889936

research-article2019
CHL0010.1177/1747519819889936Journal of Chemical ResearchChoudhary et al.

Research Paper

Journal of Chemical Research

Atomic polarizability: A periodic descriptor 2020, Vol. 44(3-4) 227­–234

© The Author(s) 2019
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DOI: 10.1177/1747519819889936
https://doi.org/10.1177/1747519819889936
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Shalini Choudhary1,2, Prabhat Ranjan3

and Tanmoy Chakraborty1,4

Abstract
Atomic polarizability is an essential theoretical construct to define and correlate many physicochemical properties. It
exhibits periodicity and has a relationship with other periodic descriptors. Although a number of scales are available
to compute atomic polarizability, the final scale is yet to be designed. In this venture, we have invoked a new empirical
approach to compute the atomic polarizability of 103 elements of the periodic table, considering the conjoint action
of other periodic descriptors, namely effective nuclear charge (Zeff) and absolute radii (r). The proposed approach is
α = a[(r 3 / Zeff )e 2 ] + b , where “e” represents the electronic charge, Zeff is the effective nuclear charge, r is the absolute
radius, and α is the polarizability. Our computed atomic polarizability follows all sine qua non of the periodicity. Our
model significantly exhibits the relativistic effect too. A close agreement between our computed data and other available
theoretical and experimental results demonstrates the efficacy of our proposed approach. Furthermore, we have
established the polarizability equalization principle in terms of our computed data.

Keywords
atomic radii, effective nuclear charge, periodicity, polarizability, polarizability equalization principle
Date received: 05 September 2019; accepted: 01 November 2019

Introduction volume and an appropriate set of radii.10 Chattaraj and

It is considered that the hydrogen atom is an advantageous
system to be used for an introduction to classical or quan-
tum methods. Calculation of the polarizability is used to
determine the change of the energy level of the hydrogen
atom caused by an electric field, and is known as the Stark
effect.1 The exact calculation of atomic polarizability has
potential applications in quantum information processing
and in trapping schemes.2 Bonin and Kadar-Kallen3 have
reported the relationship between polarizability and other
physical parameters.
Atomic polarizability is a size-dependent parameter
which depends on the ease of deforming the valence elec-
tron clouds of a chemical species.4 Polarizability offers
numerous applications regarding bond energy and chemi-
cal reactions.5 Nagle6 studied how atomic polarizability
can be used in conjunction with the number of s and p
valence electrons. A semi-empirical method has been
reported by Miller7 to compute the components of molec-
ular polarizability along with the dipole tensor. Politzer
et al.8 have also proposed a relationship between molecu-
lar polarizability (α), volume (V), ionization energy (I),
Maiti11 have already reported that atomic polarizability
and hardness of atoms are two periodic properties and
their periodicity has been established by the maximum
hardness principle (MHP)12–17 and the minimum polariz-
ability principle (MPP).18,19 According to MPP and MHP,
we can say that an atom with a closed shell structure is the
most stable and the least polarizable among all the atoms
in each period, and in general, polarizability decreases
along a period and increases along a group, while the
hardness follows the reverse trend. Thus, it reveals that
the global hardness and polarizability of elements are the
periodic function of the atomic number. Ghanty et al. have
reported the relationship between the size, the polarizabil-
ity, and the hardness of different chemical species. This
relationship supports the use of these periodic properties
1Department of Chemistry, Manipal University Jaipur, Jaipur, India
2Department of Chemistry, Alankar P.G. Girls College, Jaipur, India
3Department of Mechatronics Engineering, Manipal University Jaipur,
Jaipur, India
4Department of Chemistry, School of Engineering, Presidency

and mean local ionization energy. Furthermore, Ghosh University, Bengaluru, India
and Chakraborty9 have also computed global atomic hard-
Corresponding author:
ness taking into account the relationship between polariz- Tanmoy Chakraborty, Department of Chemistry, School of Engineering,
ability and ionization energy. Polarizability can be Presidency University, Bengaluru 560064, Karnataka, India.
expressed with good accuracy by invoking relationship to Email: tanmoychem@gmail.com
228 Journal of Chemical Research 44(3-4)
for qualitative characterization of the hard–soft acid–base
concept.20–22
In this analysis, we have proposed a new equation to
compute atomic polarizability invoking the relationship
between atomic radii and effective nuclear charge.
Importance of absolute radii to
compute the atomic polarizability
During a chemical reaction, the bond distance changes with
a change of covalent radii and molecules become distorted.
So, the use of covalent radii places a hindrance on the deter-
mination of the exact values of other periodic descriptors.
Ghosh and Chakraborty9 have already established that the
electronegativity of the atom cannot be an in situ property.
The validity of the electronegativity equalization principle
strongly supports this concept. Also, there is a distinct dis-
advantage of in situ properties that it is not transferable.
Since atomic polarizability is a similar theoretical construct
like electronegativity, we may assume that atomic polariz-
ability cannot be an in situ property. The use of covalent
radii has certain disadvantages over the accurate calcula-
tion of periodic descriptors. Over a long period, scientists
have utilized reported covalent radii to compute radial-
dependent periodic descriptors.23 However, there has been
much debate about whether we should use covalent radii or
not for computing theoretical descriptors.9 The higher val-
ues of covalent radii24–27 compared to absolute radii for
some atoms demonstrate this anomalous relation. Also, it is
a well-known fact that the covalent radii of atom can be
transferred from one compound to other. So the use of
absolute radii in place of covalent radii will be more useful
to compute an absolute property of atoms. Ghosh et al.25
computed absolute radii in terms of orbital exponent con-
sidering Slater’s rule. Chakraborty et al.26 also proposed an
approach for computing absolute radii of the 103 elements
of the periodic table considering conjoint action of two
periodic properties, namely ionization energy and effective
nuclear charge. We have followed this verdict in our com-
putation and proposed an approach invoking the absolute
radius of an atom.
Method of computation
Molecular polarizability is a vital descriptor to explain
intermolecular interactions.28–32 Polarizability has been
established as an essential factor in determining the chemi-
cal reactivity.33 In this analysis, we have tried to propose a
theoretical model to compute atomic polarizability invok-
ing other periodic properties.
It is well established that polarizability is considered
equal to r3, where r is the radius of the conducting sphere.34
The generality of linear volume with polarizability has
been assessed quantum mechanically in the case of atoms.
We can write the following equations as suggested by Hati
and Datta35
α = Kr 3 (1)
where K is a constant.
For atoms, the value of K was determined by Dmitrieva
and Plindov36 through atomic oscillation theory, as 0.585,
whereas Hati and Datta35 used the value of K as 0.792.
Equation 1 reveals a direct relationship between atomic
polarizability and the size of atoms. It supports the fact that
atomic polarizability is periodic in nature and can be com-
puted in terms of other periodic descriptors.
Electronegativity, an important periodic descriptor, has
already been defined in terms of an energy model as37
Z 
χ = e 2  eff  (2)
 r 
Ghosh and Chakraborty9 have also proved that another
periodic descriptor, hardness, is numerically equal to elec-
tronegativity, that is, χ = η .
So we can assume the following relationship
Z 
χ = η = e 2  eff  (3)
 r 
Szarek and Grochala38 suggested a simple relationship
between atomic radius, atomic hardness, and electronic
polarizability as
r = α η (4)
From equation (4), it can be concluded that there is a
relationship between atomic polarizability with effective
nuclear charge and atomic radii.
We propose that atomic hardness is directly proportional
to the effective nuclear charge (ηαZeff ) and inversely pro-
portional to the atomic radius (ηα(1 / r )) .
From the relationship between atomic hardness, effec-
tive nuclear charge, and absolute radii, we can propose the
following
Zeff e 2
ηα (5)
r
Now we have proposed that atomic polarizability is not
2 2
equal to the parameter r / ( Zeff e ), but it is proportional to r3.
The proposed equation is
 r3 2 
α =a e  + b (6)
 Zeff 
where “a” and “b” are regression coefficients and “e” rep-
resents electronic charge.
In this report, we have tried to maintain the proper
dimension of evaluated polarizability as an energy unit. It
is already reported that the exact value of hardness is cal-
culated from the absolute radii, and not from the covalent
radii. In formula (6), we have used the absolute radii from
the literature.38 In addition to the resolution of the funda-
mental problems relating to the correct dimension of the
measured quantity and the proper size descriptors of
atoms, many researchers39–41 have calculated the screen-
ing constants and effective nuclear charge theoretically.
We have used the most reliable set of effective nuclear
charge (Zeff) from the reported data,9 and have considered
the charge in an atomic unit and the distance in Å to com-
pute the polarizability in the energy model.
Choudhary et al. 229

Table 1.  Periodic table with computed atomic polarizabilities of the first 103 elements.

1 2
H He
0.09 Periodic Table with Atomic Number, Element Symbol, and 0.02
Computed Polarizability
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
9.10 1.34 1.51 0.73 0.52 0.54 0.46 0.43
11 12 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
11.80 3.18 5.23 2.19 1.34 1.30 1.02 0.91
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
19.69 6.22 5.09 4.49 4.48 4.33 3.48 3.07 3.01 3.12 3.01 2.24 4.47 2.55 1.97 1.90 1.67 1.56
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
22.14 7.60 5.57 4.63 4.45 4.08 3.80 3.64 3.49 2.87 3.29 2.54 5.01 3.02 2.37 2.22 1.97 1.82
55 56 57–71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
26.99 11.07 3.19 2.47 2.40 2.40 2.15 2.05 2.05 2.00 1.85 7.00 4.16 4.04 2.98 2.40 2.11
87 88 89–103  
Fr Ra
22.05 10.73

57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
8.68 10.35 9.92 9.38 8.97 8.62 8.38 7.78 7.91 7.74 7.58 7.46 7.35 7.26 7.73
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103
AC Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
10.86 9.63 8.85 7.88 7.46 7.30 7.18 7.11 6.65 6.48 6.31 6.18 6.07 5.98 8.13

Equalization of polarizability In this report, we have computed the molecular polariz-

The equalization of the periodic property is an essential
theoretical concept and comes into play during molecule
formulation from atoms. Sanderson42,43 first popularized
the concept of equalization regarding electronegativity.
According to his research, when two or more atoms that
are initially different in electronegativity combine chemi-
cally, their electronegativity becomes equalized in the
molecule. The equalization of electronegativity occurs
through the adjustment of the polarities of the bonds,
which is pictured as resulting in a partial charge on each
atom. Electron loss causes an increase and electron gain
causes a decrease in electronegativity. When an electro-
phile interacts with a nucleophile, the electrophilicity of
the former is reduced (via electronic charge transfer and
other related processes, from the nucleophile to the elec-
trophile) and that of the latter is increased until they
become equalized (roughly the geometric mean or arith-
metic mean).44,45 It is expected that as a periodic descrip-
tor, polarizability is also equalized like electronegativity.
The equality between local and global polarizability val-
ues reaffirm this fact. Beg et al.46 proposed an approach to
compute molecular polarizability invoking the polarizabil-
ity equalization principle (PEP)
1
α av =
3
( α xx + α yy + α zz ) (7)
ability in terms of our evaluated atomic polarizability on
the basis of PEP.
Result and discussion
Using our proposed approach, we have computed the
atomic polarizability of the first 103 elements of the peri-
odic table, with the data presented in Table 1. All elemen-
tal values demonstrate a similar periodic trend as expected
from the periodic table.25,47 From Table 1, it is evident that
the value of the computed polarizability of the nitrogen
atom is lower than oxygen. This proves the half-filled
shell characteristics of nitrogen. Due to the half-filled
shell structure, nitrogen is less polarized under perturba-
tion than oxygen. The computed polarizability values
show a minimum for alkali metals and a maximum for
noble gas atoms.
It is also apparent from Table 1 that the magnitude of
the polarizability of mercury and gold are exceptionally
very low, indicating that these atoms would hold electrons
very tightly and are less polarizable. The above observa-
tions support the intrinsic inertness of mercury and gold
similar to with the relativistic effects of such atoms.48,49
Our computed data successfully explain the half-filled and
full shells of the structures of d-block and p-block
elements.
230 Journal of Chemical Research 44(3-4)

Figure 1.  Comparison between computed molecular polarizability and ionization energy (IE).

Figure 2.  Comparison between computed molecular polarizability and experimental values of alkanes.

Lanthanide contraction in terms of atomic polarizabil-
ity is also established through our computed data. The
same trend is presented in Figure 1, which correlates
the computed polarizability values with ionization
energies.50
In order to apply computed atomic polarizability to the
real field, we have adopted the PEP and computed molecu-
lar polarizability (mean polarizability) for some com-
pounds. The computed molecular polarizability has been
compared vis-à-vis with available experimental data51 in
Figures 2–10.
Since alkanes are non-polar compounds and have
only carbon and hydrogens, they require more heat to
combust. They respond poorly to other polar and ionic
species. The same trend is observed in Figure 2. Among
the hydrocarbons, methane shows the least polarizability
and reactivity. For the alcohol series, due to inclusion of
a polar oxygen atom, the magnitude of polarizability of
alcohols increases compared to alkanes containing
equivalent numbers of carbon atoms. A comparative
analysis of the polarizability of alcohols is presented in
Figure 3.
From Figure 4, it is established that nitrobenzene has the
highest polarizability as it has both nitrogen and oxygen
atoms.
In Figure 5, formaldehyde exhibits the lowest value of
polarizability due to the absence of a nitrogen atom.
A similar trend of polarizability with experimental val-
ues for cyanomethane compounds is observed in Figure 6.
Cyanomethane has the lowest polarizability in comparison
to other compounds.
The close agreement between our computed polariza-
bilities and experimental results are observed for some
halo and sulfur compounds in Figures 7 and 8,
respectively.
The impact of the half-filled shell structure of nitrogen
on the polarizability is distinct in Figure 9.
Due to the lower electronegativity of mononuclear dia-
tomic molecules, H2 shows the least polarizability. This
trend is visible in Figure 10.
In Figure 11, the computed polarizabilities of some mol-
ecules such as hydrogen, carbon, nitrogen, oxygen, fluo-
rine, sulfur, chlorine, bromine, and iodine are compared
with the ab initio (mean) linear polarizabilities proposed by
Choudhary et al. 231

Figure 3.  Comparison between computed molecular polarizability and experimental values for alkanols.

Figure 4.  Comparison between computed molecular polarizability and experimental values for alkenes.

Figure 5.  Comparison between the computed molecular polarizability and experimental values of carbonyl compounds.

Figure 6.  Comparison between computed molecular polarizability and the experimental values for alkyl cyanides.
232 Journal of Chemical Research 44(3-4)

Figure 7.  Comparison between computed molecular polarizability and the experimental values for halogenated compounds.

Figure 8.  Comparison between computed molecular polarizability and the experimental values for sulfur compounds.

Figure 9.  Comparison between computed molecular polarizability and the values for various molecules.

van Duijnen and Swart.51 A close agreement between the
two data is distinct from the Figure 11.
Conclusion
Based on the potential energy concept, we have estab-
lished a new scale of atomic polarizability invoking two
other periodic descriptors, namely effective nuclear
charge and absolute atomic radius. Our proposed approach
establishes the dependence of chemical reactivity on
polarizability. The computed atomic polarizability dis-
tinctly exhibits all periodic properties. The relativistic
effect is also pronounced in our computations. Comparative
analysis with available data, considered as a benchmark,
reveals the efficacy of our proposed equation. Furthermore,
we have computed molecular polarizability in terms of
our computed atomic polarizability through the PEP.
Excellent correlation with experimental data establishes
our model.
Declaration of conflicting interests
The author(s) declared no potential conflicts of interest with
respect to the research, authorship, and/or publication of this
article.
Choudhary et al. 233
Figure 10.  Comparison between computed molecular polarizability and the experimental values for diatomic molecules.
Figure 11.  Comparison between computed molecular polarizability and the experimental values for some elements.
Funding
The author(s) received no financial support for the research,
authorship, and/or publication of this article.
ORCID iD
Tanmoy Chakraborty https://orcid.org/0000-0002-3374-8125
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