Ab initio calculation of atomic axial tensors and vibrational rotational strengths using density functional theory
Ab initio calculation of atomic axial tensors and vibrational rotational strengths using density functional theory
复制标题
DOI：
10.1080/00268979609482495
复制
发表时间：
1996-04
影响因子：
1.7
通讯作者：
P. Stephens;C. S. Ashvar;F. Devlin;J. Cheeseman;M. Frisch
中科院分区：
文献类型：
--
作者：
P. Stephens;C. S. Ashvar;F. Devlin;J. Cheeseman;M. Frisch
我们记录了一种新的密度泛函理论（DFT）方法，使用直接分析导数方法和规范不变原子轨道（GIAO）基组从头计算原子轴张量（AAT）。 AAT 是针对环氧乙烷计算的。使用 AAT 求和规则以及实验电偶极矩和顺磁化率张量来评估其准确性。针对手性分子 6,8-二氧杂双环[3.2.1]辛烷计算的 AAT 与 DFT 谐波力场和原子极张量相结合，用于预测振动旋转强度和振动圆二色性 (VCD) 光谱。通过与实验旋转强度和 VCD 谱进行比较来评估其准确性。探讨了计算结果对密度泛函和基组的依赖性。将 DFT 计算与并行执行的 SCF (Hartree-Fock) 计算进行比较。
We document a new density functional theory (DFT) methodology for the ab initio calculation of atomic axial tensors (AATs) using direct, analytical derivative methods and gauge-invariant atomic orbital (GIAO) basis sets. AATs are calculated for ethylene oxide. Their accuracy is assessed using AAT sum rules and the experimental electric dipole moment and paramagnetic susceptibility tensor. AATs calculated for the chiral molecule 6,8-dioxabicyclo[3.2.1]octane, in combination with DFT harmonic force fields and atomic polar tensors, are used to predict vibrational rotational strengths and vibrational circular dichroism (VCD) spectra. Their accuracy is assessed by comparison with the experimental rotational strengths and VCD spectrum.The dependence of calculated results on density functional and basis set is explored. The DFT calculations are compared to SCF (Hartree-Fock) calculations carried out in parallel.