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
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DOI：
10.1016/0009-2614(96)00154-6
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发表时间：
1996-04-12
影响因子：
2.8
通讯作者：
Stephens, PJ
中科院分区：
文献类型：
--
作者：
Cheeseman, JR;Frisch, MJ;Stephens, PJ
首次将密度泛函理论（DFT）应用于原子轴向张量（AAT）的计算。采用解析导数方法和规范不变原子轨道（GIAOs）。采用[8 s6 p3 d/6s 3 p]基组和Becke 3-Lee-Yang-Parr杂化密度泛函，结合DFT谐波力场和原子极性张量（APTs）计算了反式-2，3 d（2）-环氧乙烷的DFT/GIAO AAT，得到的振动转动强度与实验结果比Hartree-Fock水平的计算结果更符合。理论和实验之间的最大剩余偏差归因于实验误差。
The first application of the density functional theory (DFT) to the calculation of atomic axial tensors (AATs) is reported. Analytical derivative methods and gauge-invariant atomic orbitals (GIAOs) are employed. DFT/GIAO AATs for trans-2,3 d(2)-oxirane calculated using a [8s6p3d/6s3p] basis set and the Becke 3-Lee-Yang-Parr hybrid density functional, in combination with a DFT harmonic force field and atomic polar tensors (APTs), yield vibrational rotational strengths in better agreement with experiment than comparable calculations at the Hartree-Fock level. The largest remaining deviations between theory and experiment are attributed to experimental error.