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VI,

271-279 (1972)

**The Non-Crossing Rule in Molecular
**

Quantum Mechanics

K. RAZI NAQVI*

Atomic and Molecular Physics Group, The Schuster Laboratory, University of Manchester,

Manchester M I 3 9 P L , England

AND

W. BYERS BROWN

Department of Chemistry, University of Manchester, Manchester MI3 9 P L , England

Abstracts

Previous mathematical proofs of the non-crossing rule concerning the potential energy

curves of a diatomic molecule are examined and criticised. A new treatment is presented

which is simple and mathematically rigorous.

U n traitement 8 la fois simple et avec rigueur mathkmatique est donnC pour la “noncrossing rule” concernant les courbes de potentiel dans les molkcules diatomiques. Un

examen minutieux et critique des preuves que jusqu’8 present ont ttk donneks d e cette

rtgle prtctde notre deduction et en justifie sa nkcessite.

Hier werden bisherige mathematische Beweise der “non-crossing” Regel in Verbindung

mit Potentialenergiekurven eines zwei-atomigen Molekuls untersucht und kritisiert. Es

wird eine neue Behandlung vorgeschlagen, die einfach und mathematisch rigoros ist.

**The non-crossing rule, which is continually invoked in constructing the
**

correlation diagrams for the electronic states of diatomic molecules, asserts that

potential energy curves of the electronic states of the same symmetry species cannot

cross as the internuclear distance is varied [I]. The rule is of immense importance

in quantum mechanics and applies, in fact, to any system whose energy depends

on a variable parameter which occurs in the Hamiltonian of the system. There is

massive experimental evidence in spectroscopic literature for the validity of the

non-crossing rule; the doubt which some earlier experiments cast on its ubiquity

has now been dispelled, and in no instance does the rule seem to be violated [2].

I t is our intention to point out in this paper that, of the two attempts that have

been made at proving this indispensable rule, one is based on a non-sequitur, while

the other incurs a defect by considering only two wave functions in a variational

discussion; and to present a new derivation which seems to lack these deficiencies.

The most frequently cited proof, due originally to Teller [3] and quoted with

or without some minor alterations by a number ofother authors [4-91, is reproduced

below for the sake of completeness. We assume that we already know all the correct

* Rutherford Scholar of the Royal Society (1968-71). Present address: Department of Chemistry, The University, Sheffield S3 7HF, England.

21 1

0 1972 by John Wiley & Sons, Inc.

The energy levels can be determined by solving the secular equation where Hij = ($*I = H. hence the non-crossing of the two curves. Further.272 K.I = [ -sin cos 8 7 [.. RAZI NAQVI AND W. Let H ( R ) be the electronic Hamiltonian of the molecule. Thus it is almost impossible that by varying one parameter. BYERS BROWN eigenfunctions of the molecule except those corresponding to the two potential curves whose intersection we wish to investigate. As this fallacy seems to have been overlooked so far. and that it is logically deficient.. However. if dl and d2 belong to two different irreducible representations of the symmetry group of H. We will now demonstrate that the foregoing argument proves the non-crossing rule only by begging the question a t issue.) is also zero.(R. R. H12 will be identically zero (at all R ) and crossing is possible.. j:[ cos 8 = [sin e -sin 8 cos J[j .). conversely. which are orthogonal to all the known wave functions and to each other. 2 = Wll + f Wll .. Since and 4. the two unknown wave functions may be written as linear combinations of d1 and $2. where R denotes the internuclear distance. it will be a mere accident if Hl2(R.I cos sin 8 where 8 is some angle which will depend on R . If a t some value of R ( = Roysay) Hll(Ro) = H. Thus 4 . belong to the same function space as that spanned by the two unknown eigenfunctions y1 and y. we can relate the two pairs of functions by the following orthogonal transformation matrices : [. a detailed discussion may not be amiss. let us have two wave functions d1 and 4. we will achieve the condition El = E.H22)2 H22) +4 IH121211'2 The two values of E will be equal only if the two conditions Hll = H22 and H12 = 0 are satisfied simultaneously.

. which has also been given in slightly modified forms by Landau and Lifshitz [ 1 11 and by Heine [ 121.(R) are to intersect at some point. since any discussion of the eigenvalues is inherently restricted to the particular value of R for which 4. If two energy curves El(R) and E.(R(O) + 6R) can be regarded as + 6R H(Ro is a small correction term.and it seems extremely artificial that one does not start with the correct wave functions themselves. does not follow unless it is shown that El cannot equal E . must vary with R..(R(O) + 6R) and E.E.E.. It will be seen later that only by considering two suitably chosen neighbouring points is it possible to derive two independent conditions and prove the theorem stated in the non-crossing rule. But the former possibility can be ruled out only if we know that El # E. = El cos2 8 H. Let y?’ and y$’ be the corresponding wave functions.NON-CROSSING RULE IN QUANTUM MECHANICS 273 We now calculate the relevant matrix elements : H.E2) cos 28 I t can now easily be seen that when H I .. . they cannot be constructed without a knowledge of the eigenfunctions yl. H. and the eigenvalues El.H2. must either be zero or &(El. . = 0 will not be satisfied simultaneously.. the argument that the two conditions Hll = H.). thus.. .. We now change the internuclear distance to R(O) 6R and see whether E l and E. and H.) sin 28 + E. = $(El . As 4. become equal. .. Further.. It proceeds as follows. Increasing the internuclear distance by a n amount 6R changes the Hamiltonian to H(O) V . sin2 8 = El sin2 8 + E . aR E. as a perturbation to the operator H‘O). V. given by + V = H(R‘O’ + aH‘0’ + 6R). and 4.. which is to be proved. have values Eio’ and EP) which are very close but not equal to each other. where V. .H(O)= 6R+**. they must have values which are very nearly equal in the vicinity of the crossing point. and 4. cos2 8 H.. The earliest discussion due to von Neumann and Wigner [lo] was based on a somewhat different proof. Let us consider a point R(O)where the electronic Hamiltonian is H(0) and the two functions El and E. whence H. = (El . have been defined. = H. it is impossible to examine the intersection of two potential curves. eigenvalues of the new Hamiltonian.

of course. unlike those derived by Teller. in a certain approximation. lift the degeneracy which was initially present. = 0 I t should be noted that these conditions. 1 1 . However. BYERS BROWN We look in the zeroth approximation for a solution of the form * + by?’ and evaluate E. .El We see then that the conditions for crossing to occur are: (2) Eio). y = ayy’ (1) I t is easy to arrive at the secular equation EP) + V.V2. . the contribution due to the states not included in the truncated expansion of Equation (1) will vanish in the limit 6R --+ 0 only if EP) = EP) a t R = R‘O). are not interdependent.ELo’ + V. and a proof which hinges on the veracity of Equation ( 1 ) loses its rigour when applied to a diatomic molecule with a plethora of energy curves many of which may have close values at a particular internuclear distance.E Ep + v 1 2 v 2 2 L o . all other functions except the two shown in Equation ( 1 ) . though correct in its logical form + * Von Neumann and Wigner start by expressing the wave function in terms of a complete set. rather than as a linear combination of the complete set of functions is a legitimate use of perturbation theory. But then the two curves will intersect by definition and the degeneracy will persist as V will also vanish at R(0)and there will no longer be a perturbation.. The inclusion of the previously neglected terms in the Hamiltonian is tantamount to the introduction of a perturbation in the system and would. The wave function of Equation (1) is admissible if the molecule has only two potential curves. At first sight it might seem that writing the zero-order wave function at (R(O) SR) as a linear combination of yio)and y r ) . employment of Equation (1) is difficult to accept. in the later stages.. 131 that if. But this argument. and the lefthand sides of Equations (2) and (3) are not explicit functions of (El . in the absence of any knowledge about the other eigenstates of the molecule. I t is often remarked [ 1. then taking into account the small terms in the Hamiltonian that were originally ignored would obviate the seeming crossing and the curves would “repel” each other.E2). . = 0 (3) v. but drop.(R(O) + 6R) and E2(R(0)+ 6R) by applying perturbation theory.. The rest of the argument is identical with the concluding part of Teller’s proof and will not be repeated.2 74 K. or if the operator H(0)has two close eigenvalues E Y ) and EP’ and all other eigenvalues lie far from these two. RAZI NAQVI AND W. for y?’ and y p ) will then form a complete set by themselves. However. two energy curves belonging to the same symmetry species intersect.

vindicates the analysis which follows. what. . as the states may be degenerate for all values of R. and integrate to get (6) (w3 6H I w 3 = W ( w : I 34) By repeating the above analysis with the Schrodinger equation for the second state and multiplying by the complex conjugate of yy it follows that . it will be enough to mention that a completely rigorous treatment. Consider the crossing of two energy eigenvalues El(R) and E. presented in the Appendix.so that (5) 6E1 # 6E2 This inequality will now be used to derive an additional requirement for crossing.) = EZ(R0) = Eo (4) Note that this condition does not by itself guarantee crossing.(R) at R = R .6El)y: = 0 Should one choose to argue that. in order to obtain the above equation. is not altogether conclusive.E l h = 0 Consider a small change from R . The crossing of two eigenvalues as functions of R means that for R = R . Multiply the complex conjugate of the last equation by the second eigenfunction y: for R = R . we have immolated mathematical rigour by discarding the terms which are quadratic in 6. + 6R) = E . one may ask. are dzyerent. + 6R the energies + 6R) = E . would happen if one knew the exact eigenfunctions and a Hamiltonian which takes account of all the terms? We now proceed to derive a n alternative proof of the non-crossing rule by considering the exact eigenfunctions and the complete Hamiltonian for a diatomic molecule. . + 6El E1(Ro and E2(R. to R . + SE.) 6w1 + 6R and let the perturbed Schrodinger + (6H . so that El@.NON-CROSSING RULE IN QUANTUM MECHANICS 275 and physical contents. Let the Schrodinger equation for the first state be (H .E. equation be ( H .

276 K. two conditions * are required : E. forces us to conclude that the overlap integral must vanish even when El = E 2 . if we so desire. retaining only the first-order term for simplicity. where Fl2 = (Wll F Iyz) = -(. It is. this argument is not only unnecessary but misleading. however. in which case (yl y 2 )will be identically zero at all R because of the different symmetries of the two functions.t unless one of them vanishes automatically for all R .we deduce 1 (Y? Y 3 = 0 (8) I t will be well to pause here momentarily and discuss the implications of Equation (8). that it would also be true at R . .(R) = E.(Ru) (10) F12(R. it can now be seen that the inequality (5) implies the further condition : I I (9) (w?l 6 f f I W 3 = 0 Let us suppose that SH can be expanded as a power series in 6R.(R. R . it seems likely. not strictly impossible that both are fulfilled for just one value of R (accidental crossing). on account of continuity..lull aH/aR Iy2) Thus for crossing. This is the underlying * If the eigenfunctions y1 and ys cannot be chosen to be real (which is unlikely). Equation (6) requires that F. orF12(R) = 0 for all R due to symmetry ( F =: . either the degenerate case E.(R. and there is no way of making the overlap integral different from zero at any R. that is. RAZI NAQVI AND W.) = 0 (degeneracy) (crossing) The usual argument now applies: there is no reason why these should be satisfied simultaneously. 6H = -F6R + * * * Then. The only exception occurs when the two functions belong to different irreducible representations of the symmetry group of H. However. . BYERS BROWN and.(R).) = E. I t is tempting to argue that. that Teller’s simplified formulation fails to arrive at the essential condition for crossing because it gives no special consideration to a value of R distinct from the crossing point.aH/aR will have the symmetry of the Hamiltonian). and crossing is even less likely. in conclusion. for we know that degenerate eigenfunctions need not be orthogonal. . then the equation F12(Ro) = 0 is equivalent to two real conditions. knowing that 6El # 6 E 2 .) = 0. Returning to Equation ( 6 ) . We emphasize. Our demand that the two potential curves intersect a t R . indeed we can choose them a t will and make them to be non-orthogonal. since (yl y 2 ) = 0 for all R in the vicinity of R = R . t .

the terms “crossing” and “intersection” for the behaviour specified in the preceding sentence. We begin by writing the Schrodinger equation for the first state ( H .. Our treatment seems more satisfactory than the pioneering discussion due to von Neumann and Wigner. Ep)(Ro)= Ep)(Ro) (R. if the differencef(a h ) . for the analysis is obviously rigorous and does not require the use of a n approximate form of degenerate perturbation theory. i.E. Appendix A. in the parlance of differential calculus.g(a h ) has opposite signs for small positive values of h and for numerically small negative values of h[ 141. we will now discuss the “no-contact” rule and explore the conditions under which energy levels of like symmetry can touch each other when the parameter R is allowed to vary.)W1 = 0 Differentiation with respect to R.(R. I n other words. and use the more general words “contact” and “touch” to describe what we have been indiscriminately calling crossing of curves. . we obtain .) # * . . for a contact of nth order to occur at R = R .E. we must also have (1 1) and (12) Ei(R.) = &(R0).* * (R.EO)Wi(R. + (4’) + El(R0) = EdR. Cooper are gratefully acknowledged.) where the superscripts denote differentiation with respect to R.(R) which have a contact a t R = R. We will reserve. Baker and Dr. in the Appendix.) = El(Ro). I. Acknowledgements Some useful discussions with Dr. to cross at the point of contact.e.E. G. yields + (Ho .NON-CROSSING RULE IN QUANTUM MECHANICS 277 difference between Teller’s approach and that adopted by von Neumann and Wigner and by us.(R) and E.(Ro)M = 0 If we multiply the complex conjugate of this equation by yi and integrate.) = Eo Now. Further discussion of crossing Two curvesf(x) and g ( x ) which touch each other at a point for which x = a are said. Consider two curves E. at the point R = R . L.) P ’ ( R 0 ) . J.

at Equation (8). 109 (1937). R. we must have. [3] E. Bates. Flugge (Springer-Verlag Berlin.).) = E. S.E. 1 (D. 1968). New York.). i. Substitution of Equation (8) into Equation (13) gives us the equation which is identical with the second of the pair of Equations (10) of the text. Vol. 60-68. Vol. T.(R. if two energy curves are to have a contact at R. so that E. “Quantum Mechanics of Electronic Structure of Simple Molecules”. (Chapman and Hall. 1962).(R. “Chemical binding”. We have thus established that the requirements which must be met. p. Dissociation Energies and Sfectra of Diatomic Molecules 3rd edn. 3712. Ohno and K. Phys. Herzberg. ( R o ) . Ed. New York. but E. Kayama. Vol. RAZI NAQVI AND W. [6] C. Ed. if the contact is of first order.) = 0 (8‘) If E. arrive. Lewis. ( d (14) Iw3 Subtraction of Equation (1 4) from Equation (1 3) yields I P .) = E. Gaydon. A. 63-64. BYERS BROWN Differentiation of the Schrodinger equation for the second state. gives (YYl H’(R0) lw3 = E . 2. Bibliography [I] G.e. Chem. 41. as we found earlier in the text s = (y! I y.). Quantum Chemistry (Wiley.278 K. 206. a t the point of contact according as n is even or odd. are the same as those expressed by Equations (10) which were derived earlier in the text.) . Van Nostrand.) # E.E W O ) } + s’(R. p.) # E. New York.(R. L5] C. 1950). 1961). Valence (Oxford University Press. Molecular Spectra and Molecular Structure. Coulson.4&)}= 0 which again leads to Equation (8) of the text. 1952) pp. Coulson and J. [7] M. E. in Quantum Theory. Walter and G. pp. The curves intersect.){q(R. in the last step. J.(R.(R.). J. London.(Ro))(Y! Y 3 = 0 (15) If the contact is of zero order.) but E. G. if the contact is of order n.(R. D. pp.) = Ei(R. p. or do not intersect. and multiplication by the complex conjugate of v. K.) . 1963). A. In general. 204. Eyring.(R. . 295. in Handbuch der Physik. we differentiate Equation (15) n times and. Kimball. .(R. [4] H. Teller. remembering the set of Equations (1 l ) . (Academic Press. [2] A. London. and also Ei(R.(R. we differentiate Equation (15) with respect to R and find S{E’. 65-67. Kotani.

Phys. [I21 V. 1968). G. 1141 R. Di Bartolo. Quantum Mechanics (Pergamod Press. J. F. 163-164. London. Heine. 1960). S. 262-265. Group Theory in Quantum Mechanics (Pergamon Press. D. John. Murrell. L. pp. Landau and E. M. Valatin. pp. 1958). pp. hTew York. Tedder. Vol. New York. SOC. Z . 1 (Wiley-Interscience. London. London. 695 (1946). 1971. [8] [9] [lo] [ll] Received August 25. 154. von Neumann and E. 1970. N. 458-461. J. Courant and F. . Valence Theory (Wiley. Wigner. M. Optical Interactions in Solids (Wiley. 1965) p. 1965). Revised March 31. Lifshitz.58. 30 467 (1929).NON-CROSSING RULE IN QUANTUM MECHANICS 279 B. 223-224. Introduction to Calculus and Analysis. A. Physik. pp. [13] J. Proc. Kettle and J.

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