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首页> 外文期刊>The Journal of Chemical Physics >PROPERTIES OF PHOSPHORUS COMPOUNDS BY DENSITY FUNCTIONAL THEORY - CH3P SPECIES AS A TEST CASE
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PROPERTIES OF PHOSPHORUS COMPOUNDS BY DENSITY FUNCTIONAL THEORY - CH3P SPECIES AS A TEST CASE

机译：密度泛函理论研究磷化合物的性质-以CH3P物种为例。

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A comparison of different density functional theory (DFT) and molecular orbital (MO) methods for calculating molecular and energetic properties of low-coordinated phosphorus compounds is reported. While DFT methods include both Becke-Lee-Yang-Parr (BLYP and B3LYP) nonlocal functionals, MO methods involve second-order perturbation theory (MP2), quadratic configuration interaction [QCISD(T)], and coupled-cluster theory [CCSD(T)], in conjunction with the 6-31G(d,p), 6-311++G(3df,2p), and 6-311++G(3df,3pd) basis sets. Properties examined include geometrical parameters of the different CH3P equilibrium structures (phosphaethene, phosphinocarbene, methylphosphinidene, and a phosphacarbyne) and relevant transition structures for isomerisations and rearrangements in both the lowest-lying singlet and tripler states, vibrational wave numbers, relative energies, barrier heights, and singlet-triplet energy gaps. In addition, the heat of formation, ionization energy, and proton affinity of phosphaethene are also evaluated. Overall, the B3LYP method, when employed with a large basis set, yields energetic results comparable to the CCSD(T) results. Nevertheless, both DFT methods fail to predict the behavior of the addition/elimination reactions of the hydrogen atom in the triplet state. (C) 1996 American Institute of Physics. [References: 29]
机译：报告了不同密度泛函理论（DFT）和分子轨道（MO）方法用于计算低配位磷化合物的分子和能量性质的比较。 DFT方法同时包含Becke-Lee-Yang-Parr（BLYP和B3LYP）非局部函数，MO方法涉及二阶扰动理论（MP2），二次结构相互作用[QCISD（T）]和耦合簇理论[CCSD（ T）]，并结合6-31G（d，p），6-311 ++ G（3df，2p）和6-311 ++ G（3df，3pd）基集。检查的特性包括不同的CH3P平衡结构（磷乙烯，膦基卡宾，甲基次膦基和膦基卡宾）的几何参数，以及在最低单线态和三线态的异构化和重排的相关过渡结构，振动波数，相对能量，势垒高度，以及单重态-三重态能隙。此外，还评估了磷乙烯的形成热，电离能和质子亲和力。总体而言，B3LYP方法在具有较大基数的情况下使用时，所产生的能量结果可与CCSD（T）结果媲美。然而，两种DFT方法都不能预测三重态氢原子的加/消除反应的行为。 （C）1996年美国物理研究所。 [参考：29]

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