Journal of Theoretical and Computational Chemistry Vol. 4, No.

1 (2005) 2133 c World Scientic Publishing Company

A NEW SCALE OF ELECTRONEGATIVITY BASED ON ABSOLUTE RADII OF ATOMS

DULAL C. GHOSH Department of Chemistry, University of Kalyani Kalyani 741-235, India dulal@klyuniv.ernet.in dcghosh1@redimail.com Received 30 August 2004 Accepted 18 September 2004 A new scale of electronegativity is designed on the basis of the environment independent absolute radii of atoms. In this scale, the electronegativity is an intrinsic free-atom property and the basis of assumption is quantum mechanically viable. The qualitative relation between the size and electronegativity is relied upon and a quantitative general formula of evaluation of electronegativity in terms of the absolute radii of atoms is suggested as = a (1/R) + b, where is electronegativity and R is absolute radius of atoms, a and b are two constants determined by least square tting for each period of elements separately. A number known as electronegativity is computed for each 103 elements of periodic table through the above formula and the unit assigned to is energy. The new scale of electronegativity is found to observe the simple rules that all the scales of electronegativity must obey. The evaluated scale reproduces the silicon rule where the electronegativities of the eight elements of metalloid group are very close to each other and the electronegativity of silicon atom is smallest of the group. A striking feature of the new scale is that the electronegativity of N atom is greater than that of Cl atom. The characteristic properties of chalcogens and transition metal atoms have been nicely correlated in terms of the computed values of of such elements. The evaluated electronegativities of the elements beautifully exhibit the periodic behaviour of periods and groups of the Periodic Table. The revealed internal consistencies suggest that the present eort of introducing a scale of electronegativity based on absolute radius of atoms is largely successful. Keywords: Electronegativity and its scale of measurement; third dimension of periodic table.

1. Introduction The concept of electronegativity is very old and it is the most widely used concept for understanding chemical binding and reactivity in molecules. It is clearly
The paper was presented in the conference of Theory and Application of Computational Chemistry, Gyeongju, Korea February 1520, 2004 and the Abstract was published in the Proceedings of the Conference.

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one of the central ideas of chemistry, which generates much theoretical interest and attracts considerable attention of chemists and physicists. Coulson1 remarked that the concept of electronegativity has the astonishing success in correlating a vast eld of chemical knowledge and experience. Fukui2 pointed out that in the electronic theory, the static and dynamic behaviour of molecules are explained by the electronic eects that are based on nothing but the distribution of electrons in a molecule and the mode of charge distribution in a molecule can be sketched to some extent by the use of the electronegativity concept. The use of electronegativity concept to understand bond energy dierence is widely appreciated. Presently this ingenious concept has crossed the boundary of chemistry and permeated in the eld of physics, geology and biology. A striking dependence of the super conducting transition temperature on electronegativity is found for both solid elements and new high temperature super conductors.39 Unfortunately, electronegativity unlike atomic number, mass, ionization energy, or electron anity is neither a directly measurable experimental property of an isolated atom nor it can be precisely dened10 and there is no quantum mechanical operator whose expectation value is electronegativity.11 Since Paulings12 landmark contribution in 1932 when he dened electronegativity as the power of atom in a molecule to attract electrons to it, an experimental measure of the power of an atom has been searched for by numerous authors over nearly 60 years. A number of qualitative and quantitative scales of measuring electronegativity have been proposed. We have recently reviewed13 the prevailing scales and concepts of electronegativity and have addressed the questions of fundamental status and the unit of measurements of electronegativity. Allen and Knight10 have argued that electronegativity is an intimate property of Periodic Table and maintains a broken symmetry relationship to Periodic Tables taxonomy. Allen and Knight have further argued that the diculty in dening the electronegativity stems from the contemporary idea of broken symmetry.14 Allen15 has tried to establish that the unit of electronegativity is energy and it is the third dimension of Periodic Table. Recent density functional underpinning1618 of the problem of electronegativity seems to give a new dimension to the concept of electronegativity. However, despite considerable eorts to establish a clear denition and a commonly acceptable scale, there has been no agreement as to which scale provides the best description of electronegativity and electronegativity has remained a practical qualitative guide and the best method of evaluating electronegativity remains to be discovered.19 The position is that the qualitative understanding of the property electronegativity is distinctly clear but it is very dicult to quantify. Pasternak20 held that the concept of electronegativity is an atomic property and a crude approximation, and hence a simple empirical scale may be more useful than a sophisticated one. Each scale attempts to allot a number to each element of the periodic table and these numbers are thought to reect the tendency of atoms to attract electrons when bonded because Paulings qualitative characterization of electronegativity as the power of an atom in a molecule to attract

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electrons to itself is the most deeply implanted conceptualization of electronegativity in minds of chemists and physicists. It is ubiquitous that the unit13 associated with the number is not always properly addressed. In another controversy whether electronegativity is an in situ or intrinsic property of atom, the majority of workers logically hold that electronegativity is an intrinsic property of atoms.10,11,13,2123 Allen and Knight10 opined that the assumption that electronegativity as an in situ property is self-defeating. Iczkowski and Margrave21 observed that electronegativity is a property that is characteristic of the internal constitution of an atom. Lackner and Zweig22 seem to establish the fundamental relation between shell structure and electronegativity and opined that it is an intrinsic atomic property. Allen et al.11 and the proponents23 of density functional theory seem to hold conclusively that electronegativity is a denite property of the ground state of an atom. A search of literature on electronegativity reveals that a good number of workers converge to number of common proposition regarding electronegativity: (i) it is an intrinsic atomic property and not in situ property; (ii) it is a global property; (iii) it is a property which is associated with shell structure of atoms and stems from the screened nuclear charge; (iv) it is a property which has to be measured in energy units; and (v) it is a periodic property. Thus one may suggest, relying on the shell structure of atoms, that the electron attracting power associated with an atom, the electronegativity in general is a consequence of incompletely screened nuclear charge eective within stable outer orbital positions. The same incompletely screened nuclear charge determines the environment independent absolute size of the atoms.24 Pitzer25 pointed out that the binding energy of an electron and the atomic radius tend to change in a regular and related manner in going from one atom to another, which envisage a periodic behaviour of both electronegativity and atomic size. Thus, the radii and the electronegativity have a common origin and they should be related to each other. Moreover, the electronegativity is periodic property and the atomic size is also a periodic property. The Periodic Table shows many regularities and it is not surprising that many correlations can be found between seemingly unrelated quantities. In addition to their common origin, periodicity is probably the basis for the correlation between electronegativity and atomic radius. The purpose of the present work is to oer an alternative and independent method of evaluating the electronegativity of the elements where the absolute radius of the atoms is inputs. We have drawn a new scale of electronegativity on the basis of empirical relationship between the size and electronegativity of atoms, and it is accepted that the electronegativity is an intrinsic and global property of the atom and its unit is energy. We feel pertinent to mention here the radii dependent scale already existing before we enunciate our

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scale of electronegativity relating the absolute radii of atoms. The prevalent radii dependent scales are: 1. 2. 3. 4. AllredRochow26 Scale Gordys27 Scale Sandersons28 Scale Zhangs29 Scale 5. 6. 7. 8. Scale of Luo et al .30 The Scale of Boyd and Markus31 The Scale of Boyd and Edgecomb32 Quantum Defect Scale of St. John and Bloch33

However, all the above-mentioned scales, except the scale of St. John and Bloch,33 have used the covalent radius as the size input in formulating the scale and evaluating the number representing electronegativity. Now, a survey of the literature on the subject reveals that the majority of workers13 believe that the electronegativity is not an in situ rather an intrinsic ground state global property of atoms. We cite a few of them. Parr et al.34 hold that it is unequivocal that the electronegativity is a denite property of the ground state of an atom or molecule. St John and Bloch33 are almost inclined to hold that electronegativity is a purely atomic property, independent of molecular or crystalline environment. It is already mentioned above that Allen and Knight10 hold that electronegativity must be a free atom property and the third dimension of the Periodic Table. Now, it has to be justied whether the covalent radius or the absolute radius should be the appropriate size input in dening any scale of electronegativity involving the size of the atoms. Nagle35 suggested that there should be a direct relationship between absolute atomic size and electronegativity. The covalent24 radius is not the absolute size representation of the atoms because the magnitude of covalent radius is uncertain with respect to degree of covalency. Ruedenberg,36 in his fundamental analysis of the nature of covalent bond, concluded that the process of binding between atoms is a non-classical phenomenon and the atoms form promoted states through cluster promotion just prior to the event of chemical bonding when potential energy decreases and kinetic energy increases. Subsequently, the formation of bond is associated with lowering in kinetic interference energy but potential energy remains lowered. Thus, the atoms remain in modied state or valence state in molecules and not in the free ground state.36 There is further observation that the covalent radius is a particular measure of the size of an atom in a molecule, and is thus a valence state property37 and depends upon the state of hybridization of the atoms in molecules. Moreover, there is another diculty with covalent radius because all the atoms of Periodic Table do not form covalent compounds and the covalent radii of all the atoms are thus not available. It, therefore, transpires that scales of electronegativity involving covalent radius are not conceptually appropriate. The scale of electronegativity that may be designed in terms of absolute radius is physically more realistic and conceptually more satisfying and more consistent with the thinking that electronegativity is an intrinsic property of atoms. We have drawn a new scale of electronegativity on the basis of empirical relationship between the size and electronegativity of atoms and it is accepted that the electronegativity is an intrinsic and global property of the atom and its unit is

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energy. The impetus of the present work comes from an observation that simplest scale always gives the best results38 and we recently theoretically evaluated absolute radii of 103 elements of Periodic Table.24 The ecaciousness of such size data has been veried by computing size dependent physico-chemical properties of atoms and these new set of atomic radii have been used as benchmark for further work on atomic size.39 2. The Method of Computation We have posited above at length that the any empirical scale of electronegativity involving atomic size should incorporate the absolute radii and not covalent radii or any other size data in formulating such a scale. The Periodic Table shows much regularity, and it is not surprising that many correlations can be found between seemingly unrelated quantities.15,21 The radius and electronegativity are both periodic and hence they should be related. It follows from the shell structure that the screened nuclear charge increases horizontally along a period.24 Since the screened nuclear charge is primarily controlling the atomic and ionic size and the electron attracting power of the atom or electronegativity, the size of the atoms should decrease and electronegativity should increase monotonically along the horizontal row. This suggests that electronegativity and the atomic radius are inversely related to each other. We have therefore suggested the following general formula of evaluating electronegativity in terms of the absolute radii of atoms: = a (1/R) + b, (1)

where is electronegativity and R is absolute radius of atoms, a and b are two constants to be determined by least square tting. Such a formulation is, in fact, the computation of one atom property from other atomic properties that are related through periodic table. Scientists use this procedure conveniently to compute one atom property from other atom properties.35,40 Surprisingly, theoretical support for the new empirical formulation of electronegativity of atoms according to Eq. (1) comes from statistical FermiAmaldi41 model. Dmitrieva and Plindov41 derived, on the basis of statistical FermiAmaldi model, the chemical potential () of atomic systems = 1/R, where R is the atomic radius. The density functional denition16 of electronegativity () is = . Hence it follows from Eq. (2) that the electronegativity of atomic systems = 1/R. (4) (3) (2)

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Since periodicity of atomic size stems from the shell structure of atoms, the coecients a and b are determined by the method of least square tting for each period of elements separately. The Mulliken42 electronegativity in atomic unit scale is computed through the ionization potentials and electron anities of elements. Although the ionization potentials are available, the electron anity is denitely wanting. However electron anitities of a number of elements are evaluated and published by Schaefer et al.43 in addition to those already available from standard Tables.44 The ionization potentials are collected from standard Tables.44 The computed Mulliken electronegativity converted into atomic units are plotted against the atomic radii (in atomic unit) of respective atoms for each period. The absolute radii are taken from our work.24 It is well known that the formulation of Mullikens scale42 of electronegativity and that of the operational and working formula of density functional denition of Parr et al.16 look identical. Thus, invoking Mulliken scale is as good as invoking the density functional scale. The reason behind invoking the Mulliken scale for the purpose of evaluating the coecients in Eq. (1) is that we have dened electronegativity in energy unit and the Mulliken or the density functional scale evaluates electronegativity in energy unit. The computed a and b coecients are presented in Table 1. The electronegativities of 103 elements are computed in energy units (a.u.) through the Eq. (1) and are presented in Table 2. The computed data are plotted as a function of periodic coordinates, the atomic number of elements, in Fig. 1. The computed electronegativities of metalloid elements, elements of halogen family, chalcogens and inert gas elements are presented in Tables 36 respectively. 3. Results and Discussion We are not certain as to which scale is the best approximation to the electronegativity property of the atoms of elements and hence, as such, there is no benchmark for this particular property. However, it is at once evident from Fig. 1 that the computed electronegativities reproduce the periodicity of periods and groups of the periodic table. Each period begins with a representative element and the electronegativity increases monotonically horizontally to be maximum at the noble gas atoms

Table 1. The linear correlation coecient parameters a and b for each period. Period First Second Third Fourth Fifth Sixth Seventh a Coecient 0.2556 0.2455 0.3936 0.3921 0.4253 0.1731 0.4899 b Coecient 0.0082 0.0253 0.003 0.0399 0.0579 0.1391 0.0515

A New Scale of Electronegativity Based on Absolute Radii of Atoms Table 2. The evaluated absolute electronegativities of the elements (a.u.). Element H He Li Be B C N O F Ne Na Mg Al Si P S Cl Ar K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr Rb Sr Y Zr Tl Pb Bi Po At Rn Fr Ra Ac Th Pa U Radii (a.u.) 1 0.588246 3.07672 2.051209 1.53836 1.230726 1.02551 0.879063 0.769274 0.683673 4.090892 3.157785 2.57124 2.168556 1.874906 1.651172 1.475246 1.333333 6.726757 5.192555 4.933107 4.697846 4.484505 4.289683 4.110733 3.946523 3.794407 3.654006 3.52381 3.402116 2.959751 2.619426 2.349017 2.129441 1.947279 1.79384 9.090325 7.017196 6.666289 6.348828 5.039683 4.460128 3.999811 3.625718 3.315571 3.054422 13.68178 10.56066 10.03231 9.555745 6.999622 6.08031 Electronegativity () (a.u.) 0.2638 0.442712 0.105093 0.144986 0.184886 0.224776 0.26493 0.304575 0.344443 0.384390 0.093214 0.121644 0.150078 0.178503 0.206931 0.23596 0.263803 0.29220 0.0981896 0.1154119 0.1193833 0.1233637 0.1273344 0.1313053 0.1352844 0.1392532 0.1432363 0.1472068 0.1511716 0.1551518 0.1723773 0.1895892 0.2068208 0.2240328 0.2412578 0.2584813 0.104686 0.1185082 0.1216986 0.1248887 0.173447 0.177911 0.182377 0.186842 0.19131 0.195772 0.08731 0.09789 0.10033 0.10277 0.12149 0.13207 Element Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe Cs Ba La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf Ta W Re Os Ir Pt Au Hg Np Pu Am Cm Bk Cf Es Fm Md No Lr Radii (a.u.) 6.06028 5.796863 5.555178 5.332955 5.127929 4.93802 4.761716 4.597506 3.999811 3.539683 3.174414 2.877551 2.631519 2.422036 11.45408 8.84127 7.199924 6.071995 5.249433 4.623583 4.130952 3.733182 3.40514 3.130197 2.896447 2.695011 2.519841 2.366024 2.22997 2.108655 1.999811 1.904573 1.812925 1.731859 1.657785 1.589785 1.546107 1.469388 1.415722 5.789116 5.374717 4.458806 4.06746 3.986584 3.458617 3.21901 3.009826 2.826153 2.663643 2.518707 2.487528 Electronegativity () (a.u.) 0.1280782 0.1312672 0.1344592 0.1376494 0.1408379 0.1440276 0.1472165 0.1504066 0.16423 0.178052 0.1918774 0.2056992 0.2195176 0.2333511 0.1542125 0.1586786 0.163142 0.16761 0.17208 0.176539 0.1810032 0.185468 0.189935 0.1944 0.198863 0.20333 0.207795 0.212261 0.2167244 0.22119 0.22565 0.229987 0.234581 0.2390504 0.2435164 0.2479845 0.25106 0.25691 0.26137 0.169 0.14265 0.16137 0.17194 0.17439 0.19315 0.20369 0.21427 0.22485 0.23542 0.246 0.24844

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Fig. 1. Plot of electronegativity as a function of atomic number.

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that occur at the top of the curve. Looking at the position of each corresponding element in Fig. 1, we see that electronegativity decreases monotonically vertically downwards. Thus, the -scale exhibits a general increase left to right across rows and a general decrease down groups. We cite here a few well known groups for more distinct visualization of the vertical downward decreasing trend of in a group.

Table 3. Verication of silicon rule. Element B Si Ge As Sb Te Bi Po Electronegativity (a.u.) 0.184886 0.178503 0.1895892 0.2068208 0.1918774 0.2056992 0.182377 0.186842

Table 4. Electronegativities of halogen family. Elements F Cl Br I At Electronegativity (a.u.) 0.34443 0.263803 0.2412578 0.2195176 0.19131

Table 5. Electronegativities of chalcogens. Element O S Se Te Po Electronegativity (a.u.) 0.304575 0.2443012 0.2240328 0.2056992 0.186842

Table 6. Electronegativities of inert gas elements. Element He Ne Ar Kr Xe Rn Electronegativity (a.u.) 0.442712 0.384390 0.29220 0.2584813 0.2333511 0.195772

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Tables 46 present the s of halogen family, group VIb elements and the inert gas elements respectively. Analysis of the numerical values of all such tables reveals a distinct downward decreasing trend of in such groups. But the periodicity alone is not the surer validity test of the magnitudes of the electronegativity of any scale. No eort is made, however, to compare the magnitudes of present electronegativity scale with those of the other existing scales because of the fact that the majority of the scales are ambiguous about the unit13 of measurement and the absolute numerical values of quantities having dierent units are not comparable, because they represent conceptually dierent entities. We have, therefore, relied mainly upon the validity test of a scale of electronegativity introduced by Allen et al.11 and Allen15 in our present eort. Looking at the Table 2, we observe the following: (i) the seven atoms N, O, F, He, Ne, Ar, and Kr, have the highest electronegativities among the main group elements; and (ii) the electronegativity of N is greater than that of Cl a fact that establishes the superiority of the present scale. From Table 3, we see that the electronegativity of a group of eight metalloid elements are very close to each other and the of Si element is the minimum in the group. Thus the scale satises the silicon rule.11 3.1. Correlation of the variation of the properties of group VIb elements The s of group VIb elements are presented in Table 5. The great dierences between the chemistry of oxygen and that of other group VIb elements and then more gradual variations through the sequence S, Se, Te , Po are distinct in terms of the present computed values of of such elements. The lower electronegativities of the SPo elements lessens the ionic character of those of their compounds which are formally analogous to those of oxygen, and alters the relative stabilities of various kinds of bonds and drastically lessens the importance of hydrogen bonding. 3.2. Transition-metal electronegativity A close look at Table 2 reveals that the electronegativity of transition metal elements are small. Allen and Huheey45 identied with the atoms electron attracting power. The electron attracting power is generally equal to its electron holding power. It is well known that the size of atoms of atoms of d-block and f-block elements undergo a steady but slow contraction and the eect is well reproduced in the radii we are using in the present calculation.24 It is well known that the transition metal atoms are soft and easily deformable. This property predicts that the electronegativity of the transition metal elements should be small and according to Allen,15 it should be smaller than the lowest value in the metalloid band. A closer

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0.2 0.18 0.16 Electronegativities (a.u) 0.14 0.12 0.1 0.08 0.06 0.04 0.02 0 The atomic number
Fig. 2. A comparative study of the electronegativities of the atoms of Si and the rst transition series elements.

Si Cu Zn

Sc

Ti

Cr

Mn

Fe

Co

Ni

look at the Table 2 reveals that the s of transition elements are small. To make the position more transparent, the electronegativities of rst d-block transition series and that of silicon are plotted as a function of their atomic numbers in Fig. 2. From Fig. 2, it is obvious that the electronegativity of transition metal atoms is considerably smaller than that of Si. It is further revealed from a closer look at Fig. 1 that the s of transition elements increase slowly with increasing atomic number. This increasing trend of s of transition elements with atomic number can be rationalized in terms of the expressed relation between the radius and electronegativity. The radii of atoms decrease slowly and of such atoms increase slowly as a function of atomic number.

4. Conclusion The Periodic Table shows many regularities and it is not surprising that many correlations can be found between seemingly unrelated quantities. It, therefore, transpires that the correlation between electronegativity and the atomic radius stems through the periodic table. A new scale of electronegativity is suggested on the basis of the correlation between electronegativity and absolute radii of atoms. The present eort of introducing a new scale of electronegativity is quantum mechanically viable in view of the fact the basic hypothesis for the construction of the absolute size dependent scale of electronegativity nds justication from shell structure of atoms and screening of nuclei by its outer electrons. The method is, however, basically computation of one atom property from the other atom properties. From the survey of chemical literature, it is evident that the electronegativity is an intrinsic free atom ground state property and not an in situ property. Hence, it is argued that the

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empirical radial dependent scale of electronegativity should be formulated involving absolute radii and not the covalent radii of atoms. A quantitative relation of evaluating electronegativity in terms of absolute radii of atoms has been suggested. The unit of electronegativity of this scale is energy. The internal consistency of the computed data is tested in the light of existing idea of electronegativity, and is found to observe the simple rules which all electronegativity scales must obey. A striking feature of this new scale is that the electronegativity of N atom is greater than that of Cl atom. This important fact establishes the superiority of the present scale. The evaluated electronegativity of elements beautifully exhibits the periodic behaviour of periods and groups. The present scale is found to satisfy the silicon rule of electronegativity. We have made no eort to compare the computed values of electronegativity with those of other scales as because we are not certain as to which scale is the best approximation to the electronegativity property of the atoms of elements and which scale can be used as benchmark for this particular property. Moreover, the absolute numerical values of quantities having dierent units are not comparable, because they represent conceptually dierent entities. The results demonstrate that the attempt of introducing a radial dependent scale of electronegativity is largely successful and we have tried to posit that the denition of electronegativity of an atom in the present scale is quantum mechanically viable. References
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