chin
使用不受限制的 Hartree-Fock 波函数，对不同自旋采用不同的空间轨道，研究了由 Pariser-Parr-Pople π 电子哈密顿量描述的环状多烯模型中的键长交替问题以及经验准谐波 σ 核势。结果表明，与有利于大环状多烯中键交替的限制性 Hartree-Fock 方法相比，非限制性 Hartree-Fock 方法通过等距核间分离稳定了对称结构。检查了对无限制 Hartree-Fock 过程恢复的相关误差量的评估，并从这个角度讨论了用受限制和无限制 Hartree-Fock 波函数描述时循环多烯模型的性质不同的行为。
The problem of bond length alternation in cyclic polyene models as described by the Pariser–Parr–Pople π-electron Hamiltonian, together with an empirical quasi harmonic σ-core potential is investigated using the unrestricted Hartree–Fock wave function employing different spatial orbitals for different spins. It is shown that in contrast to the restricted Hartree–Fock method, which favors bond alternation in large cyclic polyenes, the unrestricted Hartree–Fock method stabilizes the symmetric structures with equidistant internuclear separation. An assessment of the amount of correlation error recovered by the unrestricted Hartree–Fock procedure is examined and the qualitatively different behavior of the cyclic polyene models when described by restricted and unrestricted Hartree–Fock wave functions is discussed from this viewpoint.