no.t pp. 71-82 1975 SOME ASPECTS OF GRAPH SPECTRAL THEORY OF CONJUGATED MOLECULES N. Trinajstié*’? and 1. Gutman® 2 the "Ruder Boskovié" Institute, P.0.B. 1016, Zagreb, Croatia, Yugoslavia and > chemistry pepartment, Faculty of Science and Mathema~ tics, University of Zagreb, 41000 Zagreb, Croatia, Yugoslavia Introduction In this work we will consider molecular graphs, named Hlickel graphs’, which are used to depict conjugated mole~ cules. ‘These graphs are connected and planar with the even num- ber of vertices (N). The maximal valency of a vertex (D,a,) in ulickel graphs is 3, We will use the basic definitions and con- cepts of graph theory detailed in our earlier work’, Let us first briefly discuss the equivalence between the Hickel theory and the graph spectral theory of conjugated mo- lecules?"5, Hamiltonian matrix in Hiickel theory (HJ) is given by? H-%1 +PpA a) where “J is a unity matrix, A\ is an adjacency (topological) matrix of a Hiickel graph, O€ and (4 are the Coulomb and resonan- ce integrals, respectively, of Hlickel theory. Hiickel determinant may be written as follows act] H) - 2, $| <0 @= iaie Introducing Hlickel approximations and Eq. (1) into (2), one obtains ace [ET - Als @) The adjacency matrix of a graph is defined as 1 if r and s are adjacent vertices Aus = “ 0 otherwise the set of eigenvalues x,5 X51 sss++1 ay} Delonging to the adja cency matrix A\ of the graph G is called the spectrum of the graph (sometimes the graph spectrum). The graph spectrum is the set of roots of the secular equation: act Jx- Al -0 (5) If Eqs. (3) and (5) are compared it appears that the numbers are actually making up the spectrum of a Hiickel graph: +x san, Using P as an energy unit and G{ as the zero-point, we have (6) Ey = 7) and hence, the eigenvalues of the adjacency matrix are identical with Hlickel molecular orbital energy levels. From Bq. (1) it is seen that (Hf ana A) commute and have, therefore, the same eigenvectors, Thus, the eigenvectors of the adjacency matrix are identical with the Hlickel molecular orbitals. Hlickel molecular orbitals corresponding to x > 0, x=0, and x €0 are called bonding, non-bonding, and antibonding, res~ pectively. The number of bonding, non-bonding, and antibonding MO“s is denoted as N,, Noy and N_, respectively. They are related to the total number of atoms in a conjugated molecule (N) as fo- Llows:= 93 = Ntnotulen (8) ote, that the polynomial re; = act [x 1 - Al @) is called the characteristic polynonial of the graph G and it contains Important information about the conjugated molecule. charactert- stie polynomial has the following form: 3 Nen 4 a, * (Qo) are the coefficients of the P(G; x). P(G; x) is of deq- PUG; x ree N. We wish to show in the sections which follow the relations between the a, and N,, No, and W. 2. Number of bonding molecular orbitals (N,| The following relations hetween N,, Nj, and P(G; x) exist® ayrayarT tees FAs 2 ay a2) ag) = §, (3) where ch denotes the number of changes of sign in the sequence of numbers. Example fulvene graph ( ) P(G; x) x -6 x's ext? -2x-1 a )-74- Ch (-1y -2, 8, ~ NL=N-M,- Ny characteristic polynomial of fulvene graph is constructed using the Coulson-Sachs method as decribed by Graovac et ai.” unfortunately, the evaluation of P(G; x) for larger graphs by the Coulson-Sachs graphical method becomes unwieldy. Therefore, ano- ther graph-theoretical approach may be more convenient (see Sec- tion 4). Non-bonding molecular orbitals (NBNOEN,) Tt is of importance to establish the presence of non-bonding molecular orbitals (NBMO) in conjugated structures because their existence leads to prediction® that such molecules should have open-shell ground state and should be very reactive. Here we will outline 2 simple method for determination of Nj. Since we know that the number of NEMO“s is identical with the number of zeros in the graph spectrum, and since u act A - TT x, aay sas The determinant of A will be zero if, and only if, there exists at least one zero in the graph spectrum. Therefore, the problem of determining N, is closely related to the problem of evaluation aet Al of the craph in question. We have derived the following expression for the evaluation of the determinant of adjacency matrix: aet A= yN/2 ext — 2 + 00 in where K* and Kare Kekulé structures of even and odd parity’, 5 is a Sachs graph with odd-menbered rings’*10 + g(s) and r(s) are the number of components and the number of cyclic components of the Sachs graph s, respectively. The following rule may be used- 75 - Pts if the struc- for determining the parity of two Kekulé structures ture obtained by superposition of two Kekulé graphs contains an even (oda) number of [4m]-menbered rings, the Kekulé structures in question have the same (opposite) parity. For more details about Sachs and Kekulé graphs see communication in these Proceedings by Graovac and Trinajstic!?, The use of formula (15) will be illustrated on pyracye- lene. (1) We first write down Kekulé structures and the corres- ponding Kekulé graphs of pyracyclene. Kekulé structures So OD Kekulé graphs mS Cis CS as A x m mS k, (2) Now, we determine their parities. K, structure is arbitrarily selected to be even (+1). Then, St ase (7% =Therefore, Kt = 3 and KU =1 (3) Pyracyclene has only one Sachs graph containing the odé- membered rings: Thus, it follows ad ag 98 det A= (7 3-2 + 4 ° ae) Therefore, pyracyclene must have at least one NBMO. The actual number of zeros in the graph spectrum may be obtai- ned following the Longuet-Higgins-Zivkovié algorithm®’!? for enu- meration of Nj. Let us first consider the eigenvalue equation: €,M = x,o a7 In the case of N40, x,=0 and €,= € ,= namo: CA as) x a cay k=1,2, N (19) The summation is over all vertices j joined to the vertex k.-77- It should be also noted’ that a number of independent parameters in unormalized NEMO is equal to Nj. The use of this approach will be also illustrated for pyracyclene. Each vertex for which Eq. (19) is fulfilled is denoted by e. In order that Eq. (19) is fulfilled for the last (unmarked) vertex of pyracyclene the following relation must hold: atb=0 (20) Thus, only gne parameter (b=-a) is independent, and consequently, N ‘The chemistry of pyracyclene’’ is in accord with this prediction. Number of antibonding orbitals (N_) The following relations which are formally analogous to Eqs. (11) = (13):~ 78 - =0 (2) Dyey #° N=Ng (22) Ch (Wye Dyayr eeeeee Dye Dg) = NL (23) can be used for enumeration of antibonding orbitals!®. they may be also used for enumerating W, and N,, and thus, this method may replace that one described in Section 2. Note, that Dy can be determined from the relation: get A=, ieee (24) Tt should be also noted that A\,_, is the submatrix of Ml, obtained by deletion of the n-th row and the n-th colum of l,. The Thus, isa minor of D,. Besides, by definition D, Pnaa sequence of numbers (Dy, Dy_ye «+++ Dg) may be donoted as (D nJana it is called “decomposition” of the graph G. The sequence D =(6,, 6 v1 Gy) G,) 48 the decomposition of G, no? (p21,2,+e.+4)n)+ ‘The application of the above approach is illustra~ ted for fulvene. (2) First we consider the decomposition of the fulvene graph: p—o oo © empty graph 3- 79 (2) Secondly, the D numbers are evaluated: Dg=det Al got, ogeaet A cect & (3) ch(-1, 2, 1, 0, <2, py-act Ay-t, 0 act Ao, p= act A= and D, 10,1) = N= 3 Dy # 05 NQ=0 N= NOUN) = 3 However, the whole procedure may be simplified even more because of identity: chen, +1Dg) = Ch(Dyr ees N_ = chiDy, +1Dy) + Ch(D,,.++4,D,) (25) 1D.) + N_(n) (26) Thus, if we know N_(n) it is sufficient to calculate (Dy, oD,)e The application of these considerations will be demostrated for pentalene. NL = ch(0, -2, -1) + N_(6) = 0 4 6/2=3 OF NED Nye - LEN 24 NM Pentalene should be a highly reactive electron-deficient nolecule. The experimental findings’® support this theoretical result. 5 Classification of conjugated hydrocarbons based on= 80 - their graph spectral characteristics We define a vector Mas MEMO) = OM, - NN) (27) which determines a point with integer coordinates in the upper half-plane of a two-dimensional coordinate system, Note, that m=0 (28) is necessary condition for W-electron system to be stable. The- re are also other reasons for chemical stability, hence Eq. (28) alone is not a sufficient condition for a conjugated system to be stable. If Eq. (28) holds, it is N,=N_=N/2 and all bonding MO"s are doubly occupied in the ground state. In the case N, p> N_ there are unoccupied bonding MO’s, while for N, € W_ there are occupied antibonding MO“s, both causing the high reactivity and/or instability of the W-electron system, Besides, systems with N, > N_ may be classified as electron-deficient molecules because they tend to accept electrons from a suitable donor in their empty bonding MO levels. Systems with N,< N_ are electron-excessive molecules and show tendency to generate cations. Finally, if Ny _ and N, > 0 a polyradical ground state is expected and such structures are extremely reactive. 7, Conclusions We suppose that after going through this work a question could be asked immediately: Why to develop and use the graph spec- tral theory when it does give hardly any information not available from Hiickel calculations? We,however, feel that there are several good points in favour of developing the graph spectral theory of conjugated molecules. These may be summarised as below:- 81 - (1) A number of results may be obtained without any use of computers by just a pencil and a paper. This is of importance for experimental chémists who are sometimes kept away from using current computational theories because of necessity to carry them out on computers using the specialized programs. (44) Sometimes a purely numerical computerized examination hides away the importance of a particular feature of a molecule which may encounter for some properties of the molecule. (141) The obtained graph theoretical results have a general validity and may be formulated as theorems and/or rules which may be then applied to any similar group of molecules without any further numerical or conceptual work. (iv) Pinally, it is not our intention to compete with standard HMO calculations, but rather to develop a symbolism that permits chemists to think graphically, i.e. to learn as much as possible about the chemical behaviour of the molecule by examining the properties of its molecular graph. Full account about various aspects of the graph spectral theory of conjugated molecules would appear in our Authors Review in Croatica Chemica Acta!?, Acknowledgements We thank Dr. A. Graovac, Mr. M. Milun, and Mr. T. Zivkovié for helpful discussions, The financial support from the Council of Scientific Research of Republic of Croatia is gratefully acknowledged.10. a. 12. 13. a4. 15. 16. 17. = 82 = 8, Literature A. Graovac and N. Trinajsti¢, J. Mol. Structure, in press. I. Gutman and N. Trinajsti¢, Topics Curr. Chem. 42, 49 (1973). K. Ruedenberg, J. Chem. Phys. 22, 1878 (1954). HH. Giinthard and H. Primas, Helv. Chim. Acta 39, 1645 (1956). H.H. Schmidtke, J. Chem. Phys. 45, 3920 (1966). A.G. Kurosh, Kurs vishei algebri, Nauka, Moscow 1965. A. Graovac, I. Gutman, N. Trinajstié, and T. Zivkovié, Theoret. Chim. Acta 26, 67 (1972). H.C. Longuet-Higgins, J. Chem. Phys. 18, 265 (1950). M.J.S. Dewar and H.C. Longuet-Higgins, Proc. Roy. Soc. (London) A 214, 482 (1952). D, Cvetkovié, I. Gutman, and N. Trinajstié, Chem. Phys. Lett. 16, 614 (1972). b, Cvetkovié, I, Gutman, and N. Trinajsti¢, J. Chem. Phys. 61, 2700 (1974). A, Graovac and N. Trinajstié,see in these Proceedings article entitled: "Graphs in Chemistry". 7. Zivkovié, Croat. Chem. Acta 44, 351 (1972). D. bloya, "Carbocyclic Non-Benzenoid Aromatic Compounds", Elsevier, Amsterdam 1966. I. Gutman, Chem. Phys. Lett. 26, 85 (1974). T.J. Katz and M, Rosenberger, J. Amer. Chem. Soc. 84, 865 (1962). I. Gutman and N. Trinajstié, Croat. Chem, Acta, in press.