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Chemical Physics Letters 454 (2008) 133138

www.elsevier.com/locate/cplett

Net-sign identity information index: A novel approach

towards numerical characterization of chemical signed graph theory
Prabhat K. Sahu 1, Shyi-Long Lee *
Department of Chemistry and Biochemistry, National Chung Cheng University, Chia-Yi 621, Taiwan

Received 10 July 2007; in nal form 22 January 2008

Available online 30 January 2008

Abstract

In this work, we have made an attempt to derive a novel information theoretic topological index, net-sign identity information index, Ie
from the molecular electronic structure, proposed by Lee et al. [S.-L. Lee, R.R. Lucchese, S.-Y. Chu, Chem. Phys. Lett., 137 (1987) 279]
in chemical graph theory. The performance of the net-sign identity information index along with the square root of the bonding infor-
p p
mation index, Ib and the square root of net-sign identity information index, Ie have been compared with the most widely used molec-
ular descriptors: Wiener index (W), Randics connectivity index (v) and Balabans distance sum connectivity index (J) in QSPR modeling.
2008 Elsevier B.V. All rights reserved.

1. Introduction literatures indicates that numerous topological indices have

The theoretical chemists always try to build schemes
that would allow accurate predictions of the bulk proper-
ties of matter from the knowledge of molecular structure.
It is well known fact that the structure of a compound,
both geometric and electronic, determines its properties.
Nonetheless, elucidation of the connection between molec-
ular structure and bulk properties has posed a challenge to
chemist for more than a century. Recently attention has
turned to the use of more general structural parameters,
in particular those derived from chemical graph theory.
The characterization of the bonding topology and the ste-
reochemistry of molecular graph have been emerged as
prominent one towards solving chemical problems. The
bonding topology of each molecular graph is converted
into an expression, which may be a matrix, a polynomial,
a sequence of numbers or a numerical index for the struc-
ture and properties correlation of molecules. Study of the
*
Corresponding author. Fax: +886 5 2721040.
E-mail address: chesll@ccu.edu.tw (S.-L. Lee).
1
Present address: Institut fur Organische Chemie, Universitat Wurz-
burg, Am Hubland, D-97074 Wurzburg, Germany.
been proposed in the light of chemical need [19]. Since the
eort made by pioneer Wiener [10], we can nd the contri-
butions of Balaban [11], Randic [12], Kier et al. [13], Bon-
chev [14], Trijnastic et al. [15], Hosoya [16], Basak et al.
[17], and many others, in the applicability of topological
indices to the prediction and in some cases, interpretation
of many physical, chemical and biological properties. How-
ever, for these topological indices, the applicability is quite
limited in extension, or the calculating process is compli-
cated. The topological indices that can be adapted to com-
plex molecules are limited, and those indices suitable for
complex molecules simultaneously containing heteroatoms,
multiple bonds, and rings are even smaller. One of the most
frequent criticisms about TI, since their early stages of
development, was the absence of a physical or physico-
chemical interpretation, so that many critics think about
molecular topology just like a typical heuristic and/or sto-
chastic formalism. This is why it is important to attempt
to provide an explanation about their physical meaning
or their physical applicability.
In this Letter, we would like to report a new information
theoretic topological index based on chemical signed graph
theory proposed by Lee et al. [18] and further investigation

0009-2614/$ - see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.cplett.2008.01.055
134 P.K. Sahu, S.-L. Lee / Chemical Physics Letters 454 (2008) 133138

of the reported [19] information theoretic indices derived

from edge signed graphs (ESGs). So far information the-
ory oers quantitative methods for the study of receiving,
conserving, processing, transmitting and practical use of G21 G32 G33
information [5]. The great power of information methods
in discriminating similar structures (isomers, isotopes,
etc.) is of interest for the computer processing and retrieval
of chemical information. Alternatively, the possibilities
which information theory provides for the creation of
new hypotheses are often limited since this theory describes
the mutual dependence of number of variables, but not the
behaviors of each of them. The relation that exists between G43 G43 G44
structure and properties is another eld of successful appli-
cation of information-theoretic approach to chemistry [6
9]. Moreover; the most attractive feature of the informa-
tion approach is its ability to provide a unied view on var-
ious phenomena, as well as universal language for their
description [59].
The main chemical application of the net signs
approach, so far found has been reported earlier [2028]: G44 G45 G46
the square root of the net signs over occupied MOs is
shown to be linearly correlated with the total p-electron Fig. 1. Molecular graphs, Gve (two-vertex through four-vertex).
energy of conjugated hydrocarbons [20]. In addition to
this, the net-sign approach also provides a new insight on From Ref. [19], Ik = m lb m n lb n (n m) lb |n m|,
generalizing the Huckel (4n + 2)-rule in polycyclic conju- where m and n represent the total number of positive (+)
gated molecules [20]. Lee et al. has also applied the net-sign and total number of negative () signs from edge signed
analysis in predicting the ground-state geometry of ve- graphs (ESGs) of the corresponding molecular graph and
vertex clusters [24]. A pairing-theorem-type regularity, k is the molecular orbital level.
which holds for the net signs of bipartite graphs (molecular
graphs of alternant hydrocarbons), has also been discussed 3. Results and discussions
[26]. Chemical signed graph theoretical approach has also
been applied successfully to classify non-alternant non-ben- The computed values for the new net-sign-identity infor-
zenoid conjugated hydrocarbons with regards to their mation index, Ie for the dierent molecular graphs (two-,
chemical reactivity [28]. We feel that Lord Kelvin was right three- and four-vertex) are tabulated along with the prop-
when he dictum that [29]. erties based information theoretic indices, Ib, Ia and In
When you can measure what you are speaking about, [19] in Table 1. It can be observed that, for more branching
and express it in numbers, you know something about it, molecular graph such as, G0 43 and G0 44, the numerical val-
but when you cannot measure it, you cannot express it in ues obtained for Ie low corresponding to other molecular
numbers, your knowledge is of a meager and unsatisfactory graphs. The potential usefulness of net-sign-identity infor-
kind. . . mation index has been examined through quantitative
Some progress has also been made towards quantica- structure-property relationship (QSPR). In this study, we
tion of the above-mentioned concepts [19], including char-
acterization of the net-sign approach (Fig. 1).
Table 1
Dierent information index values for the two, three and four-vertex
2. Denition molecular graphs
Gve Ib Ia In Ie
Basing on the net-sign approach to the chemical graph G21 0.000 0.000 0.000
theory, the novel information theoretic topological index, G32 3.999 3.999 0.000 31.984
Ik has been reported earlier [19] along with some properties G33 9.509 1.999 94.417
based information theoretic indices. The new net-sign-iden- G43 11.508 11.508 188.834
tity information index, Ie is dened as, the summation of the G0 43 9.509 9.509 0.000 180.842
G44 15.999 15.999 0.000 511.936
square of the numerical values obtained for Ik [19] for each G0 44 15.999 6.755 0.000 301.598
molecular orbital level, k, ranging from 1 to N: G45 23.219 12.755 0.000 701.812
X
N G46 31.019 23.997 1154.130
2
Ie I k  1 Numerical values for the dierent information indices, Ib, Ia and In are
k1 obtained from Ref. [19].
 P.K. Sahu, S.-L. Lee / Chemical Physics Letters 454 (2008) 133138 135

have considered both saturated hydrocarbons (Alkanes) Molar volume (MV)

and unsaturated hydrocarbons (Alkenes). Multiple regres-
MV 0:0252I e 52:701 2
sion analysis (MRA) has been applied in QSPR modeling
of ve dierent physical properties: molar volume (MV), n 12; R 0:892; s 7:78; F 39
boiling point (BP), molar refractions (MR), critical pres- MV 26:511v 12:827 3
sure (PC), critical temperature (TC) [3032] for saturated n 12; R 0:971; s 4:08; F 168
hydrocarbons and three dierent physical properties: molar
MV 23:241J 15:91 4
volume (MV), boiling point (BP), molar refractions (MR)
for unsaturated hydrocarbons. Moreover, the performance n 12; R 0:886; s 7:99; F 36
of the net-sign identity information index has also been MV 1:3322W 45:371 5
compared with the most widely used molecular descriptors: n 12; R 0:944; s 5:67; F 82
Wiener index (W), Randics connectivity index (v) and Bal- p
abans distance sum connectivity index (J) in QSAR/ MV 8:4624 I b 35:057 6
QSPR. The parameters and properties for the saturated n 12; R 0:985; s 2:89; F 342
hydrocarbons are tabulated in Table 2 and for the unsatu- p
MV 1:2016 I e 42:5051 7
rated hydrocarbons are tabulated in Table 3.
n 12; R 0:975; s 3:78; F 196
3.1. Saturated hydrocarbons It can be seen from relations (2)(5) for the saturated
hydrocarbons that Randics connectivity index (v) found
The correlation models for the ve dierent properties to be very good for molar volume (MV). The net-sign iden-
for saturated hydrocarbons are obtained as: tity information index, Ie, has similar relationship to that of

Table 2
Observed values and predicted values for the physical properties of 12 saturated hydrocarbons (alkanes)
p
No. Name Type Ie MV MV BP BP MR MR PC PC TC TC
(obs.) (pred.) (obs.) (pred.) (obs.) (pred.) (obs.) (pred.) (obs.) (pred.)
1 C2 G21 0.000 35.522 42.505 88.63 64.56 48.2 43.82 32.27 66.44
2 C3 G32 5.655 48.051 49.300 42.07 44.75 42.01 41.61 96.8 92.02
3 nC4 G43 13.742 61.722 59.017 0.5 16.42 37.47 38.45 152.01 128.59
4 2MC3 G0 43 13.447 61.767 58.663 11.73 17.45 36.00 38.57 134.98 127.26
5 nC5 G54 23.322 74.122 70.528 36.07 17.14 25.265 25.502 33.31 34.71 196.62 171.92
6 2MC4 G0 54 24.560 75.032 72.016 27.85 21.47 25.292 25.899 32.9 34.23 187.8 177.52
7 22MMC3 G00 54 22.626 73.917 69.692 9.50 14.69 25.724 25.279 31.57 34.98 160.6 168.77
8 nC6 G65 37.667 84.523 87.765 68.74 67.39 29.906 30.102 29.92 29.11 234.7 236.80
9 2MC5 G0 65 33.547 85.259 82.815 60.27 52.95 29.945 28.781 29.95 30.72 224.9 218.17
10 3MC5 G00 65 37.465 85.335 87.522 63.28 66.68 29.801 30.037 30.83 29.19 231.2 235.88
11 23MMC4 GIV65 37.465 84.447 87.522 57.98 66.68 29.81 30.037 30.99 29.19 227.1 235.88
12 22MMC4 GV65 37.465 85.174 87.522 49.74 66.68 29.935 30.037 30.67 29.19 216.2 235.88
M stands for methyl.
Units: MV (L/mol), BP (C), MR (m3/mol), PC (atm), TC (C).

Table 3
Observed values and predicted values for the physical properties of 13 unsaturated hydrocarbons (akenes)
p
No. Name Type Ie MV (obs.) MV (pred.) BP (obs.) BP (pred.) MR (obs.) MR (pred.)
1 Ethylene G21 0.000 31.203 37.296 103.7 74.4
2 Propene G32 5.655 43.031 44.294 47.4 53.2
3 1-Butene G43 13.742 55.659 54.299 6.3 22.9
4 2-M-propene G43 13.447 60.504 53.935
5 1-Pentene G54 23.322 67.473 66.153 29.9 12.8 24.858 25.332
6 2-M-1-Butene G54 24.559 67.407 67.684 31.2 17.5
7 3-M-1-Butene G54 24.559 71.324 67.684 20.1 17.5
8 1-Hexene G65 37.667 81.738 83.902 63.3 66.5 29.208 29.915
9 3-M-1-pentene G65 33.547 81.181 78.805 54.1 51.1 29.485 28.599
10 2-M-1-pentene G65 37.465 84.001 83.652 60.7 65.7 29.398 29.851
11 2-E-1-Butene G65 33.547 80.516 78.805 64.7 51.1 29.391 28.599
12 2,3-MM-1-butene GIV65 37.465 80.351 83.652 55.7 65.7 30.063 29.851
13 3,3-MM-1-butene GV65 37.465 79.432 83.652 41.2 65.7 29.598 29.851
M and E stands for methyl and ethyl, respectively.
Units: MV (L/mol), BP (C), MR (m3/mol).
136 P.K. Sahu, S.-L. Lee / Chemical Physics Letters 454 (2008) 133138

Balabans distance sum connectivity index (J). However,

p Critical pressure (PC)
the square root of the bonding information
p index, Ib
PC 0:0078I e 40:232 20
and net-sign identity information index, Ie [(6) and (7)]
n 12; R 0:805; s 3:51; F 18
shows even better relation as compared to Randics con-
nectivity index (v) for MV. PC 8:7201v 53:698 21
Boiling point (BP) n 12; R 0:930; s 2:17; F 64
PC 8:1765J 53:951 22
BP 0:0739I e  35:079 8
n 12; R 0:907; s 2:49; F 46
n 12; R 0:887; s 23:38; F 37 PC 0:4283W 42:802 23
BP 79:80v  156:61 9 n 12; R 0:883; s 2:77; F 35
p
n 12; R 0:993; s 5:96; F 712 PC 2:8182 I b 46:5348 24
BP 62:412J  129:37 10 n 12; R 0:955; s 1:74; F 105
p
n 12; R 0:807; s 29:88; F 18 PC 0:3907 I e 43:8278 25
BP 3:9641W  57:759 11 n 12; R 0:923; s 2:27; F 58
n 12; R 0:954; s 15:18; F 101 From relations (20)(23), Randics connectivity index
p
BP 25:0414 I b  87:8578 12 (v) found to be very good for critical pressure (PC). How-
p
ever, the square root of the bonding information index, Ib
n 12; R 0:990; s 6:95; F 521
p (24) performs even good relationship, compared to Ran-
BP 3:5031 I e  64:5607 13 dics connectivity index (v).The square root of net-sign
p
n 12; R 0:965; s 13:14; F 138 identity information index, Ie (25) shows better relation
than Wiener index (W) for PC.
From relations (8)(11), Randics connectivity index (v) Critical temperature (TC)
found to be very good for boiling point (BP). However,
p the
TC 0:0951I e 104:74 26
square root of the bonding information index, Ib (12)
performs similar to Randics connectivity index (v) and n 12; R 0:882; s 30:95; F 35
the TC 102:93v  52:182 27
p square root of net-sign identity information index,
Ie (13) shows better relation than Wiener index (W) for n 12; R 0:989; s 9:56; F 461
BP. TC 81:518J  19:468 28
Molar refractions (MR) n 12; R 0:815; s 38:04; F 19
MR 0:0053I e 22:687 14 TC 5:0865W 75:835 29
n 8; R 0:965; s 0:65; F 82 n 12; R 0:945; s 21:34; F 84
p
MR 6:3488v 12:036 15 TC 32:4707 I b 35:7653 30
n 12; R 0:992; s 8:23; F 626
n 8; R 0:841; s 1:35; F 14 p
TC 4:5228 I e 66:4423 31
MR 2:1413J 22:419 16
n 12; R 0:963; s 17:65; F 128
n 8; R 0:319; s 2:36; F 1
From relations (26)(29), Randics connectivity index
MR 0:3036W 20:277 17 (v) found to be very good for critical temperature (TC).
n 8; R 0:936; s 0:87; F 46 However,
p the square root of the bonding information
p index, Ib (30) performs even good relationship, compared
MR 2:4317 I b 15:1904 18 to Randics connectivity index (v).The square root of net-
p
n 8; R 0:912; s 1:02; F 29 sign identity information index, Ie (31) shows better rela-
p tion than Wiener index (W) for TC.
MR 0:3207 Ie 18:0238 19
n 8; R 0:971; s 0:59; F 99 3.2. Unsaturated hydrocarbons
From relations (14)(17), the net-sign identity informa- The correlation models for the three dierent properties
tion index, Ie found to be very good for molar refractions for unsaturated hydrocarbons are obtained as:
(MR), even compared to Wiener indexp(W). The square Molar volume (MV)
root of the bonding information index, Ib (18) also per-
forms good relationship, compared to Randics connectiv- MV 0:0266I e 47:459 32
ity index (v) and Balabans distance sum connectivity index n 13; R 0:909; s 7:15; F 53
(J).
p The square root of net-sign identity information index, MV 27:074v 6:5123 33
Ie (19) shows much better relation than net-sign identity
n 13; R 0:978; s 3:58; F 243
information index, Ie (14) for MR.
 P.K. Sahu, S.-L. Lee / Chemical Physics Letters 454 (2008) 133138 137

MV 25:886J 6:5804 34 From relations (44)(47), the net-sign identity informa-

n 13; R 0:913; s 6:99; F 55 tion index, Ie found to be very good for molar refractions
(MR), even compared to Wiener index (W). Randics con-
MV 1:3647W 40:062 35
nectivity index (v) (45) does not exhibit good relation for
n 13; R 0:956; s 5:02; F 118 MR. The square root of the bonding information index,
p p
MV 8:7229 I b 29:3007 36 Ib (48) also performs good relationship, compared to
Wiener index (W) and Balabans distance sum connectivity
n 13; R 0:984; s 3:07; F 333
p index (J). Moreover,pthe square root of net-sign identity
MV 1:2373 I e 37:2969 37 information index, Ie (49) shows much better relation
n 13; R 0:978; s 3:58; F 243 than net-sign identity information index, Ie (44) for MR.
For the unsaturated hydrocarbons, from relations (32) 4. Summary
(35), Randics connectivity index (v) found to be very good
for molar volume (MV). However,
p the square root of the For the saturated hydrocarbons and for unsaturated
bonding information index, Ib (36) performs even better hydrocarbons, the net-sign identity information index, Ie,
relationship, compared to Randics connectivity index p (v). has good relationship with considered molecular proper-
The square root of net-sign identity information index, Ie ties. However, on comparing with Wiener index (W), Ran-
(37) shows better relation than Wiener index (W) and same dics connectivity index (v) and Balabans distance sum
as compared to Randics connectivity index (v) for MV. connectivity index (J), it can be observed that the net-sign
Boiling point (BP) identity information index has proved to be better towards
BP 0:0796I e  43:379 38 predicting optical properties like molecular refraction for
n 12; R 0:863; s 27:22; F 29 both saturated and unsaturated hydrocarbons. It is also
BP 85:024v  174:91 39 shown that the new net-sign identity information index is
intriguing in describing optical properties as compared to
n 12; R 0:988; s 8:23; F 419
bulk properties in both saturated and unsaturated hydro-
BP 76:023J  158:69 40 carbons. Moreover, the square root of the bonding infor-
p
n 12; R 0:896; s 23:89; F 41 mation index, Ib is also found to be potential and much
BP 4:2085W  68:173 41 better, as compared to Randics connectivity index (v) for
n 12; R 0:941; s 18:24; F 77 bulk properties (MV, BP, etc.) and p the square root of
p net-sign identity information index, Ie is even found bet-
BP 26:7080 I b  99:4970 42 ter than the novel net-sign identity information index, Ie for
n 12; R 0:983; s 9:95; F 284 optical properties like, MR. Its wide applicability with
p
BP 3:7422 I e  74:4003 43 respect to QSAR/QSPR is currently under investigation.
n 12; R 0:954; s 16:09; F 102
Acknowledgement
From relations (38)(43), Randics connectivity index
(v) found to be very good for boiling point (BP). However,
p The reported research has been supported by the Na-
the square root of the bonding information index, Ib (42)
tional Science Council, Taiwan.
and
p the square root of net-sign identity information index,
Ie (43) show better relation than Wiener index (W) and
Balabans distance sum connectivity index (J) for BP. References
Molar refractions (MR)
[1] A.T. Balaban (Ed.), Chemical Applications of Graph Theory,
MR 0:0051I e 22:739 44 Academic, New York, 1976.
[2] L.B. Kier, L.H. Hall, Molecular Connectivity in Chemistry and Drug
n 7; R 0:911; s 0:80; F 24
Research, Academic, New York, 1976.
MR 6:7872v 10:514 45 [3] N. Trinajstic (Ed.), Chemical Graph Theory, vols. I and II, CRC,
n 7; R 0:655; s 1:47; F 4 Boca Raton, FL, 1983.
[4] R.B. King (Ed.), Chemical Application of Topology and Graph
MR 3:7355J 18:811 46 Theory, Elsevier, Amsterdam, The Netherlands, 1983.
n 7; R 0:717; s 1:36; F 5 [5] D. Bonchev, Information Theoretic Indices for Characterization of
Chemical Structure, Wiley-InterScience, New York, 1983.
MR 0:3089W 19:767 47
[6] A.T. Balaban (Ed.), From Chemical Topology to 3D Molecular
n 7; R 0:817; s 1:12; F 10 Geometry, Plenum Press, New York, 1997.
p [7] H. Kubinyi, G. Folkers, Y.C. Martin (Eds.), 3D QSAR in Drug
MR 2:6051 I b 14:1057 48 Design, vols. 13, Kluwer, ESCOM, 19961998.
n 7; R 0:872; s 0:95; F 15 [8] M. Karelson, Molecular Descriptors in QSAR/QSPR, Wiley-Inter-
p science, New York, 2000.
MR 0:3195 I e 17:8815 49
[9] R. Todeschini, V. Consonni, Handbook of Molecular Descriptors,
n 7; R 0:933; s 0:70; F 34 Wiley-VCH, Weinheim, Germany, 2000.
138 P.K. Sahu, S.-L. Lee / Chemical Physics Letters 454 (2008) 133138
[10] H. Wiener, J. Am. Chem. Soc. 69 (1947);
J. Chem. Phys. 15 (1947) 766.
[11] A.T. Balaban, Chem. Phys. Lett. 89 (1982) 399.
[12] M. Randic, J. Am. Chem. Soc. 97 (1975) 6609.
[13] L.B. Kier, L.H. Hall, W.J. Murray, M. Randic, J. Pharm. Sci. 64
(1975) 1971.
[14] D. Bonchev, N. Trinajstic, Int. J. Quantum Chem. Symp. 12 (1978)
293;
D. Bonchev, A.T. Balaban, A. Mekenyan, J. Chem. Inf. Comput. Sci.
20 (1980) 106.
[15] I. Gutman, N. Trinajstic, J. Chem. Phys. 62 (1975) 3339.
[16] H. Hosoya, Int. J. Quantum Chem. 6 (1972) 801.
[17] S.C. Basak, B.D. Gute, G.D. Grunwald, J. Chem. Inf. Comput. Sci.
36 (1996) 1054.
[18] S.-L. Lee, R.R. Lucchese, S.-Y. Chu, Chem. Phys. Lett. 137 (1987)
279.
[19] P.K. Sahu, S.-L. Lee, Chem. Phys. Lett. 396 (2004) 465.
[20] S.-L. Lee, I. Gutman, Chem. Phys. Lett. 157 (1989) 229.
[21] S.-L. Lee, Y.-N. Yeh, Chem. Phys. Lett. 171 (1990) 385.
[22] S.-L. Lee, F.-Y. Li, F. Lin, Int. J. Quantum Chem. 39 (1991) 59.
[23] S.-L. Lee, Y.-L. Luo, E.B. Sagan, Y.-N. Yeh, Int. J. Quantum Chem.
41 (1992) 105.
[24] S.-L. Lee, Theor. Chim. Acta 81 (1992) 185.
[25] S.-L. Lee, Y.-N. Yeh, J. Math. Chem. 13 (1993) 75.
[26] I. Gutman, S.-L. Lee, Y.-N. Yeh, Chem. Phys. Lett. 191 (1992) 87.
[27] I. Gutman, S.-L. Lee, Y.-N. Yeh, Int. J. Quantum Chem. 49 (1994)
87.
[28] P. K. Sahu, S.-L. Lee, submitted for publication.
[29] Lord Kelvin, Baltimore Lecture on Molecular Dynamics and the
Wave Theory of Light, C.J. Clay, London, 1904, pp. 439, 619.
[30] N.E. Diane, I.C. Wei, P.G. Seybold, J. Am. Chem. Soc. 110 (1988)
4186.
[31] L. Xu, C. Hu, Application of Chemical Graphs, Scientic Press,
Beijing, 2000.
[32] L.S. Wang, Z.L. Zhi, Molecular Connectivity and Molecular Struc-
ture Activity, Chinese Environment Science Press, Beijing, 1992.