Acta Chim. Slov. 2002, 49, 497-514. 497 SOME TOPOLOGICAL INDICES DERIVED FROM THE vmdn MATRIX. PART 5. SUMMATION-DERIVED SUSCEPTIBILITIES FOR BRANCHING AS BIA TYPE INDICES Anton Perdih*, Branislav Perdih Mala vas 12, SI-1000 Ljubljana, Slovenia Received 02-12-2001 Abstract The SWA(m,n) indices derived from the vmdn matrix raise expectations that at least two groups of them might be good branching indices of BIA type. The indices of one of these groups indicate that a peripherally substituted alkane is more branched than a centrally substituted one, whereas the indices of the other group indicate the reverse. Some of the SWA(m,n) indices correlate well, having | r | > 0.99, with physicochemical properties co and Tc/Pc. Several ones have | r | > 0.9 with BP/Tc, Tc2/Pc, C, AHf°g, Pc, and AHv. Introduction Several hundred topological indices have been developed and tested for their performance as branching indices or indices of substances’ properties.1,2 A substantial part of them is derived from one or another matrix associated with molecular structure. Several authors considered, for example, the adjacency matrix, the distance matrix, and the reciprocal distance matrix to be different types of matrices. Ivanciuc3 mentions even 14 different types of matrices as sources of topological indices. Estrada4 developed a matrix that enables the derivation of an infinite number of indices. We5 presented some types of matrices that enable the derivation of an infinite number of indices and we have shown that these matrices represent a step in unification of several matrices used to derive topological indices, i.e. of the adjacency matrix, the distance matrix, the reciprocal distance matrix, etc. Topological indices have been correlated with several physical, chemical, and biological properties of molecules. However, even several properties of alkanes still cannot be well described with particular available indices6 and combinations of them are to be used.7 In spite of that, interest in topological indices has grown remarkably during recent years. Therefore, the study of those topological indices that might be good branching indices remains an important area of research. A.Perdih, B. Perdih: Some topological indices derived from the vmd n matrix. Part 5. Summation... 498 Acta Chim. Slov. 2002, 49, 497-514. In previous papers8-10 the suitability of 13 topological indices as branching indices, as well as of 25 physicochemical properties as reference properties for branching of alkanes was studied. The properties were divided into intrinsic and interaction-dependent ones and it was explained why most of the latter ones are not suitable as primary references for branching. The best reference properties to assess branching indices were found to be ?Hf°g, BP/Tc, and Tc/Pc. Two definitions of branching were presented, the Methane based definition as a general definition and the n-Alkane based definition as its subdefinition, more familiar to chemists working in this field. The indices obeying these definitions were labelled BIM and BIA indices, respectively. The search for true branching indices that would not necessarily fit particular properties but would only index branching has been encouraged. In the present paper are evaluated the BIA indices derived from a generalized distance matrix,5 the vmdn matrix. This generalized matrix allows the derivation of an infinite number of indices and we present here the properties of two sets of 225 indices derived from it. Data and notations The structures of alkanes are presented in shorthand, e.g. Hp is n-heptane, Oct is n-octane, 223M5 is 2,2,3-trimethylpentane, 3E2M5 is 3-ethyl-2-methylpentane, etc. The other terms are explained on 2,2-, 2,3- and 2,5-dimethyl hexane (22M6, 23M6 and 25M6) as examples. The two branches (i.e. the number of branches, Nbr = 2) in 22M6 are positioned on a quaternary carbon (2q) placed on the periphery (per) of the molecule. The two branches in 23M6 and 25 M6 are positioned on tertiary carbons (2t). In 23M6 the branches are adjacent (adj) and those in in 25M6 are distant (dist). The branches on carbons No. 2 and 5 are placed on the periphery of the molecule, and the one on carbon No. 3 is placed near the centre (ctr) of the molecule. 25M6 is symmetric, whereas 22M6 and 23M6 are not. The physicochemical properties The data for the boiling point (BP), density (d), the critical data Tc, Pc, Vc, Zc, ? c, and dc, as well as the standard enthalpy of formation for the ideal gas (?Hf°g), the enthalpy of vaporisation (?Hv), the Antoine constants A, B, and C, as well as the A.Perdih, B. Perdih: Some topological indices derived from the vmd n matrix. Part 5. Summation... Acta Chim. Slov. 2002, 49, 497-514. 499 Pitzer's acentric factor (co) and the refractivity index (nD) were taken from the CRC Handbook11 or from Lange's Handbook.12 The data for the liquid molar volume (Vm), the ratios Tc2/Pc and Tc/Pc used instead of the van der Waals parameters a0 and b0, the ratio BP/Tc (i.e. reduced BP), and the molar refraction (MR) were calculated from data presented in the handbooks. Methods The susceptibility for branching The susceptibility for branching is defined as the normalised difference of the indices' or properties' values,9 Eq. 1, Sn,i = Xi/Xn - 1 (1) where Sn,i is the susceptibility for branching, X is an index or a property, the subscript n referers to the n-alkane of a particular carbon number and the subscript i refers to any alkane of the same carbon number. For example, in S8,i the digit 8 refers to n-octane and i to any octane. In S8,2m7, 2M7 refers to 2-methyl heptane. Results and discussion The vmdn matrix is in general nonsymmetric. It has been shown that m = 0 and n = -oo give the adjacency matrix, the case m = 0, n = 1 gives the distance matrix, the case m = 0, n = -1 gives the reciprocal distance matrix, etc.5 It has the main diagonal elements gii = 0 and the nondiagonal elements gij (i*j) = vjmxdij n, where vj is the degree of vertex j (in alkanes it is the number of C-C bonds the carbon in question is involved in) and dij is the shortest distance from vertex i to vertex j (in alkanes it is the smallest number of bonds between the carbons in question). The indices can be derived from the generalized matrices introduced above e.g. by summation of its elements, like the Wiener13 index or by calculating the leading eigenvalues of the matrices. In present paper we consider the indices derived from the vmdn matrix presented above by summation of its elements. In a previous paper5 we studied the W(m,n) indices, which were derived from the vmdn matrix by summation of its elements. They are the BIM type of indices, i.e. they obey the Methane based definition of branching. To derive the BIA type of W(m,n) A.Perdih, B. Perdih: Some topological indices derived from the vmd n matrix. Part 5. Summation... 500 Acta Chim. Slov. 2002, 49, 497-514. indices, i.e. the indices obeying the n-Alkane based definition of branching and labelled here as WA(m,n) indices, we can use the susceptibility for branching14 of the W(m,n) indices.5 We label this type of BIA indices, which are derived from the vmdn matrix by summation of its elements followed by deriving their susceptibilities for branching, the SWA(m,n) indices. The properties of SWA(m,n) indices The SWA(m,n) indices of n-alkanes are equal to zero by definition. Some of the SWA(m,n) indices are negative and their absolute values seem an attractive possibility to be used. Later shall be shown that in several cases there are the properties of the abs(SWA(m,n)) indices different from the genuine SWA(m,n) indices and they present an additional set of the BIA type indices. How the values of SWA(m,n) indices depend on exponents m and n Fig. 1 serves as an illustration that the dependence of values of the SWA(m,n) indices on exponents m and n is saddle-like. Fig. 1. Two views of the values of SWA(m,n) indices of 2,2,3,3-tetramethyl butane in the plain of exponents m and n. A.Perdih, B. Perdih: Some topological indices derived from the vmd n matrix. Part 5. Summation... Acta Chim. Slov. 2002, 49, 497-514. 501 The values of SWA(m,n) indices are higher at 2233M4 than at 234M5, especially when n < 2 and m > 0 or m < -1. At m > 0 the effect is caused i.a. by the higher contribution of quaternary than tertiary structures. SWA(m,n) indices which are integers Few SWA(m,n) indices are integers. SWA(m,n) = 0 when m = 0 and n = -? or 0, as well as when m = -1 and n = -?, and when m = 1 and n = 0, as it was observed among the W(m,n) indices of BIM type,5 from which the SWA(m,n) are derived. The SWA(m,n) indices are in general not integers. Degenerated SWA(m,n) indices The SWA(m,n) indices, Table 1, are highly degenerated when n = -? or 0 as well in some cases when n = -1 or 1 or 2 and m = -? or -1 or 0 or 1 or 2. m 3 2 1 1/2 < m < 1/4 0 -1/4 < m < -1/2 -1 -2 < m < -6 -00 15 15 15 16 4 2 16 18 4 2 15 15 18 2 18 4 15 15 18 15 4 2 15 15 16 2 16 6 4 -oo -oo< n < -1 -1 -Kn < 0 0 0 < n < 1 1 2 3 n Table 1. Degeneration of the SWA(m,n) indices among octanes expressed as the number of data having at least one equal counterpart among 18 possible ones. How the structural features influence the SWA(m,n) indices When we studied the physicochemical properties of alkanes we have shown that they are influenced by several structural features, e.g. by the size of molecule, by the number of branches, by the type of the branched structure, by the position of branches, by the separation between branches, etc.8 By definition (see Eq. 1) all SWA(m,n) indices of n-alkanes are equal to zero. Thus the direct influence of the size of molecule is A.Perdih, B. Perdih: Some topological indices derived from the vmd n matrix. Part 5. Summation... 502 Acta Chim. Slov. 2002, 49, 497-514. excluded. A qualitative presentation of the influence of particular structural features on the SWA(m,n) indices, based on sequences of isomers, is presented in Tables 2-5. Number of branches The influence of the number of branches is presented in Table 2. In Table 2 there are two regions where the values of the SWA(m,n) indices of octanes decrease with the number of branches. The values of these indices are negative. One region is observed at high n, the other at low n and they are observed especially but not exclusively at -1 < m < 1. Between them is the region where the values of SWA(m,n) indices of octanes increase with the number of branches and they are positive. On the boundaries of these regions there is an intermediate region where the values of the SWA(m,n) indices are either equal to 0 or seem to depend on the number of branches in an irregular way. m 3 t t t t t t t t 1- 4+ 3-i 4 2 t t t t t t t 4- 2+ 4 4 1 1/2 t t t t t t ! t 0 i 4 4 4 4 4 4 4 4 4 4 4 2+ 4 4 1/3 t t t i 1+ 4 4 4 4 4 4 4 1/4 t t t t 4 4 4 4 4 4 4 0 -1/4 0 t t t t 0 i 4 4 4 4 4 4 4 4 4 4 ^ 4 t ! 3+ 4 -1/3 -1/2 -1 4 4 4 4 i t i t t t t t t t t : 4+ 11- 3+ 1+ 5- 4 2+ 2- 4 4 4 4 4 4 t 4 0 t t t 1+ 2- 4 -2 -4 t t t t t t t t t t t t t t t t 2+ 4 4 t 1+ 2-i 4 -6 t t t t t t t t t 1+ 6-i 4 -00 t t t t t t t t t 1+ 8-i 4 -00 -6 -4 t Op Op Op Op Op Op Op q>t p>c p>c p>c p>c c>p Op 2 q>t Op Op Op Op Op Op Op q>t p>c p>c p>c c>p Op Op 1 q>t Op Op Op Op Op Op Op 0 Op Op Op Op Op Op v2 q>t Op Op Op Op Op Op c>p q>t Op Op Op Op Op Op v3 q>t Op Op Op Op Op Op c>p q>t Op Op Op Op Op Op v4 q>t Op Op Op Op Op Op Op q>t Op Op Op Op Op Op 0 0 Op Op Op Op Op Op Op 0 Op Op Op Op Op Op -V4 q>t Op Op Op Op Op Op Op q>t c>p Op Op Op Op Op -V3 q>t Op Op Op Op Op Op q>t p>c c>p Op Op Op Op -V2 q>t Op p>c Op Op Op Op Op q>t p>c p>c c>p Op Op Op -1 0 p>c p>c Op Op Op Op Op q>t p>c p>c p>c c>p Op Op -2 q>t p>c p>c Op Op Op Op q>t p>c p>c p>c c>p Op Op -4 q>t p>c p>c Op Op Op q>t p>c p>c p>c p>c c>p Op -6 q>t p>c p>c Op Op Op q>t p>c p>c p>c p>c c>p Op -? q=t p>c Op Op Op q=t p>c p>c p>c p>c c>p Op -? -6 -4 -2 -1 n Table 3. The SWA(m,n) indices of octanes indicate which position of branches seems to contribute more to the degree of branching. The contribution of the position of branches is superimposed to the direction of the contribution of the number of branches, Table 2. The contribution of two branches in a quaternary (q) structure is higher than the contribution of three branches in tertiary structures (2q>3t) The contribution of two branches in a quaternary structure is equal to that of three branches in tertiary structures (2q=3t) The contribution of two branches in a quaternary structure is higher than in tertiary structures (2t<2q<3t) The contribution of two branches in a quaternary structure is equal to that in tertiary structures (2q=2t) 0 The position of branches has no influence Empty space: The position of branches seems to have little influence c>p: ctr>2233>...>Oct>per p>c: per>2233>...>Oct>ctr c>p: 2233>ctr>...>Oct>per p>c: per>2233>...>Oct>ctr c>p: ctr>2233>...>per>Oct p>c: per>2233>...>Oct>ctr c>p: 2233>ctr>...>per>Oct p>c: per>2233>...>Oct>ctr Example for c>p (at SWA(-1/2,1/2): 3E3M5 < 233M5 < 2233M4 < 3E2M5 < 33M6 < 223M5 < 3E6 < 34M6< 234M5 < 23M6 < 4M7 < 24M6 < 224M5< 3M7 < 22M6 < Oct (= 0) < 25M6 < 2M7 q>t q>t q>t q=t This is the consequence of the saddle-like dependence of their values on the exponents m and n, cf. ref.5 If absolute values of SWA(m,n) indices are taken, then the correlations with indices in the intermediate regions alter their values whereas those in regular regions may change only the sign. Absolute values of the SWA(m,n) indices in A.Perdih, B. Perdih: Some topological indices derived from the vmd n matrix. Part 5. Summation... 504 Acta Chim. Slov. 2002, 49, 497-514. the intermediate regions of Table 2 present thus a second group of BIA type indices that should be also tested for their possible usefulness. From this point on we do not consider any more whether the values of an index are positive or negative, or, more positive or more negative, but only whether a structural feature causes that an index presents the octane having that structural feature as more branched or less branched than the other octanes. What holds true for octanes, holds true also for lower alkanes if not explicitly indicated otherwise. Position of branches Regarding the influence of the position of branches is the situation among the SWA(m,n) indices quite complex, Table 3. There are two regions where the position of branches has no influence on the SWA(m,n) indices: SWA(m,-?) and SWA(m,0). There are three triangle-like regions where the SWA(m,n) indices indicate that an octane having the branch(es) near the periphery of molecule is more branched than that having the branch(es) near the centre of molecule. One region is, roughly speaking, at m > 1 and 0 < n < 2, another is at m < -1/3 and -? < n < -1 or -2, and the third one is in a triangle at m < -1/4 and 0 < n < 2. The majority of tested SWA(m,n) indices indicates that an octane having the branch(es) near the centre of molecule is more branched than that having the branch(es) near the periphery. The positions in the plane of exponents m and n, where the influence of the position of branches is higher than the influence of their number are presented in boldface. Separation between branches The contribution of the separation between branches is presented schematically in Table 4. The values of the indices SWA(m,-?) and SWA(m,0) do not depend on the separation between branches. The situation is otherwise to some extent similar to that in Table 3: at low m and n values, i.e. at m < -1/2 and n < -2, as well as at m < -1/4 or m > 1 and 0 < n < 2 or 1, respectively, the values of SWA(m,n) indices indicate that the larger the separation between branches the more branched seems an octane isomer. In other cases, the values of SWA(m,n) indices indicate that an octane isomer is the less branched the larger is the separation between branches. A.Perdih, B. Perdih: Some topological indices derived from the vmd n matrix. Part 5. Summation... Acta Chim. Slov. 2002, 49, 497-514. 505 m 3 0 i i i 0 T t T i i i 2 0 i i i 0 T T i i i i -1/4 > > > > = < < < > 2 = > > > > > = < < > > -1/3 < m < 1 = > > > > > = > > > > -1/2 = > < > > > = < > > > -1 = < < > > > = < < > > -2 = < < < > > = < < < > -4 = < < < < > = < < < > -6 = < < < < > = < < < > -00 = < < < < > = < < < > -00 - 6 -4 -2 -1 -1/2< n< -1/4 0 n 0 < n < 1/3 1 / 2 1 n>2 Table 5. The contribution of the type of branches to the values of SWA(m,n) indices. > The ethyl substituted octane is represented by that SWA(m,n) index as more branched than the methyl substituted one. < The ethyl substituted octane is represented by that SWA(m,n) index as less branched than the methyl substituted one. = The index does not distinguish between the ethyl and methyl substituent, important is only the number of them. A.Perdih, B. Perdih: Some topological indices derived from the vmd n matrix. Part 5. Summation... 506 Acta Chim. Slov. 2002, 49, 497-514. Type of branches There are also some differences when the branches are of different type, i.e. whether a branch is methyl or ethyl, Table 5. The values of SWA(m,-?) and SWA(m,0) indices do not depend on the type of branches. At low m and n values, i.e. at m < -1/2 and n < -1, as well as at m < -1/3 or m > 1 and 0 < n < 2, the values of SWA(m,n) indices indicate that the structure containing branches in form of ethyl groups are less branched than those containing methyl groups. In other cases, the values of SWA(m,n) indices indicate that an octane isomer is more branched if it contains an ethyl group as a branch. This situation is to some extent similar to that in Table 4. Which SWA(m,n) indices could be good branching indices? There do not exist agreed criteria what characteristics should have a good branching index. Consequently, there exist several definitions of branching. One of the definitions is, for example, based on the Wiener13 number,15 some other ones are based on the leading eigenvalue of adjacency matrix,16 or the leading eigenvalue of path matrix.17 We presented the Methane based definition of branching as well as the n-Alkane based one8 and evaluated a set of 13 most frequently used topological indices by a number of criteria, including partial sequences of isomers having equal number and type of branches.10 By intuition, the next step in evaluation of indices would be the assumption that a good branching index should have a regular sequence of all isomers. What would be a regular sequence? Studying 21 physicochemical properties of alkanes,8 we came to the conclusion that in a regular sequence of isomers the influence of the number of branches should be higher than that of the position of branches, followed by the separation between branches and the type of the branched structure. Consequently, branching should not be defined by topological indices but by structural features of molecules. Taking this conclusion as a guide, we can extend the principle of a regular sequence to all isomers in order to construct some “ideal” sequences of octanes of increasing branching, e.g., Oct < 2M7 < 3M7 < 4M7 < 3E6 < 25M6 < 24M6 < 23M6 < 34M6 < 3E2M5 < 22M6 < 33M6 < 3E3M5 < 234M5 < 224M5 < 223M5 < 233M5 < 2233M4, which indicates that a centrally substituted alkane is more branched than a peripherally substituted one, or, A.Perdih, B. Perdih: Some topological indices derived from the vmd n matrix. Part 5. Summation... Acta Chim. Slov. 2002, 49, 497-514. 507 Oct < 3E6 < 4M7< 3M7 < 2M7 < 3E2M5 < 34M6 < 23M6 < 24M6 < 25M6 < 3E3M5 < 33M6 < 22M6 < 234M5 < 233M5 < 223M5 < 224M5 < 2233M4, which indicates that a peripherally substituted alkane is more branched than a centrally substituted one. The sign can be either < as above, or >. The Wiener13 number, identical with W(0,1),5 from which the index SWA(0,1) is derived and on which is based the approach of Bonchev and Trinajstiæ,15 has the sequence: Oct > 2M7 > 3M7 > 4M7 > 25M6 > 3E6 > 22M6 = 24M6 > 23M6 > 34M6 > 33M6 = 3E2M5 > 224M5 > 234M5 > 3E3M5 > 223M5 > 233M5 > 2233M4. The leading eigenvalue of adjacency matrix, X1,16 has the sequence: Oct < 2M7 < 3M7 < 4M7 = 25M6 < 3E6 < 24M6 < 23M6 < 34M6 < 3E2M5 < 22M6 < 234M5 < 224M5 < 33M6 < 3E3M5 < 223M5 < 233M5 < 2233M4. The leading eigenvalue of path matrix17 has the sequence: Oct > 2M7 > 3M7 > 4M7 > 25M6 > 3E6 > 24M6 > 23M6 > 22M6 > 34M6 > 3E2M5 > 33M6 > 224M5 > 234M5 > 3E3M5 > 223M5 > 233M5 > 2233M4. Neither the Wiener13 number, nor the leading eigenvalue of adjacency matrix16 and the leading eigenvalue of path matrix17 has an “ideal” sequence of octane isomers. Therefore these indices are not good bases to define branching. The physicochemical properties, found to be the most appropriate references to assess branching9 have the following sequences of isomers: CO : Oct < 2M7 < 4M7 < 3M7 < 3E6 < 25M6 < 23M6 < 24M6 < 34M6 = 22M6 < 3E2M5 < 33M6 < 234M5 < 3E3M5 = 224M5 < 223M5 < 233M5 < 2233M4 Tc/Pc Oct < 2M7 < 3M7 < 25M6 < 4M7 < 22M6 < 3E6 < 24M6 < 23M6 < 33M6 < 34M6 < 224M5 < 3E2M5 < 234M5 < 223M5 < 3E3M5 < 233M5 < 2233M4 BP/Tc Oct < 2M7 < 4M7 < 3M7 < 25M6 < 3E6 < 24M6 < 22M6 < 23M6 < 34M6 < 3E2M5 < 33M6 < 224M5 < 234M5 < 223M5 < 3E3M5 < 233M5 < 2233M4 Tc2/Pc Oct < 2M7 < 3M7 < 4M7 < 3E6 < 25M6 < 23M6 < 22M6 < 34M6 < 24M6 < 3E2M5 < 33M6 < 3E3M5 < 234M5 < 233M5 < 223M5 < 224M5 < 2233M4 C: Oct < 3M7 < 4M7 = 3E6 < 2M7 < 23M6 < 25M6 < 24M6 < 34M6 < 22M6 < 3E2M5 < 33M6 < 234M5 < 223M5 < 3E3M5 < 233M5 < 224M5 < 2233M4 AHf°g °ct < 3E6 < 3E2M5 < 4M7 < 3M7 < 34M6 < 23M6 < 3E3M5 < 2M7 < 233M5 < 234M5 < 24M6 < 33M6 = 223M5 < 25M6 < 224M5 < 22M6 < 2233M4 whereas AHv °ct < 3M7 = 4M7 < 2M7 < 3E6 < 34M6 < 23M6 < 3E2M5 < 3E3M5 < 234M5 < 25M6 < 24M6 < 33M6 < 233M5 < 22M6 < 223M5 < 2233M4 < 224M5 BP Oct < 3M7 < 3E6 < 3E3M5 < 34M6 < 4M7 < 2M7 < 3E2M5 < 23M6 < 233M5 < 234M5 < 33M6 < 223M5 < 24M6 < 25M6 < 22M6 < 2233M4 < 224M5 ctr > per:&, Tc/Pc, BP/Tc per > ctr: AHf°g, AHv, BP A.Perdih, B. Perdih: Some topological indices derived from the vmd n matrix. Part 5. Summation... 508 Acta Chim. Slov. 2002, 49, 497-514. None of them has a regular or “ideal” sequence. Among all of them in some instances the influence of the position of branches overrides the influence of the number of branches. The physicochemical properties co, Tc/Pc, and BP/Tc indicate that a centrally substituted alkane is more branched than a peripherally substituted one, whereas AHf°g, AHv, and BP indicate that a peripherally substituted alkane is more branched than a centrally substituted one. The situation is not as clear at Tc2/Pc and C. m 3 2q>3t ® ® ® ® ® ® 2q>3t ** ** ** 2 2q>3t ® ® 2q=3t 1 2q=3t 0 1/2 q>t # # q>t 1/3 q>t # # q>t 1/4 q>t # # q>t 0 0 0 -1/4 q>t q>t -1/3 q>t ® # q>t -1/2 q>t # # # # # # q>t -1 0 * # # # # q>t -2 q>t * * q>t -4 q>t * q>t -6 q>t q>t -00 Nbr Nbr -Qo -6 -4 -2 -1 -1/2 -1/3 -1/4 0 n 1/4 1/3 1/2 2 3 Fig. 2. The position of SWA(m,n) indices considered as the best candidates for good branching indices. The sequences of isomers and the meaning of labels *, **, #, and ® are presented in the text. Nbr: The index depends only on the number of branches q>t: The number of branches and the type of the branched structure influence these indices. Two branches on a quaternary carbon have a higher contribution than two branches on tertiary carbons, in fact 2q>2t. The question, whether some SWA(m,n) indices have the “ideal” sequence of octane isomers is answered in Fig. 2, where the position of the SWA(m,n) indices, candidates for good branching indices, is presented in the plane of exponents m and n. There is a number of tested SWA(m,n) indices having one or another “ideal” sequence of isomers. 1 A.Perdih, B. Perdih: Some topological indices derived from the vmd n matrix. Part 5. Summation... Acta Chim. Slov. 2002, 49, 497-514. 509 Four of them, namely SWA(-1,-4), SWA(-2,-4), SWA(-4,-4), and SWA(-2,-6) have the sequence: *: Oct < 3E6 < 4M7< 3M7 < 2M7 < 3E2M5 < 34M6 < 23M6 < 24M6 < 25M6 < 3E3M5 < 33M6 < 22M6 < 234M5 < 233M5 < 223M5 < 224M5 < 2233M4 indicating that a peripherally substituted alkane is more branched than a centrally substituted one. The indices SWA(3,1/2), SWA(3,1/3), and SWA(3,1/4) have the sequence: **: Oct < 3E6 < 4M7< 3M7 < 2M7 < 3E2M5 < 34M6 < 23M6 < 24M6 < 25M6 < 234M5 < 3E3M5 < 33M6 < 22M6 < 233M5 < 223M5 < 224M5 < 2233M4 indicating also that the structure 3t is felt less branched than the structure 2q. Seventeen SWA(m,n) indices, namely SWA(-1/3,-1/4), SWA(-1/2,-1/4), SWA(-1,-1/4), SWA(-1/2,-1/3), SWA(-1,-1/3), SWA(-1/2,-1/2), SWA(-1,-1/2), SWA(-1/2,-1), SWA(-1,-1), SWA(-1/2,-2), SWA(1/2,-4), SWA(1/3,-4), SWA(1/4,-4), SWA(1/2,-6), SWA(1/3,-6), SWA(1/4,-6), and SWA(-1/2,-6) have the sequence: #: Oct < 2M7 < 3M7 < 4M7 < 3E6 < 25M6 < 24M6 < 23M6 < 34M6 < 3E2M5 < 22M6 < 33M6 < 3E3M5 < 234M5 < 224M5 < 223M5 < 233M5 < 2233M4 indicating that a centrally substituted alkane is more branched than a peripherally substituted one. Nine tested indices: SWA(3,-6), SWA(2,-6), SWA(3,-4), SWA(2,-4), SWA(-1/3,-4), SWA(3,-2), SWA(3,-1/2), SWA(3,-1/4), and SWA(3,-1/3) have the sequence: ?: Oct < 2M7 < 3M7 < 4M7 < 3E6 < 25M6 < 24M6 < 23M6 < 34M6 < 3E2M5 < 234M5 < 22M6 < 33M6 < 3E3M5 < 224M5 < 223M5 < 233M5 < 2233M4 Most of SWA(m,n) indices, candidates for good branching indices, have n < 0. Among physicochemical properties of alkanes as well as among topological indices associated with their molecular structure we do not observe the same direction of dependence on the structural features. There do not increase all physicochemical properties with the size of molecule or with increasing degree of branching, be it expressed as the number of branches, their position, the separation between branches, their type, etc. Therefore, there is not to be expected that only one branching index or only one set of them should exist. The results presented above indicate that at least two (independent) sets of branching indices should be sought for. One set of branching indices should indicate that a centrally substituted alkane is more branched than a A.Perdih, B. Perdih: Some topological indices derived from the vmd n matrix. Part 5. Summation... 510 Acta Chim. Slov. 2002, 49, 497-514. peripherally substituted one, whereas another set of them should indicate that a peripherally substituted alkane is more branched than a centrally substituted one. Correlation between the SWA(m,n) indices and physicochemical properties The correlation between the SWA(m,n) indices and 20 physicochemical properties, assuming the linear relationship, is presented in Fig. 3 and 4. The indices SWA(1,0), SWA(0,0), SWA(0,-oo), and SWA(-1,-oo) do not index branching. m 3 2 1 1/2 1/3 1/4 0 -1/4 -1/3 -1/2 -1 -2 -4 -6 -00 i Vm : * C t/p : B/T CO AHv ......J ® ** ac T2/P ....... ...... i ## i Zc : B Pc A -00 -6 -4 -2 -1 -1/2 -1/3 -1/4 0 1/4 n 1/3 1/2 1 2 3 Figure 3. The position of 20 physicochemical properties determined by the highest correlation coefficient (r; data in parentheses) for data of abs((SWA(m,n)) indices of octanes, in the plane of exponents m and n. Single standing ones: C (0.97), AHv (-0.93), ac (-0.74), ro (-0.996), Vm (-0.69), Zc (0.64), B (-0.74), Pc (0.95), A (-0.77), T/P: Tc/Pc (-0.99), B/T: BP/Tc (-0.99), T2/P: Tc2/Pc (-0.98), ##: dc (0.83), Vc (-0.84), ®: AHf°g (0.94), BP (-0.88), *: d (0.70), nD (0.68), **: Tc (0.70), MR (-0.89), In Fig. 3 the positions of the best correlation coefficients between the 20 tested physicochemical properties and abs(SWA(m,n)) indices of octanes are presented in the plane of exponents m and n. Some of them, i.e. those of the properties AHf°g (0.94), BP (-0.88), Tc (0.70), MR (-0.89), dc (0.83), Vc (-0.84), and B (-0.74) are placed in the A.Perdih, B. Perdih: Some topological indices derived from the vmd n matrix. Part 5. Summation... Acta Chim. Slov. 2002, 49, 497-514. 511 transition region marked with dotted lines, whereas most of them are positioned outside the transition region. In Fig. 4 the positions of the best correlation coefficients between 20 tested physicochemical properties and SWA(m,n) indices of octanes are presented in the plane of exponents m and n. In this case, the best correlation coefficients of the following properties, AHf°g (0.95), BP (-0.87), MR (0.89), B (-0.74), and Tc (-0.75) are placed in the transition region. Markedly different is the position of Tc, dc, and Vc. The differences in the absolute values of their correlation coefficients relative to those with abs(SWA(m,n)) indices are marginal. Thus both sets of indices are nearly equivalent if we neglect the difference in the sign of the correlation coefficients. The best correlation coefficients, r (SWA(m,n), Property), were observed among the pairs: SWA(0,-2) and cd (-0.996); SWA(1/2,-1/2) and Tc/Pc (-0.994), SWA(1/4,-1) and BP/Tc (-0.987), SWA(1/2,1/4) and Tc2/Pc (-0.981), SWA(2,-1) and C (0.97), SWA(3,1) and AHf °g (0.94), as well as SWA(2,1/4) and AHv (-0.93). m 3 : <8> MR 2 1 1/2 C T/P AHv T2/P ac 1/3 1/4 B/T 0 -1/4 : i Vm CO ## -1/3 ! * -1/2 -1 ..... Zc : : -2 -4 !- B Pc -6 -00 A Tc i -00 -6 -4 -2 -1 -1/2 -1/3 -1/4 0 n 1/4 1/3 1/2 1 2 3 Figure 4. The position of 20 physicochemical properties determined by the highest correlation coefficient (r; data in parentheses) for data of SWA(m,n) indices of octanes, in the plane of exponents m and n. Single standing ones: MR (0.89), C (0.97), AHv (-0.93), ac (0.74), a (-0.996), Vm (-0.69), Zc (0.64), B (-0.74), Pc (0.95), A (-0.77), Tc (-0.75), T/P: Tc/Pc (-0.99), B/T: BP/Tc (-0.99), T2/P: Tc2/Pc (0.98), ##: dc (-0.83), Vc (0.84), ®: AHf°g (0.95), BP (-0.87), *: d (0.70), nD (0.68), A.Perdih, B. Perdih: Some topological indices derived from the vmd n matrix. Part 5. Summation... 512 Acta Chim. Slov. 2002, 49, 497-514. Fig. 5 illustrates how different SWA(m,n) indices have similar correlation coefficients with a physicochemical property. This is represented by seven physicochemical properties having the best correlations. The positions of the five best correlations are grouped in particular areas (co, BP/Tc, Tc2/Pc, C) or spread (Tc/Pc, AHf°g, AHv) in the plane of exponents m and n. In several cases there is no great difference in the quality of the correlation among two or more possible indices, so several of them may be useful. m 3 v3 fl 2 1 v2 c2 CÖ2 cl CÖ5 b3 c3 b5 © c4 c5 vl f4 f2 al a4 v3 CÖ3 b2 © a5 v4 CÖ4 bl © © a3 a2 0 -V4 ©1 b4 © -V, -V2 -1 ...... v4 f3 v5 f5 -2 -4 i -6 i -00 : -00 -6 -4 -2 -1 -V2 -v3 -v4 0 n v4 v3 v2 1 2 3 co: Figure 5. SWA(m,n) indices of octanes having the highest correlation coefficient (r) for data of physicochemical properties. ©! (-0.9964), co2 (-0.9962), co3, co4 (-0.9959), co5 (-0.9958) Tc/Pc: © (-0.9935), © (-0.9934), © (-0.9928), © (-0.9911), © (-0.9897) BP/Tc: bl,b2 (-0.9871), b3 (-0.9870), b4 (-0.9852), b5 (-0.9844) Tc2/Pc: al (0.9815), a2 (0.9813), a3, a4 (0.9805), a5 (0.9800) C: cl (0.9706), c2 (0.9704), c3 (0.9703), c4 (0.9700), c5 (0.9696) AHf°g: U (0.9479), f2 (0.9338), f3 (0.8833), f4 (0.8772), f5 (0.8667) AHv: vl (-0.9317), f4 (-0.9313), v3 (-0.9294), v4 (-0.9244), v5 (-0.9237) A.Perdih, B. Perdih: Some topological indices derived from the vmd n matrix. Part 5. Summation... Acta Chim. Slov. 2002, 49, 497-514. 513 Conclusions Some of the SWA(m,n) indices correlate well, having | r | > 0.99, with the physicochemical properties co and Tc/Pc. Several ones have |r| > 0.9 with BP/Tc, Tc2/Pc, C, AHf°g, Pc, and AHv. The SWA(m,n) indices derived from the vmdn matrix raise expectations that some of them, especially those having the combination of exponents (m,n): (-2,-6), (-1,-4), (-2,-4), and (-4,-4), as well as (-1/2,-6), (1/2,-6), (1/3,-6), (1/4,-6), (1/2,-4), (1/3,-4), (1/4,-4), (-1/2,-2), (-1/2,-1), (-1,-1), (-1/2,-1/2), (-1,-1/2), (-1/2,-1/3), (-1,-1/3), (-1/3,-1/4), (-1/2,-1/4), and (-1,-1/4) might be good branching indices of BIA type. The indices of the former group indicate that a peripherally substituted alkane is more branched than a centrally substituted one, whereas the latter group of indices indicates the reverse. Such a dualism is also observed among some physicochemical properties of alkanes: co, Tc/Pc, and BP/Tc indicate that a centrally substituted alkane is more branched than a peripherally substituted one, whereas AHf°g, AHv, and BP indicate the reverse. These facts do not indicate that a molecule has more than one branching, one described with one set of indices and another with another set of indices, or alternatively, one defined by one set of properties and the other by another set of properties. A molecule has only one branching, but this one branching is reflected differently in different physicochemical properties as well as it is evaluated differently by different topological indices. Therefore, branching should not be defined by a topological index or by a physicochemical property. A better choice to define branching seems to be the use of structural features of a molecule. References 1. Randiæ, M.; Basak, C; Pompe, M.; Noviè, M. Acta Chim. Slov. 2001, 48, 169-180. 2. Todeschini, R.; Consonni, V. Handbook of Molecular Descriptors, Wiley-CH, New York 2000. 3. Ivanciuc, O. J. Chem. Inf. Comput. Sci. 2000, 40, 1412-1422. 4. Estrada, E. Chem. Phys. Lett. 2001, 336, 248-252. 5. Perdih, A.; Perdih, B. Acta Chim. Slov. 2002, 49, 67-110. 6. Randiæ, M.; Guo, X.; Calkins, P. Acta Chim. Slov. 2000, 47, 489-506. 7. Nikoliæ, S.; Trinajstiæ, N.; Randiæ, M. Chem. Phys. Lett. 2001, 333, 319-321. 8. Perdih, A.; Perdih, M. Acta Chim. Slov. 2000, 47, 231-259. 9. Perdih, A. Acta Chim. Slov. 2000, 47, 293-316. 10. Perdih, A. Acta Chim. Slov. 2000, 47, 435-452. 11. Lide, D. R. CRC Handbook of Chemistry and Physics, 76th Ed., CRC Press, Boca Raton 1995-96. 12. Dean, J. A. Lange's Handbook of Chemistry, McGraw-Hill, New York 1985. 13. Wiener, H. J. Am. Chem. Soc. 1947, 69, 17-20. A.Perdih, B. Perdih: Some topological indices derived from the vmd n matrix. Part 5. Summation... 514 Acta Chim. Slov. 2002, 49, 497-514. 14. Perdih, A. Acta Chim. Slov. 2001, 48, 241–246. 15. Bonchev, D.; Trinajstiæ, N. J. Chem. Phys. 1977, 67, 4517–4533. 16. Lovasz, L.; Pelikan, J. Period. Math. Hung. 1973, 3, 175–182. 17. Randiæ, M. Acta Chim. Slov. 1997, 44, 57–77. Povzetek Indeksi vrste SWA(m,n), izvedeni iz matrik vmdn, obetajo, da bi vsaj dve skupini njih lahko bili dobri predstavniki indeksov razvejanja tipa BIA. Indeksi ene od teh skupin nakazujejo, da so bolj razvejani tisti alkani, ki imajo veje pri koncu verige, indeksi druge skupine pa, da so bolj razvejani tisti, ki imajo veje blizu sredine verige. Nekateri indeksi vrste SWA(m,n) dobro korelirajo ( | r | > 0.99) s fizikokemijskima lastnostma co in Tc/Pc, drugi pa tudi ( | r | > 0.9) z BP/Tc, Tc2/Pc, C, AHf°g, Pc in AHv. A.Perdih, B. Perdih: Some topological indices derived from the vmd n matrix. Part 5. Summation...