Polarized Molecular Orbital Model Chemistry 3. The PMO Method Extended to Organic Chemistry
Polarized Molecular Orbital Model Chemistry 3. The PMO Method Extended to Organic Chemistry
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DOI：
10.1021/ct300509d
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发表时间：
2013-01-01
影响因子：
5.5
通讯作者：
Truhlar, Donald G.
中科院分区：
文献类型：
--
作者：
Isegawa, Miho;Fiedler, Luke;Truhlar, Donald G.
极化分子轨道（PMO）方法，一种忽略双原子微分重叠（NDDO）的半经验分子轨道方法，以前被参数化为由O和H组成的系统，这里扩展到碳。利用遗传算法和包含静电和能态的数据库，对PMO哈密顿量中的所有参数进行了优化；新的参数集称为PMO2。所得到的预测质量与以前的NDDO半经验分子轨道方法得到的结果进行了比较，包括和排除色散项。我们还将PMO2的性质与SCC-DFTB计算结果进行了比较。在半经验分子轨道方法中，PMO2方法在极化率、原子化能、质子转移能、非共价络合能和化学反应势垒高度等方面被发现是特别准确的，并且在包括偶极矩、部分原子电荷和分子几何形状在内的一系列其他性质方面具有良好的全面准确性。
The polarized molecular orbital (PMO) method, a neglect-of-diatomic-differential-overlap (NDDO) semiempirical molecular orbital method previously parametrized for systems composed of O and H, is here extended to carbon. We modified the formalism and optimized all the parameters in the PMO Hamiltonian by using a genetic algorithm and a database containing both electrostatic and energetic properties; the new parameter set is called PMO2. The quality of the resulting predictions is compared to results obtained by previous NDDO semiempirical molecular orbital methods, both including and excluding dispersion terms. We also compare the PMO2 properties to SCC-DFTB calculations. Within the class of semiempirical molecular orbital methods, the PMO2 method is found to be especially accurate for polarizabilities, atomization energies, proton transfer energies, noncovalent complexation energies, and chemical reaction barrier heights and to have good across-the-board accuracy for a range of other properties, including dipole moments, partial atomic charges, and molecular geometries.