ELECTRONEGATIVITY EQUALIZATION METHOD FOR THE CALCULATION OF ATOMIC CHARGES IN MOLECULES
ELECTRONEGATIVITY EQUALIZATION METHOD FOR THE CALCULATION OF ATOMIC CHARGES IN MOLECULES
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DOI：
10.1021/ja00275a013
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发表时间：
1986-07-23
影响因子：
15
通讯作者：
SHANKAR, S
中科院分区：
文献类型：
--
作者：
MORTIER, WJ;GHOSH, SK;SHANKAR, S
本文根据电负性均衡原理，发展了一种计算分子中原子电荷的形式，它与分子的连接性和几何形状有关。分子中原子的有效电负性等于分子电负性，由等式34给出，其中n和分别是中性原子电负性和硬度，qa和qg是原子a和qb上的电荷，并且R1是核间距离。参数n和n是对由于成键而产生的中性原子电负性和硬度的修正。在密度泛函理论的框架内提供了上述配方的理论依据。并且是通过小分子计算校准而获得的，并且是可转移的并且一致地可用于计算任何分子中的电荷。通过计算几个小分子和大分子中的原子电荷，包括丙氨酸二肽和核糖，这是生物学上的重要性的形式主义进行测试。本文还研究了相互作用分子即水二聚体中的原子电荷，电负性均衡原理导致了计算分子中原子电荷的形式主义的发展，它依赖于分子的几何形状和连接性。[1]这种形式主义在霍恩伯格和科恩定理中有严格的理论基础，[2]通过将分子密度划分为类似原子的密度，调用了分子中原子的概念。帕尔等人3已经证明，任何化学物质的电负性4都是负的
On the basis of the principle of electronegativity equalization, a formalism has been developed for the calculation of atomic charges in molecules which are connectivity and geometry dependent. The effective electronegativity of an atom in a molecule, which is equal to the molecular electronegativity, is given by eq 34where „and are the neutral atom electronegativity andhardness, respectively, qa and qg are the charges on atoms a and ß, and R^ is the internuclear distance. The parameters „and are the corrections to the neutral atom electronegativity and hardness that arise as a consequence of bonding. A theoretical justification for the above formulation is provided within the framework of density functional theory. and are obtained by calibrating through small-molecule calculations and are transferable and consistently usable for calculating charges in any molecule. The formalism is tested through calculation of atomic charges in several small and large molecules including alanine dipeptide and riboses which are of biological importance. Atomic charges in interacting molecules viz. water dimers are also studied.The principleof electronegativity equalization has led tothe development of a formalism for the calculation of atomic charges in molecules which are geometry and connectivity dependent. 1 This formalism, which has a rigorous theoretical basis in the Hohenberg and Kohn theorem, 2 invokes the concept of an atom in a molecule through partitioning of the molecular density into atomic-like densities. Parr et al. 3 have shown that the electronegativity,, of any chemical species4 is nothing but the negative