Self‐Consistent Molecular‐Orbital Methods. VII. Convergence of Gaussian Expansions of Slater‐Type Atomic Orbitals in Calculations of First‐ and Second‐Order Properties
Self‐Consistent Molecular‐Orbital Methods. VII. Convergence of Gaussian Expansions of Slater‐Type Atomic Orbitals in Calculations of First‐ and Second‐Order Properties
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计算一阶和二阶性质时斯莱特型原子轨道的自洽分子轨道方法。
DOI：
10.1063/1.1674036
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发表时间：
1970
影响因子：
4.4
通讯作者：
J. Pople
中科院分区：
文献类型：
--
作者：
R. Ditchfield;D. Miller;J. Pople
斯莱特型原子轨道通过高斯型轨道之和的最小二乘表示用于一阶和二阶性质的自洽分子轨道计算。四极矩和电场梯度被认为是一阶性质的例子。抗磁磁化率，磁屏蔽常数，电极化，和核自旋耦合常数使用有限微扰理论计算。结果表明，除了核自旋耦合常数，结果迅速收敛（随着高斯展开尺寸的增加）到适合于纯斯莱特型轨道的值。计算结果与实验数据的比较将在未来的出版物。
Least‐squares representations of Slater‐type atomic orbitals by a sum of Gaussian‐type orbitals are used in self‐consistent molecular‐orbital calculations of first‐ and second‐order properties. Quadrupole moments and electric field gradients are considered as examples of first‐order properties. Diamagnetic susceptibilities, magnetic shielding constants, electrical polarizabilities, and nuclear spin coupling constants are calculated using finite perturbation theory. It is shown that, except for nuclear spin coupling constants, the results converge rapidly (with increasing size of Gaussian expansion) to the values appropriate for pure Slater‐type orbitals. A comparison of calculated results with experimental data will be made in a future publication.