Chemical Physics Letters 407 (2005) 213216 www.elsevier.

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On the principle of maximum overlap in molecular orbital theory

Valerio Magnasco
*
` , Via Dodecaneso 31, 16146 Genova, Italy Dipartimento di Chimica e Chimica Industriale dellUniversita Received 2 February 2005; in nal form 22 March 2005 Available online 13 April 2005

Abstract Making the usual assumptions typical of elementary Hu ckel theory including overlap it is shown that the Hu ckel energy of the two-electron bond is minimized for orbitals having maximum overlap, which yields maximum strength for the straight bond. Analysis of the bond energy for the general AB bond shows for the molecular orbital description a more complicated dependence on the one-electron exchange-overlap densities of A and B than that recently derived by us in a corresponding valence bond treatment. 2005 Elsevier B.V. All rights reserved.

1. Introduction The principle of maximum overlap has often been assumed as one of the fundamental rules of chemical bonding since the early applications of quantum mechanics to the study of the electronic structure of molecules [13]. The principle states that bonding is stronger for atomic orbitals (AOs) having maximum overlap, and has the important consequence that straight bonds are stronger. Even if of great importance in the qualitative applications of the theory of valence [4], explicit demonstrations of this principle have not been given in the Literature, not even at the level of simple models. We have recently shown [5] that a model valence bond (VB) description of the chemical bond indicates that covalent bonding is strongest for AOs maximizing the strength of the complete exchange-overlap component of the bond energy. It will be shown in this Letter that a similar treatment inside a molecular orbital (MO) model, making the usual assumptions typical of elementary Hu ckel theory including overlap [6,7], says (i) that the Hu ckel energy of the two-electron bond is minimized for orbitals having maximum overlap, and (ii) that the
*

MO description of the bond energy for the general AB bond has a more complicated dependence on the one-electron exchange-overlap densities of A and B than that recently derived by us in a corresponding valence bond treatment [5].

2. The molecular orbital model of directed valency Let bA be a directed orbital (atomic or hybrid) centred at the nucleus of atom A and making an angle h with the interbond axis AB directed along z from A to B, and vB a spherical orbital on atom B a distance R apart. Then, overlap SAB and bond integral bAB [6,7] can be written as S AB S cos h; bAB b cos h; 1 where S and b are integrals characteristic of the bond AB, which depend on R but are independent of the orientation h. The secular equation for the corresponding bond orbital / in a one-electron Hu ckel-type approximation including overlap can then be written as    aA e b eS cos h    0; 2  b eS cos h  aB e which expands to the quadratic equation in 

Fax: +39 010 3536199. E-mail address: magnasco@chimica.unige.it.

0009-2614/$ - see front matter 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.cplett.2005.03.101

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1 S 2 cos2 he2 aA aB 2bS cos2 he aA aB b cos h 0:

2 2

In the above formulae, aA, aB, and b are all negative energy quantities, the rst two having to be interpreted as atomic integrals pertaining to orbitals bA and vB, while b is a bond integral depending on the nature of A and B [6,7]. The two real roots are e aA aB 2bS cos2 h D 21 S 2 cos2 h 4

With reference to Eq. (7), we easily obtain   of 2 b eS sin 2h; fh oh e fhh  o2 f 2 2b eS cos 2h; oh2 e   of fe oe h 2e1 S 2 cos2 h aA aB 2bS cos2 h: For the lowest root (4), e = e, we have
2

14

15

16

the bonding root and aA aB 2bS cos2 h D e 21 S 2 cos2 h 5

fh e b e S sin 2h; fe e D; so that Eqs. (9) and (13) become de b e S 2 sin 2h ; D dh

2

17 18

the antibonding root, where [7] n o1=2 2 > 0: D aB aA 4b aA S b aB S cos2 h 6 To examine the dependence of the orbital energies e on h, it is convenient to consider the determinantal Eq. (2) as an implicit function of the two variables h and e f h; e aA eaB e b eS cos2 h 0:
2

19

d2 e 2b e S cos 2h : 20 D dh2 The stationarity condition of e against h says that d e 0 dh for h = 0, so that  2  2 d e 2 b e S >0 D dh2 h0 21

From the derivation rules for implicit functions [8] it follows:     of of df dh de 0; 8 oh e oe h of de fh oh e o f dh fe oe h provided   of fe 6 0 oe h 9

22

provided both numerator and denominator are evaluated at h = 0. From Eqs. (21) and (22) follows that h = 0 is a stationarity point for which e has a true minimum value. Hence, the Hu ckel energy for the two electrons in the bond orbital /
E h 0 2e h 0 n o1=2 2 aA aB 2bS aB aA 4b aA S b aB S 1 S2 23

10

and using the Schwartz equality for the second partial derivatives d2 e fhh fe 2 fee fh 2 2f he fh fe : 3 dh2 fe 11

When the calculation of the second derivative involves a stationarity point for e, which implies   of fh 0; 12 oh e expression (11) simplies to d2 e fhh ; 2 fe dh 13

is a minimum for h = 0, corresponding to a maximum strength for the straight bond AB. In the same way, it can be shown that h = 0 corresponds to a maximum for E+ = 2e+, since d e b e S 2 sin 2h ; D dh d 2 e 2b e S 2 cos 2h ; D dh2 so that  2  2 d e 2 b e S < 0: D dh2 h0 24

25

provided both members are evaluated at the stationarity point for e.

26

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For orthogonal AOs, such as those of the original Hu ckel theory, S = 0, and formulae (19) and (20) become de b2 sin 2h ; D dh d2 e 2b2 cos 2h D d h2 27

exchange-overlap densities than was the case of the corresponding VB formulation [5]. On the other hand, both factors above contribute to the determination of the polarity parameter k of the bonding MO / [9]: bA kvB : / p 1 k2 2kS cos h 32

and the same conclusions still hold.

3. Analysis of the MO bond energy In our MO model, the bond energy dened as DE 2e aA aB S b aA S b aB S cos2 h 2 2 1 S cos h D 1 S 2 cos2 h 28 is made by two terms, the second being the bonding term (<0, attractive), the rst a repulsive term (>0) correcting for non-orthogonality. For h = 0, if aA aB a; n o1=2 2 D 4 b aS 2j b aS j > 0 and the bond energy becomes DE h 0 2S 2j b aS j b aS 1 S2 1 S2 2S 2 b aS b aS 2 1S 1 S2 b aS <0 2 1S 29 30

Rather than from the homogeneous system corresponding to the secular Eq. (2), it is convenient to obtain k for the lowest eigenvalue e as the appropriate solution of the quadratic equation1 b aB S cos hk2 aB aA k b aA S cos h 0; 33 k aB aA D 2b aB S cos h ss D aB aA jb aA S j : D aB aA jb aB S j

34

31

as it must be for homonuclear bonding. Hence, the correction term in (28) is essential in order to avoid overestimation of the bond energy. This is in agreement with the well known asymmetric splitting of the MO levels occurring in Hu ckel theory for S 6 0 [7], where nonorthogonality of the basic AOs yields a bonding level less bonding, and an antibonding level more antibonding, than those of the symmetric splitting occurring for S = 0. As far as the bonding term in (28) is concerned, Eq. (6) shows that D, in turn, depends (i) on the atomic energy dierence (aB aA), and (ii) on the product of bond energy integrals, (b aAS)(b aBS)cos2 h, arising from the exchange-overlap densities on A and B, [a(r)b(r) Sa2(r)] and [b(r)a(r) Sb2(r)], respectively, and which contains all dependence of D on the orientation h. So, it is apparent that the MO description of bonding and of its directional properties in the general case B 6 A involves a rather more complicated dependence (through the square root dening D) on such

Eq. (34) allows then for the MO description of the electric dipole moment l of the bond. We must recall that the VB treatment presented elsewhere [5] concerns only the formation of a covalent bond between A and B, so that for accounting for bond polarity ionic structures should be considered as well. Formula (31), and its extension to include the eect of antibonding orbitals, was used by us in [6] to show that the Hu ckel treatment including overlap for the series of r homonuclear diatomics H 2 , H2, He2 , He2 not only gives the correct qualitative description of bonding and antibonding behaviour along the series, but also semiquantitative agreement with experimental or accurate theoretical predictions in the bond region. As a matter of fact, Hu ckel theory including overlap appropriately describes the physically relevant part of the interaction in this region, showing that the possibility of forming a chemical bond lies in the attractive nature of the one-electron part of the exchange-overlap component of the interaction energy [11]. These considerations were further extended to cover the homonuclear diatomics of the rst row [7], which involve p bonding as well, and the heteropolar bond in the orthogonal approximation [9]. All these eects are also those determining the straight bond when directed orbitals overlap.

4. Conclusions Under the usual assumptions of elementary Hu ckel theory including overlap [6,7], we have shown that the Hu ckel energy of the two-electron bond is minimized
1 Arising from the matrix formulation of the full 2 2 nonorthogonal eigenvalue problem [10].

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for atomic orbitals having maximum overlap, what yields maximum strength for the straight bond (h = 0). Analysis of the bond energy for the general AB bond shows for the MO description a more complicated dependence on the one-electron exchange-overlap densities of A and B than that was recently found by us in a corresponding VB treatment [5]. Acknowledgements Support by the Italian Ministry of Education University and Research (MIUR) under Grant No. 2004 03 4838 009 and by the University of Genoa is gratefully acknowledged. I thank Prof. Giuseppe Figari for useful suggestions.

References
[1] E. Hu ckel, Z. Physik 60 (1930) 423. [2] L. Pauling, J. Am. Chem. Soc. 53 (1931) 1367; J. Am. Chem. Soc. 53 (1931) 3225. [3] C.A. Coulson, Proc. Cambridge Phil. Soc. 33 (1937) 111. [4] C.A. Coulson, Valence, second edn., Oxford University Press, Oxford, 1961. [5] V. Magnasco, C. Costa, Chem. Phys. Lett. 403 (2005) 303. [6] V. Magnasco, Chem. Phys. Lett. 363 (2002) 544. [7] V. Magnasco, J. Chem. Edu. 81 (2004) 427. [8] V.I. Smirnov, Corso Di Matematica Superiore, vol. I, Editori Riuniti, Roma, 1993. [9] V. Magnasco, Chem. Phys. Lett. 380 (2003) 397. [10] V. Magnasco, Unpublished calculations, 2002. [11] V. Magnasco, R. McWeeny, in: Z.B. Maksic (Ed.), Theoretical Models of Chemical Bonding, Part 4; Theoretical Treatment of Large Molecules and Their Interactions, Springer, Berlin, 1991, p. 133.