Charge distribution in Mn(salen) complexes

The charge and spin distribution in manganese‐salen complexes were analyzed using different basis sets and density functionals. Five population analysis methods [Mulliken, Löwdin, Natural population analysis (NPA), atoms in molecules (AIM), and CHelpG] were used to characterize the charge distribution. Results show that NPA and AIM were the only methods capable of giving charges with the correct sign for all cases under study. According to the analysis of the natural charge and spin distributions, the salen ligand shows a complex behavior, counteracting the effect of the chloro and oxo ligands on the metal center. Furthermore, the presence of a chloride counter ion increases the oxo‐radical character of Oxo‐Mn(salen) complexes, which may play an important role in the rationalization of the catalytic properties of Mn(salen) complexes. © 2014 Wiley Periodicals, Inc.     

Theoretical Study of Electron Transfer in Bimolecular System of NH3 and H2O

1 INTRODUCTION Electron transfer is one of the most important reactions in chemistry. This fundamental reaction plays a crucial role in a myriad of processes including acid-base neutralization, electrophilic addition, and a score of enzymatic reactions. Ab initio molecular orbital methods are capable of providing information that can complement experimental data and circumvent solvent effects. The bimolecular system of NH_3 and H_2O has been extensively studied. Kollman et al.[1] report…     

Charge distribution in the water molecule--a comparison of methods

The charge distribution in the water molecule has been analyzed using a broad variety of basis sets, four different quantum mechanical methods (Hartree-Fock, Becke3LYP, MP2, and QCISD), and six population analysis methods (Mulliken, NPA, AIM, CHELPG, Merz-Kollman, and Resp). The influence of the molecular structure on the calculated atomic charges has been studied using small perturbations of the experimentally determined structure.     

Generalized charge sensitivity analysis

Charge sensitivity analysis was originally introduced in the trivial-atom resolution. Here, we extend this resolution into force-field atoms. The AMBERff99 force-field resolution was employed. The effective electronegativities and hardnesses were derived for five different population analyses (Mulliken, Hirschfeld, AIM, NPA and Voronoi charges) by applying evolutionary algorithms.     

DNA碱基的电子相关效应

分别在Hartree-Fock和二级Moller-Plesset微扰理论MP2的电子相关校正水平, 用6-31G^*^*基函数对四种DNA碱基胞嘧啶、胸腺嘧啶、鸟嘌呤和腺嘌呤的能量、偶极矩、电荷分布和分子静电势等性质进行了系统的从头计算研究。其中, 采用Z矢量方法在波函数中加入MP2级别的电子相关校正; 分别用Mulliken布居分析、静电势导出电荷CHELPG以及自然布居分析NPA方法计算分子中原子电荷。在上述计算结果的基础上, 系统地分析了DNA碱基的电子相关效应。     

Voronoi deformation density (VDD) charges: Assessment of the Mulliken, Bader, Hirshfeld, Weinhold, and VDD methods for charge analysis

We present the Voronoi Deformation Density (VDD) method for computing atomic charges. The VDD method does not explicitly use the basis functions but calculates the amount of electronic density that flows to or from a certain atom due to bond formation by spatial integration of the deformation density over the atomic Voronoi cell. We compare our method to the well-known Mulliken, Hirshfeld, Bader, and Weinhold [Natural Population Analysis (NPA)] charges for a variety of biological, organic, and inorganic molecules. The Mulliken charges are (again) shown to be useless due to heavy basis set dependency, and the Bader charges (and often also the NPA charges) are not realistic, yielding too extreme values that suggest much ionic character even in the case of covalent bonds. The Hirshfeld and VDD charges, which prove to be numerically very similar, are to be recommended because they yield chemically meaningful charges. We stress the need to use spatial integration over an atomic domain to get rid of basis set dependency, and the need to integrate the deformation density in order to obtain a realistic picture of the charge rearrangement upon bonding. An asset of the VDD charges is the transparency of the approach owing to the simple geometric partitioning of space. The deformation density based charges prove to conform to chemical experience.     

原子电荷计算方法的对比

原子电荷是对化学体系中电荷分布最简单、最直观的描述形式之一,在理论和实际应用中都有重要意义.本文介绍了12种重要的原子电荷计算方法的原理和特点,通过大量实例从不同角度比较了它们的优缺点.这些方法包括Mulliken、分子环境中的原子轨道(AOIM)、Hirshfeld、原子偶极矩校正的Hirshfeld布居(ADCH)、自然布居分析(NPA)、Merz-Kollmann(MK)、分子中的原子(AIM)、Merck分子力场94(MMFF94)、AM1-BCC、Gasteiger、电荷模型2(CM2)以及电荷均衡(QEq)方法.最后本文对如何在实际应用中选择合适的计算方法给出了建议.     

Atomic properties of N(2)O(4) based on its experimental charge density

Nitrogen dioxide, being known to exist as a dimer N2O4 in the crystal with a very long N-N bond length of 1.76 A, was crystallized at low-temperature conditions on a diffractometer. High-resolution X-ray data (sin(theta/lambda) = 1.249 A-1) were recorded with a CCD area detector to allow the generation of an experimental charge density distribution. By making use of Bader's AIM theory, zero-flux surfaces were calculated, and we examined atomic volumes and atomic charges obtained from this experiment and various theoretical calculations. Four commonly used methods of computing atomic charges (Mulliken, AIM, NPA, and CHELP) were considered. The AIM charges are rather independent from the used basis set. Interestingly, the evaluated atomic volumes are very similar between experiment and theory, although in theory isolated molecules are considered. For the long N-N bond a bond order n of approximately 0.5 was derived from a comparison with appropriate model compounds.     

Charge distributions of phosphorylcholine and its derivatives

Hartree–Fock self-consistent field calculations on the 3-21G(*) level of approximation have been performed to phosphorylcholine and its derivatives in a geometry close to an X-ray structure of an antibody/antigen complex. Wave functions have been analyzed using different methods for derivation of atomic charges used as Coulomb charges in empirical force fields for molecular dynamics simulations. Among the three applied methods—Mulliken population analysis, natural population analysis, and electrostatical fit—the natural population analysis seems to give best results for these molecules.     

On the charge distribution in ethanes and disilanes and correlations with equilibrium bond lengths; an ab initio study

The equilibrium electronic wave-functions for a series of fluoro- and chloro-ethanes and disilanes of general formula M₂H_6−nX_n, (M=C, Si; X=F, Cl), were analysed by the most commonly used methods for electron distribution, using the Mulliken and Löwdin populations, natural atomic orbital (NAO) populations and atoms in molecules (AIM) electron densities. Although the numerical values for local atomic charges vary greatly, all the methods correlate, but in markedly differing ways. The Mulliken charges seem the most selective in relation to systematic change of substituents in the current type of molecular structure. A number of examples occur where the AIM charges at C, Si centres are effectively identical in different molecules, where some differences might have been anticipated. These are often distinguished by Mulliken populations. The fluoroethanes exemplify this, since a plot of the AIM charges (for example on either the F or H centres) against the Mulliken charges for all members of the series, shows three nearly parallel lines, corresponding to those centres with 0, 1 or 2 fluorine atoms on the centre under study. The bond critical points at which the AIM charges are determined seem to be counter to intuition in some cases. This is a density rather than atomic orbital size issue however. The Mulliken and NAO charges seem more reasonable than those from the AIM method. There is an unexpected correlation of the local bond dipoles from the Mulliken analyses, with the calculated equilibrium bond lengths. These correlations lead to bond length values for the non-polarised bonds MX, which agree with data based on covalent radii for some bonds.     

Rapid Estimation of Basis Set Error and Correlation Energy Based on Mulliken Charges and Mulliken Matrix with the Small 6-31g* Basis Set

Good, density functional quality (B3LYP/6-31G*) ground state total electronic energies have been approximated using single point Hartree–Fock-self consistent field (HF-SCF/6-31G*) total energies and Mulliken partial charges versus. Mulliken matrix (electrons assigned to atoms and atoms pairs from Mulliken population analysis). This is a development of our rapid estimation of basis set error and correlation energy from partial charges (REBECEP) method, published earlier (see references [21,22,30]. The development is as follows: (1) A larger set of atoms (H, C, N, O, F, Si, P and S) are considered as building blocks for closed shell, neutral, ground state molecules at their equlibrium geometry; (2) geometries near equilibrium geometry are also considered; (3) A larger set, containing 115 molecules, was used to fit REBECEP parameters; (4) most importantly, electrons belonging to chemical bonds (between atom pairs) are also considered (Mulliken matrix) in addition to the atoms (Mulliken charges), using more REBECEP parameters to fit and yielding a more flexible algorithm. With these parameters a rather accurate closed shell ground state electronic total energy can be obtained from a small basis set HF-SCF calculation in the vicinity of optimal geometry. The 3.3 kcal/mol root mean square deviation of REBECEP improves to 1.5 kcal/mol when using Mulliken matrix instead of Mulliken charges.     

Charge calculations in molecular mechanics. V. Silicon compounds and π bonding

A previously published scheme for the calculation of partial atomic charges has been extended to include silicon, and has been parameterized for a range of Si? X bonds (X?C,H,O,F,Cl,Br). For the silicon–halogen and silicon–oxygen bonds, a comparison is made between charges calculated with and without the inclusion of π-bonding. An extensive data set consisting of experimental geometries and dipole moments for the silicon compounds considered is presented and this leads to the selection of standard Si? X bond lengths. The calculated dipole moments for the above compounds are in good agreement with those obtained experimentally only when the π charges are included. A comparison has also been made between the partial charges from this scheme and those obtained from computational methods using the Mulliken population analysis. There is considerable disagreement between the methods. Finally, the implications of the charges and structural data are considered in terms of application to zeolite systems.     

An ab initio study of crystal field effects,part 3: Solid- and gas-phase geometry of formamide,modeling the changes in a peptide group due to hydrogen bonds

A model of the solid state of formamide is constructed by optimizing a central molecule in an electrostatic field of the proper symmetry. Attention is paid to the way the electrostatic charges are obtained. Point charges obtained from a Mulliken population analysis yield a final set of atomic charges in the central molecule that agree reasonably well with those obtained experimentally after ak-refinement of formamide. Point charges from a so-called stockholder partitioning agree slightly less. Furthermore, the simple crystal field adaptation of standard ab initio methods reproduces within experimental limits the differences in C=O and C-N lengths, observed between the gas-phase and the solid state geometry. Again, a Mulliken field agrees slightly better than a stockholder field, but the difference in performance is statistically insignificant. In a survey of 221 high-quality single-crystal x-ray determinations of compounds containing the peptide group N-C=O, we found evidence supporting quantitatively the conclusion that the increase of C=O and the decrease of C-N bond length in the gas-to-solid transition is dominated by the effects of hydrogen bonding. It was shown that the C=O bond lengthens by about 0.011 å per H-bond it accepts, while the N-C bond diminishes by about 0.015 å per H-bond it donates.Part 2, see Ref. [5].     

Representation of molecules by atomic charges: A new population analysis

For the calculation of atomic charges in molecules, a new fast procedure based on extended Mulliken population analysis is presented. The reliability of the new population analysis is tested within the AM1 approximation and the results are compared in detail with those obtained by different methods reported in the literature.     

氧在CuCl(111)表面吸附的密度泛函理论研究

运用广义梯度密度泛函理论的PW91方法结合周期平板模型,在DNP基组下研究了氧分子和氧原子在CuCl(111)表面上的吸附.对氧分子在CuCl(111)表面吸附的相关计算和比较发现,覆盖度为0.25单层时的吸附构型为稳定的吸附构型,氧分子倾斜地吸附在CuCl(111)表面的顶位时比较稳定,吸附后O2分子的伸缩振动频率与自由O2分子相比发生了红移.态密度和Mulliken电荷布居分析结果表明,整个吸附体系发生了由Cu原子向O2分子的电荷转移.氧原子在CuCl(111)表面吸附的计算结果表明,氧原子倾向于以穴位(hollow)吸附在CuCl(111)表面,通过Mulliken电荷布居和态密度分析对氧原子在CuCl表面的吸附行为作了进一步探讨.     

Charge distributions in polyacetylene chains containing a positively charged defect

We present a comparative study of the AIM, CHELPG, GAPT, MK, Mulliken, NPA, and RESP charge distributions associated with a positively charged soliton on increasingly large trans‐polyacetylene chains, at HF, MP2, and DFT levels of theory. The charge storage in the soliton‐bearing systems is explored in detail, including charge magnitude, charge separation, charge alternation, and chain length effects. The grouping of the charge distributions at a given level of theory, as well as the sensitivity of a given charge distribution to the inclusion of electron correlation in its computation, are investigated using similarity analysis. Several of the charge definitions have been applied for the first time for charged soliton‐bearing systems, and there are substantial differences between the charge distributions for the charged and neutral systems. Thus, AIM charges are no longer one of the largest charge values, the AIM charges can be in counterphase with other definitions, and the GAPT charges for neutral systems are quite different from the GAPT charges for charged systems, e.g., the magnitudes of the GAPT charges are anomalously large and increase with the size of the charged system. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005