Electronegativity Methods

For nonmolecular solids, called coordinated polymers, he substitutes the Madelung part of the lattice energy 

Heats or Atomization (kcal mol ) of Monofluorides by Sanderson s Method  

Fluoride Partial charges on each atom Calculated Experimental Difference 

The validity of the method was rechecked with data from Herzberg s recent compilation on gaseous diatomics 121) (Table XI). Calculated heats of solid halides are in better agreement with experimental values. In some molecules the use of more than one value of fluorine bond energy is required to reproduce experimental heats. Thus PF5 or AsFj require two fully weakened values and three unweakened values, which is sensible on chemical and structural grounds. 

The method has been confined to main-group compounds presumably because of irregularities expected with unsjnnmetrical charge distributions in transition metal ions. The noble gas compounds remain outside the scope of the method because of the way in which electronegativity is defined (atom compactness relative to interpolated noble atom compactness). The main weakness of the method when applied to fluorides is in the somewhat arbitrary choice of fluorine bond energies. 

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No, K. T., J. A. Grant, M. S. Jhon, and H. A. Scheraga. 1990. Determination of Net Atomic Charges Using a Modified Partial Equalization of Orbital Electronegativity Method 2. Application to Ionic and Aromatic Molecules as Models for Polypeptides. J. Phys. Chem. 94, 4740-4746. 

M It should be noted that inasmuch as the ionization energy of most atoms is an order of magnitude larger than the electron affinity, electronegativity methods which are fundamentally related only lo ionization energies are still successful. 

Determination of Net Ionic Charges Using a Modified Partial Equalization of Orbital Electronegativity Method. 1. Application to Neutral Molecules as Models for Polypeptides. 

Bratsch, S.G. (1985). A Group Electronegativity Method with Pauling Units. J.Chem.Educ., 62, 101-103. 

No, K.T., Grant, J.A., Jhon, M.S. and Scheraga, H.A. (1990a) Determination of net atomic charges using a modified partial equalization of orbital electronegativity method. 2. Application to ionic and aromatic molecules as models for polypeptides. /. Phys. Chem., 94, 4740-4746. 

However, arriving at the moment of comparison with another STO density non-related electronegativity method, we mention the recent work of Ghosh Biswas (2002). In that work using the STO electronic representation it was derived the atomic radii scales trough the equation ... 

TABLE 4.16 Atomic Radii Scales as Computed From Related Electronegativity Methods, within the Slater (STO) Electronic Density Picture (Putz, 2012c)... 

FIGURE 4.30 The plots as local representation (upper draws) and linear regressions like global representation (lower draws) for the atomic radii scales abstracted from Slater electronic density picture, both in related and non-related electronegativity methods, as indicated in the brackets < > referred to the Table 4.16 after Putz et al. (2003,2012b,c). 

Bratsch SG (1985) A group electronegativity method with Pauling units. J Chem Educat 62 101-103... 

Batsanov SS (1964) Calculating the degree of bond ionicity in complex ions by electronegativity method. Zh Neoig Khim 9 1323-1327 (in Russian)... 

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