communications a mathematical no. 47, January 2003 mete MATCDY (47) 87- 105 (2003) {and in computer chemisty ISSN 0340 - 6253 Distinction between modifications of Wiener indices Damir Vukicevié Department of Mathematics, University of Split, Croatia Abstract The Wiener index of a tree T is W'(T) = 235, d(éj) = Lem (e) ne), where my (e) and na (e) are the numbers of vertices on the two sides ofthe edge e- Recently, two modifications of this index were put forward "Ws (P) = 32, (14 (€)-na)* and Wa (T) = $2,,(d(e,9))". We show that for each 1,Az > 0, the indices "Wa, snd "Ws, are essentially different, more precisely we show there are two chemical trees that are differently ordered by the indices "Ws, and ™W,,. We also show that for each 41,42 > 0, the indices Wa, and Wa, are also essentially diferent (Received November 11, 2002) 1 Introduction ‘The molecular-graph-based quantity, known under the name Wiener index or Wiener number, is one of the most useful and most thoroughly studied molecular-structure-descriptors (1-3) and itis still a topic of current research. Details of the theory of Wiener numbers and an exhaustive bibliography is given in the recent reviews [4,5] AA large munber of modifications and extensions of the Wiener index was considered in the chemical literature; an extensive list of references on this matter can be found in the reviews (6.7) ‘The definition of the Wiener index is given by wey= Dawa io where the summation goes over all unordered pairs of vertices and d(i,3) denotes the distance between vertices ¢ andj. An immediate generalization of the Wiener number is = Yee on wy) where A is some real number. In an explicit form of this Wiener-type invariant was first pat forward in the works (8) and [9] Ics shown in [2] and 3] that the Wiener index of a tree (= a connected acyclic graph) satisfies the relation mle) m (e) where 1 (e) and v2 (¢) are the number of vertices of T lying on the two sides of He edge € and where the summation goes over all edges of T. ‘This formula inspired another modification WG) = "(G) = Son (e) male first consideresd a (10) Wy has bee shown |S. 10} that for A > 0. hotly modification of the Wiener index are suitable menses fof branching. In P10) it is demonstrated that if all trees are ordered with regard to EQ (G). then in the general case this ordering is dalferent for different A ‘This difference in otdering ways demonstrated for88 pairs of trees with clfferent nuniber of vertices and maximal vertex degree much greater than 4, hence for trees that do not pertain to isomers, aud thar ae not molocuar graphs Inv this paper, we prove the analogous elaiin but for pairs of chenaeal trees with the sare munber of vertices, (Recall that a chemical troe is a tee inv which 1 trees are the graph represeutations of alkanes [2, 3). 1 nyucl stronger ean those in [10] and have aur anmiediate chemical relevance. In dition to this. we also ‘alogous statement holds for indices Wy More precisely, we prove vertex has degree greater than 4 such chemical lis, the results communicated in this paper are Theorem 1 Let Ay, Ay € RY. such that S, # Az There are chemscul trees Gy and Gy wath the same naonber of vertices, such that "Wa (Gi) > "Ws, Ga) WAG) < Ws, (G2) Theorem 2 Let Aj. Ay € RY. such that Ay # Ap. There are chemneal trees Gy and Gz with the same number of vertices, such that, Wa (Gi) > Ws, (Ga) Way(Gi) << Wa, (G2) 1.1 Proof of the Theorem 1 Let a,b,c € (0,4) be any numbers, let q be the greatest common divisor of their nominators. and let nn be an arbitrary natural aunber. Denote by G(rt,q.4,6) the graph whose structure is stiown on the following diagram . : se eee ee oe where d (ry. e4) = nga, d(ey.e5) = nge and d(vpe4) = ng—1. Also, denote by G(n.9,¢) the graph given fon the following diagram: where d(e.04) = ngh and d(v 0%) =a 1 We start with a few anxibiary results Lemma 3. bet 4 RY and let atic & (0.4) such thal a ny, ae have san P(E Orgone) Wa (Con g.b))) san [2h 0) (a ay fe 2)89 Proof. We have [Ws (Gon. qaed) —"" WW CG (4, 9.8))] = Senge -ap~ 55 pans 2-of (+20 et \ est i ign -i?+ ]* ey [ign = P+ nt] ~ © lem 2 [ pau | Note that 35 [ign 1? + gn +]? een holes e [sat [Eee rm sem vd | ta" so that there is a sufficiently large n, such that for each n > my ~(Elea)-Elesl-Elss1)- "Elsa" )- a Sl | SS [ign - 8 ons 1p — “Eben 2 pai een : [| SE figm 2? + 29m 24]? Sn fur = 24 al wre fulfilled a wv a) any (1). it follows that if one of the conditions (1") and (1°) is Fulfilled, then both conslitionss (1) aud90 We have ee 1 | fam 18 an ca i [ean - 22 + qn] de aha fey Using the Lagrange theorein of medium value, we get =. [sgn ~ =? + qn]*! (qn ~ 22), [yar ~ uv? + an)” ~ [tan 2 + an” ve where = = =(n) is some number from the interval (i,y) tfollows that 2 + gn)” - fign 2? + fem = 24am) om Theretore, SS [ign — 2 + an] fian = 22 + gn] a [fea ee <0 em = + an) 4 —————-] =0 2 DenateWe have From (2) and (3), it follows that Analogously. we get o1 ) w (9) (6) a v2 OS fog #2 4 gn" s. fig — 2 +2" a a -0 ") Fe 22 + px 2] Pian — 2 + an} ai F fign ~ 22 + 21] ae- Jim | i — o ") — Fee 220m aap From (7). it follows that if one of the conditions (7") and (7) is fulfilled, then both conditions (7") and (7") ate fulfilled ing Taylor's theorem of medium value, we get (ign - B+ gn)* (ign — 28) 4 (ae tn teayt = (Ma eel) 2 ( (m2) 4x. (im = 21 Gon = 204+ (an =F 4 B= 24)" = ( Na wrestentae2)" G9, =) where ry = 1) (n).72 = re(n) and 75 = ra (0) ate some numbers from the interval (0,1), Thea sa T+ [inate TL esl I Ks fim) oa ws op lomes o AAD (wp aE on ja (2? 2) 4X (ign — 22)" (gn - 21) 4 a a (2yn — 2)? (oe ¢ i( a ae a AA pec =) ag — 20?93 Now, note that [Zee Uo fs, Se AL(A=1)- (ign ~ 2 + rign)*"? . ae adn { ee Denote - fod: (ign 2) gn di ee = Then we have A (ign = 2) gn edt b= > {on = agn) “> agn vin (egint agin?) ' } agit)! Jim >0. cy a so that F(a (ign —22)°78 gn ¢ AOaVenestorvan)” tans?) tim =e S =“ fA Ggn— 2) gna x(t) psec Geswene i gee rere errr eee TA Gane _ ht = m" (8) Analogously. we get (3 (ign 8)! pg SOLD Gotan * or?) Ss oo A (qn 2)" bi sand oa X (ape PY" (Qn — 28) + aa : =1 (10) PX Gan 2)" (gn94 From (8). (9) ancl (10). it follows FQ on ey ong Bere gn) d= Aa A up LL Gn 8y so that there is a sufficiently large ng, such that for each 1 > ns, T (m0 oes ton?) ai f (a (gn) te 2 cee “) ai an Xd {ian - _ y 2am = 28) + sen r ie) gt J (gn sen] oH ar) = Pa tom 2 2m = 207-48 Te (ig = AT gn g MAC UG Pareen) ton?) . Te (ign = PYP4 2 4 MO) we a A (ion oe em -2)+ UA paeem Gemeente ail! gn 25? Fx (ag — 2)" gna "0 fag = PoE 26a lin 0 ay fs (a - 2) (2g 21) dt Fon (11). it follows that if one of the conditions (11”) and (11") is fulfilled, then both conditions, (10) aul (10) ane flied,95 Now, we have Fam = 2) d (2qn = 21) com oa #0. = PA (ign 2) gn = 21) at bn ‘Therefore the condition (11) is not fulfilled, and then (11”) is also not fulfilled. [t follows that (7"") is not Fulfilled, but then (7”) is also not fulfilled. This implies that (1) is not fulfilled, Therefore, (1°) (7), (11') and (12') are fulfilled. From (1"). (7'). (11') and (12), it follows that for each 1 > max {rej tay) . we have san [IVa (reg. ae) =" Ws Oe qb) = = sen -8y nly (et s0 it is sufficient to take mg = max (%),M2. 23h Lemma 4 Let As. 42 © RY, such that A, # Ay. There exss! numbers ate © (0.4) 1Q. such that ac bcc and either 2(b- BY (wat) fe Ay 0 2(b- BY — (a) (ey o> 0 2(b~ WY fu ab) ~ (ey 2Qb— BY fant fee co Proof. Let « defined by fy (2) = defined by eq be any real uiuners, such that ay < ru Note that the fanetion fy (U4) = R Thew ao the fanetion fe (0.4) + R (2 2)", is monotonically inetens ” Sale) = 2(0 9) feo at) fen)96 is monotonically increasing, and J (ag) < O and f (cy) > 0. It follows that there ix a number by € (a, co) such that fo (bp) = 0 Let us prove that Suppose to the contrary that It follows that ay From fz (by) = 0, it follows that (2) Relations (1) and (2) imply that | (ag — a3)" = *4/ (eo = 08)” + (co - 8)" = Note that ng ~ a8 ¥ co ~ eG, but then the latter equation cannot hold. Therefore, 2 (bo #8) ~ (00 ~ 08)" ~ (co ~ 8) 40. Define the functions fa. fe + (0.5) * (0,4) x (0,5) + R by Aalems) = (2-22) + (yw) 4 (= Blems) = (e+ yay + (2 Distinguish two cass: 1) CASE 1: 2(bp ~ #@)"* ~ (ao ~ @3)"* ~ (co ~ «8)"* > 0. ‘Since f, is continuos. there is a sufficiently small ¢ > 0. such that 2((6~ 2) ( —€94)"" (an 8)" (y=) > 0 ye > a We have Jalav.by~ ee) < 0 Lalag.bo~ sta) > 0. Since fy and fy are continwos functions. there are rational numbers a, b and ¢ sufficiently close to.) —€ and ep. such that Salado) < filabe) > ° ° 1 ae € (03) which proves the elas in this ease TN) CASE 2% 2 (ty - WY" (an a) (eu) 097 Since fy is continuous, there is a sufficiently stall © > O such that 2 (tbo +2) — (by +)" — (ay 08)” (co 8)" > 0 nie < oe We now have falaosbo + ec) > 0 Lrlao.bo + £0) < 0. Since fy and fy are continuous functions, there exist rational numbers a,b and e, sufficiently close to fo,by +£ and co, such that Iala,bc) > 0 Laladc) < 0 are « (ot \ ) a < bee. which proves the clainy in this case. Now, we can prove Theorem 1, From Lemune 4, it follows tat there are numbers a,b.€ € (0,4)9Q, such that @ 0 2(b-b)" (aa?) 2(b- 2) — (aa) ~(e- ay" > 0 ~(e-e@)* < 0. Without loss of generality, we may assume that 2(b~ ey — 2 (be) — jaa)" (ce) > 0 a)" ~(c-2)" < 0 From Lemma 3 it follows that there is a number st (2t,b.c, Ax), suel that for each 1 > nig (a.b.¢. 44) "Ws, (G(n,4.4,6)) ~" Wa, (G(n.9.6))} = (b— By — fa a2)" — (e | Therefore. for each 1 > ng (act e, Ay), we have "Ws, On.q.a.0) —" Ws, (0.4.0) > 0 From the sae Lewin. if follows that there isa munber 2g (ir bee. Az) ste that for enc n> (er bees Na) san ["W, (G (1.4.0.9) Wa, (G 04.4, 6))) . san [2 (0 By (a= at) (e~ )**] efore. lor each 11> my (a,b. 6,22) Wa (G Orga) Wa (Gln. 9.0) <098 Ws, (G (max {r19 (a,b, 6 4) m0 (bye, Aa)} + Legeace)) ( PUK, (G (amas (ran (4, 8,6, Xa) 30 (tb, A2)) + 1.9, 6) ) a {anax {00 (4, 8,6,41) 19 (4b, 6 Aa) + 1.400) — ) ; ( MIR G "Ig, (G (ana (ng (48,6, 41) m0 (a,b, 2)} + 1g, b)) In view of this. it is sufficient 10 take Gy = Gas {no (a,b, 6, r) na (a4 bye, Av) } + Lege ae) Gz = Gimax {ng (a. b,c 1) na (a, be, Az) } + 14.6) 2 Proof of the Theorem 2 We start with a few auxiliary results. Lemma 5 Letp.q € R., such that p # q andp,q > 1, and let cy € (0,}). There as a number ay € (0,4) such that This is equivalent to the requirement that foreach a: € (0,4), qiea-ert (eel as aconstant. Therefore f; (a1) = 0 for each ay € (0, ) and consequently, [e-per? +o aay] faa] [a= arts a= na-aye] fart a art] . for each ay € (0.$). i.e 4 a? aaa) +0 -a)? Fea) for ene a, € (0.4). 1 follows that the funeti falar)99 which is a contradiction, Len na 6 Let p,q ER, such that p #4 and p.y > 1. There are numbers u.b,¢ € (0,4). such that either ah + (1a) + (1— oP +e - 2-21 - by > 0 ate (lat tLe) e826" 201) <0 a? +(1—a)? +(1—c)? +c? — 2 - 2(1- 6" < 0 a + (1 =a)" + (1-0) 4% - 2b" -2(1- 6)" > 0 Proof. Let a; and cy be the numbers that satisfy the conditions of the previous Jemma. Consider the function fy : (0,1) +R, defined as Ja(z) = 2? + (1 = 2) Note that fy(2) = pe?! ~ p= 2)" <0, which means that fs is a strictly decreasing function. Now, consider the function fs (0, $) ~ R, defined by Sulla) =f + (= ay} + (1 = en)? + ef 208 201 BP It follows that fy is a strictly increasing function, that slim, fab) <0 and lim, fo (bx) >0 ‘Therefore there exists a uunber by € (U.$). such that falta) = 0. We have to distinguish three cases: CASE L af (1 — ay)" + (1 ey)" ef HY 2(1 by)" 0. Denote by J: (0.4) -+ R the function defined by Sls) =a (1 aye (heyy ee 28 20 ay Obviously, fs bz) > O. Since f, #8 m contiamos function and fy is a strictly increasing function, for suffi tly stall > 0. ww have ae (he a 4 (Le ex be 2b = ey 20 (by P< 0 AP aie sey bef Bde = 2)" 20 he aay > 0 bee Taking «= 1-b = by © and ¢ = ¢1, we proce the clainy CASE 2 of + (1a V4 (1 en) 4 ef 204-2 = bay eo100 Denote by fy (0.4) ~+ R the function defined by Bola) =a} (La 4 ett ef = 20" 21 - ay Obviously. f5(b2) <0. Since fy is continuos ant fy i strictly increasing, for sufficiently small ¢ > 0, we have abe (Lay (Le) + ~ Ube Fe)? 21 Cr te)? > 0 al + (1 ay)" + (1c) + ef ~ 2(b2 + 2)" 2(1 - (bo te)" < 0 1 2 bate < Taking a = ay, b= by + €.€ = ¢), we prove the claim CASE 3: af + (1 ~ ay)" + (1 ~ e1)" + cf ~ 20§ - 2(1 ~ by)" =0. Distinguish 2 subcases sUBcasE 31-44 There is @ number & Define the function oom Jo (2) = (a, +2)? & (1~ (ay +2)? (er + hay? + (1 ~ (ey + ke))P — 205 — 2(1 bal? We have by Fe (2) = ple + 2)! ~ pL — (ay + 2))P"" + per + heh! — pk(1 (er + kz)" and therefore slim Fé (2) = = mt p= arts [pet . (1 ay"! af > pa" p= ary" + foof" — p= ey") Define the function nfo. a by Fe2) = (an #2" (1 (ay by) + (er # ka)" + (1 = (ey + hay)" 268 ~ 200 ~ ba We hive FEU = ate ay G(T (ay by! + gk (er + key" ~ gh (1 ~ (er + ayy! implying stig £0) = mt ga ah! [act =a ey hs eet ai gags facet ait et] fee 0101 ‘Therefore there is a sufficiently small «. sucl that for each 2 € (0,2), Silr) > 0 file) < 0. Since La(0) = fr(0) = 0, for each xg € (0.2), Jo(ro) > 0 Si(zo) < 0, (“ + x0)” + (1 = (ay + x0)? + (or + kro)? + ) a (1 (ey + bra) ~ 205 ~ 201 ~ be) ( (a1 + 20)" + (1 — (ay + 0)" + (Cr + et)" + ) (1 (cy + hg)" ~ 26§ — 2(1— be)? 0, so by taking @ SUBCASE 3.2: by and ¢ = cy + kxo for any 29 € (0.¢) we prove the claitn Define the function by Sox) = (ay + 2) + (V~ (ay + 2yyP + (ey 4 YP 4 (1 = (ey 4 hey) — 205 20 ~ bP We have Go(2) = play + 2" ~ pC ~ (ar + x)" + ph (or 4 hey! — pk (I~ (ey + kxy)P* lim, f6(2) = po pay + [pe a-ak ey 0. Since fo(0) = fr(0) =0, for each x9 € (0.c), we have fe(xo) < 0 Srl) > 0, (ay + x0)? + (1 ~ (a, 4 x0)? + (01 + bao? + ( (1 (ey + Aza))? ~ 265 ~ 2(1~ ba)? ) : (Orie cto gta Vea) sg (1 (61+ hag)}* ~ 204-200 by)? a so by taking a = a) +9, b= by and ¢ = ¢, + kxo for any 29 € (0.:). we prove the claim, a Because the functions fr. fs : (0. ) x (0,3) * (0.4), defined by Srlabje) = ah (1 a)h + (1 0)” + oF ~ 207 — 2(1 YP Jalabic) = a4 (1—a}*4(1—o) +et 26" 211-5)" are continues, from the last lemma it directly: follows: Lemma 7 Let p.q € R. suck that p # q and p.q > 1. Then there are are numbers a,b. € (0,3)0Q, such that exther we (La + (1 oP et WF 21 > ata (Lea) 4 (Lo bet 268 20 ah eal (eee 2b <0 ata (laayh e(- bet 2 oy" > 0. Denote the graphs G (019.06) and G (ot gee) as in the previous section Now, we ean prove Theorenn 2. Replacing = Aa-+ Lin the previous Lemma, we get Ut theve exist smumbers a,b, ¢-€ (0.4) Q. such that eith 1D and ah may the (Legit tttt — abett a(n atl > 0 EE aha Mt A AE 21 OPO 0103 abet gen ate aye eben tte 2 (lib) strc <0) ata (Lapel a( ohtt ys Aett onde 2 opt! oo 0 Without loss of generality, we may assume that there are nurubers a,,¢ € (0, 4) Q. such that o's eat ae ac wt 20a os 0 ath (a ayetty (1 ety ett vt 2 opt co Note that ae Wa, (GC (,4.0,6)) — Wa, (Glna.e)) ce #(—a) "+01 toh 4! — abd 41 901 nage = tim Si _isi__ ORT esta aca) age ai Paes Tae Paes a a a dott fete veamngb? eT eae -2 fade 2 Pde ba ae ee ee , rey aa ee aaa oe ( att (Daa) tha acy te ) (ray eet. 2th 9() Bt pacman UM | ger Gagenges ys ) ap + (1 = ay 4 pod tt ie ott gett agape) eM ‘Thus, there exists a sufficiently large m, € N. such that for each n >, Wa (COrg ab) — Wa, (Gua) Actnec sg. ( hg (Day ett ) (ag) ee eT It follows that for each > ny WS, (Gong ab) Wa, (Gln, qe)) > 0104 Also, uote that Wa, (G (n.q.a,b}) ~ Ws, (Gnned) athe (Letty aot bt! — 201 — opt ) i) “0 fim. = lim tsa a) +( Aree Tatars > tim S—1_____#_____@__ a Cae hth Dp 2 — yt ase! a (ngangngt SL + esmebier Oe splesengesgt sey ~ Dig — = fim 4 fest 7 est “Te = ats (La a) pet seat (a ) (a) ht abbey 1 wer so that there is a sufficiently large nz € N, such that for each n> na, we have Ws, (G(n.4.0.8)~ Wa (Glad) sg ( ath (1—ay tls (1 yt ) (ny! ett apd oc Bye 1t follows that for each 1 > np Wa, (GO. 4. 0,0) ~ Wa, (Gn.4.0)) <0. Therefore, Wa, (G (anax ng maf + Lege a.b)) > Wa, (Glmax {any.me} + 1g.) Wy, (Gonax fmy ma} + Lege a.b)) << Wy, (Gfmax (my.mz} + Lge) so that it is sulliciont to take Gy = Wa, Glas rn} + Lagad)) Gz = Wa (Gnas (yma) + Lae)) 3° References [1 R. Todesehini and V. Consonni, Handbook of Molecular Descriptors, Wiley-VCH, Weinkwin, 2000. [2] S. Tinajsti€. Chemical Gruph Theory. CRC Press. 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