Abstract: A general problem that arises in the treatment of substituent effects on rates and equilibria of chemical reactions
is evaluating the changes in energy and geometric structure that occur when a fragment is removed from a molecule and replaced
by a new one. This question is approached from an a b initio viewpoint using analytical S C F H a r t r e e F o c k theory. For different
series of compounds, relative substituent effects on reaction rates, equilibria, or molecular properties a r e often very similar
and can be described in terms of group contributions plus interactions between groups. The origin of this phenomenon is examined
by considering a common geometry constraint, which has been generalized to define a hemistructural relationship. For diatomics
(AA, AC, CC), it is equivalent to bondlength additivity. An important consequence of the hemistructural relationship
is that all of the information necessary for determining the properties of the hemistructural molecule (AC) can be obtained
f r o m the two parent structures (AA and CC). No new information is needed. Ultimately, all empirical observations of
transferable substituent effects and molecular properties can be traced to this fact. T h e hemistructural relationship serves
as a fundamental basis for transferability within the BornOppenheimer, nonrelativistic limit. S o m e of the consequences of
this transferability a r e examined, a n d it is shown that the response of the total energy ( E ) ,the kinetic energy ( T ) , and the
total potential energy (V) to multiple substituent effects is fundamentally simpler than the corresponding response of the orbital
I. Introduction invariant from one molecule to another has been thought t o depend
on the extent t o which each molecular fragment experiences similar
I t is well k n o w n t h a t t h e e n e r g y of a molecule c a n o f t e n b e attractions and repulsions in different environment^.^ This concept
expressed a s t h e s u m of t h e energies of its individual b o n d s a n d of bond or fragment transferability has played a f u n d a m e n t a l role
t h a t these bond energies can frequently be “transferred” from one i n s h a p i n g o u r c o n c e p t s of c h e m i c a l b o n d i n g a n d structure.
molecule t o T h e d e g r e e t o which bond energies a r e A s i m p l e e x a m p l e illustrating t h e s e points is a c o m p a r i s o n of
Table I. Experimental Heats of Atomization and Ionization Potentials of Benzene and Azabenzenes
M A
(kcal/mol)a IP, ( e v l b
@
pyridine
1194.3 9.59 (n) 9.73 (nA) 10.50 (ns)
p y r az ine
pyrimidine
a Reference 6. Reference 7.
for benzene, toluene, and pxylene. The three experimental kcal) higher than the corresponding mean for pyrimidine and
heats of formation are 19.82, 11.95, and 4.29 kcal/mol, respec benzene, while the symmetric a orbital (a B,) is 0.675 eV (15.6
t i ~ e l y . The
~ average heat of formation for benzene and pxylene kcal) lower than the mean. The combined deviation from the mean
is 12.055 kcal/mol, which deviates by only 0.105 kcal from the amounts to 2.1 kcal which is an order of magnitude larger than
experimental value for toluene. This close correspondence to the deviation observed for the heats of atomization (0.20 kcal).
additivity can be easily “explained” by two arguments: (1) the The ionization data (through Koopmans’ t h e ~ r e m )show ~ , ~ that
“electronic structures” of the methyl groups, the benzene rings, the lone pair orbitals of pyrazine and pyrimidine are split by
and the 1,4 hydrogens do not depend on the particular molecule roughly 40 kcal. Significantly, the splitting is unsymmetrical
of which they are a part; (2) interactions between the 1 and relative to the lone pair orbital of pyridine, so that the lone pair
4substituents are n e g l e ~ t e d . ~ orbital energy of pyridine is over 20 kcal higher than the mean
However, there are cases of comparable additivity where the lone pair orbital energy of pyrazine or pyrimidine. These ob
applicability of the “constant structure” argument could be servations do not provide a convincing argument that the additivity
questioned. For example, the heat of atomization (AHA) for observed in the heats of atomization is due to a uniform electronic
pyridine is only 0.25 kcal lower than the mean heats of atomization structure of the nitrogens in pyrazine, pyrimidine, and pyridine.
for benzene and pyrazine or pyrimidine (Table I).6 This degree Additivity is also frequently observed for electronic energies
of additivity is somewhat surprising, since the structural pertur calculated using S C F HartreeFock techniques.I0 In one such
bations are taking place within a “delocalized” aromatic ring. It example,loaVbthe electronic energy of pyridine has been calculated
may seem a bit rash to assume that each of the two nitrogens in as 210.88630 au (Table 11). The mean electronic energy of
pyrazine or pyrimidine is simply the electronic equivalent of the benzene and pyrazine (using the same basis set and experimental
nitrogen in pyridine. If the electronic energy of pyrazine or geometries) is 210.89019 au. The deviation amounts of 2.4 kcal.
pyrimidine is analyzed in classical terms, we might expect to find By contrast, the sum of the orbital energies for pyridine deviates
a dipolar contribution arising from the interactions of the two from the mean by over 65 kcal (Table 11). The core orbitals alone
nitrogens. Classically, this might be described as an internal contribute 8 kcal to the total deviation. The core orbitals of the
dipoledipole repulsion, and it should lead to a breakdown in the nitrogens in pyrazine are influenced by the other nitrogen since
additivity of AHA for pyrazine and pyrimidine, since the effect the orbital energy of each nitrogen 1s core is about 30 kcal lower
is not only different for pyrazine and pyrimidine, but is absent than in pyridine. The lowering of the N1s core energies in
for pyridine and benzene. pyrazine relative to pyridine shows that the field experienced by
If the ionization potentials’ of pyrimidine, pyridine and benzene an electron close to the nucleus of the 1nitrogen is altered sub
(see Table I) are compared and interpreted within the framework stantially by replacing a CH group at the 4 position with another
of Koopmans’ theorem, it is apparent that additive heats of nitrogen. Even though both CH and N carry the same nuclear
atomization do not necessarily require additive orbital energies. charge and the same formal electronic charge, the effective field
The antisymmetric a orbital of pyridine (a B,) is 0.585 eV (13.5 of each group at even “remote” centers in the molecule is different.
The CH and N at the 4 position are not behaving as either
spherical charge distributions centered on nuclear point charges
(1) (a) L. Pauling, “The Nature of the Chemical Bond”, Cornel1 University or as multipoles whose field falls off so rapidly that it is ineffective
Press, Ithaca, N.Y., 1960. Some recent extensions of Pauling’s work include: near the 1 position.
(b) J. C. Phillips, “Bonds and Bands in Semiconductors”, Academic Press,
New York, 1963; (c) N. D. Epiotis, J. R. Larson, R. L. Yates, W. R. Cherry, Constant electronic structure and lack of interaction between
S.Shaik, and F. Bernardi, J. Am. Chem. Soc., 99, 7460 (1977); (d) B. M. substituents are sufficient conditions for observing additivity re
Gimarc, S . A. Khan, and M. C. Kohn, ibid., 100, 1996 (1978); ( e ) J. F. lationship~.~,~*” It has also been thought that these conditions
Liebman, ibid., 96, 3053 (1974); (f) J. R. Liebman and J. S. Vincent, ibid.,
97, 1373 (1975). (8) S. W. Benson and J. Buss, J . Chem. Phys., 29, 546
(1958). (8) T. A. Koopmans, Physica, 1, 104 (1933).
(2) (a) T. L. Allen and H. Shull, J . Chem. Phys., 35, 1644 (1961); (b) (9) M. J. S. Dewar, “The Molecular Orbital Theory of Organic
M. Levy, W. J. Stevens, H. Shull, and S. Hagstrom, ibid., 61, 1844 (1974). Chemistry”, McGrawHill, New York, 1969.
(3) R. F. W. Bader and P. M. Beddal, Chem. Phys. Lett., 8, 29 (1971). (10) (a) R. E. Christoffersen, J . Am. Chem. SOC.93,4104 (1971); (b) D.
(4) Strictly speaking, the 1,4 interactions in toluene must be the average W. Genson and R. E. Christoffersen, ibid., 94, 6904 (1972); (c) R. J.
of the 1,4 interactions in benzene and pxylene. Buenker, J . L. Whitten, and J. D. Petke, J . Chem. Phys., 49, 2261 (1968);
(5) D. R. Stull, E. F. Westrum, Jr., and G. C. Sinke, “The Chemical (d) J. D. Petke, J. L. Whitten, and J. A. Ryan, J . Chem. Phys., 48,953 (1968);
Thermodynamics of Organic Compounds”, Wiley, New York, 1969. (e) J. Almlof, B. Roos, U. Wahlgren, and H. Johansen, J . Electron Spectrosc.
(6) J. Tjebbes, Acta Chem. Scand., 16, 916 (1962). Related Phenom., 2, 51 (1973).
(7) (a) R. Gleiter and E. Heilbronner, Angew. Chem., Int. Ed. Engl., 9, (1 1) For example: (a) J. D. Cox and G. P. Icher, “Thermochemistry of
901 (1970); (b) R. Gleiter and E. Heilbronner, Helu. Chim. Acra, 55, 255 Organic and Organometallic Chemistry”, Academic Press, New York, 1970;
(1972). (b) J. Gasteiger and 0. Mammer, Tetrahedron, 34, 2939 (1978).
590 J . Am. Chem. SOC.,Vol. 104, No. 2, 1982 Murdoch
Table 11. Calculated Energies of Benzene, Pyridine, and Pyrazine
bEmean a 6Emean b &Emean c
T ’ 0 ’ o,core’
ET(au) kc al E&Og kcal Ezore(au)g kcal (kcal/mol)
a T = ET(pyridine) 
&Emean = E,(pyridine)  1/2[Eo(benzene)+ E (pyrazine)].
[ET(benzene) C E ~ ( p y r a z i n e ) ] . &Emean
=E y ( p y r i d i n e )  l/IIEye(benzene) + E y ( p y r a z i n e ) ] . Reference 10a,b. e Reference 10c,d. ?Reference 10e. gEo
and E F are the sum of the appropriate orbital energies (ref 10) and have not been multiplied by two.
are n e c e s ~ a r y . ~Support
.~ for this idea has come from firstorder molecule, it is useful to distinguish between electronic structure
perturbation t h e ~ r y which
,~ shows that additive changes in the and geometric structure. Geometric structure pertains to the
+
Hamiltonian (HI H,) translate into additive changes in the coordinates of the nuclei, while electronic structure includes the
firstorder energy, 6Em(’): spatial distribution of electron density. It is well established that
bond lengths and bond angles are often transferable between
molecules and that bond lengths frequently can be predicted by
where +: is the unperturbed wave function. Since the firstorder assigning covalent radii to various at0ms.l In such a case, an origin
can be defined for each of three diatomic structures (e.g., AA,
energy correction is additive and does not involve changes in wave
function, it may seem natural to associate energy additivity with AB, BB) so that the nuclear coordinates of “A” in AB are
constant electronic structure. the same as for the corresponding “A” in AA. Likewise, the
The secondorder energy correction is given by coordinates of “B” in AB are the same as for the corresponding
“B” in BB.
6Eg) = C (+RIHi + Hz(+!)/(E“,  @) (2) This idea can be generalized in order to specify a hemistructural
k#m
relationship. If an origin can be defined so that a subset of nuclei
The secondorder energy correction is due to changes in wave in molecule C have the same nuclear charges and coordinates as
function and is generally nonadditive because of the squared term a subset of nuclei in molecule D and the remaining nuclei in C
in the numerator of eq 2. Consequently, it has been thought that have the same nuclear charges and coordinates of a subset of nuclei
energy additivity will hold to the extent that the wave function in molecule E, then C is hemistructural to D and E. C can be
remains constant and secondorder energy corrections are neg referred to as a hemistructural molecule which is derived from
ligible. Energy additivity apparently depends on the degree to the parent molecules, D and E. It would also be possible for C
which electronic structure is constant and the degree to which net to share a hemistructural relationship with more than two other
interactions between substituents are absent or constant. However, molecules, and further generalization can be introduced by al
this conclusion is not in accord with experimental examples6 (e.g., lowing C to represent more than a single molecule.
pyridine and others5) which indicate that additivity can apparently A simple example of a hemistructural relationship is illustrated
be observed even when large interactions (compared to deviations by the geometry of toluene compared to the corresponding ge
from additivity) occur between substituents. This, in turn, implies ometries of benzene and pxylene. To a good approximation,’*
that compensating changes in electronic structure take place in onehalf of the toluene molecule can superimpose on a corre
other portions of the molecule so that additivity is somehow sponding half of pxylene, while the other half of toluene can
preserved. Such a result is a fundamental departure from existing superimpose on benzene. As a result, toluene is approximately
ideas o n substituent effects and would not be anticipated from hemistructural to benzene and pxylene.
models based on classical or traditional concepts. This prompts It is interesting that the hemistructural relation holds to a
us to find a more general description of the energy changes and reasonable degree for the examples of energy additivity discussed
structural perturbations which accompany replacement of one in section I. The CC and CN bond lengths in benzene and the
molecular fragment by another. azabenzenes are essentially c ~ n s t a n t ,as
’ ~are the corresponding
bond lengths and bond angles in benzene, toluene, and pxylene.12
11. A Theory of Nuclear Substitution
A. Hemistructural Relationship: Definition. In considering (12) “Tables of Interatomic Distances and Configuration in Molecules and
the energetic consequences of replacing a subset of nuclei in a Ions“, The Chemical Society, London, 1958.
Nuclear Substitution and Hemistructural Relationship J . Am. Chem. SOC.,Vol. 104, No. 2, 1982 591
Other examples include methane, bromomethane, and dibromo a and is independent of the nuclear coordinates. Since +i and
methane where heats of formation are additive to within 0.5 4, do not depend on nuclear coordinates, the same kinetic energy
k ~ a l . ~ . In
' ~ addition, it is noteworthy that the hemistructural integrals can be used in setting up the Fock matrices for ABA,
relation also holds for cases of energy nonadditivity.' This suggests ABC, and CBC.
that the hemistructural relationship is a suitable point to begin The electron repulsion integrals are of the form:
a theoretical study of substituent effects and the initial breakdown
from energy additivity that occurs for larger perturbations. We
shall initially inquire as to what constraints the hemistructural
relationship imposes upon the total energy and the nuclear forces
of the hemistructural molecule. In Appendix 11, it is shown that The operator, l / r a S ,depends on the distance between electron a
the hemistructural geometry may correspond to an equilibrium and electron 0 and is independent of nuclear coordinates. The
geometry as a consequence of these constraint^.'^ basis functions + i , +j, &, are also independent of nuclear
B. The Hemistructural Relationship: A Fundamental Basis of positions so that the same electronrepulsion integrals can be used
Transferability. The theoretical consequences of the hemistructural for the Fock matrices corresponding to ABA, ABC, and CBC.
relationship (at the HartreeFock level) can be discovered by The nuclearelectron attraction integrals are of the form:
examining how the Fock matrix differs for the three molecules
sharing the hemistructural relationship. For convenience the
structures of the three hemistructural molecules can be symbolized
as
The operator, 1 /rau,depends on the coordinates of nucleus a and
ABA (3) electron a,while the basis functions + i and +j are independent
of nuclear position. As a result, each nuclear attraction integral,
CBA (4a) cj:,depends on the coordinates of only one nucleus. This co
ordinate for ABC can be obtained from one of the two parents,
(4b) ABA or CBC, if nuclear geometry is additive (Le., the hemis
tructural condition is applicable). Consequently, each of the
CBC (5) nuclearelectron attraction integrals for ABC can be obtained from
where A, B, and C represent molecular fragments containing one or the other of the two structures (ABA and CBC) to which
arbitrary nuclei. ABC is hemistructural to ABA and CBC, and it is hemistru~tural.'~
it could be said that the three molecules form a hemistructural The fundamental significance of the hemistructural relationship
set. is now apparent: the hemistructural relationship is special, since
The Fock matrix elements are dependent upon the kinetic all integrals necessary for constructing the Fock matrix for hemi
energy integrals, electron repulsion integrals, nuclearelectron structural ABC (Le., Tij, VL;"'.Vi:) can be obtained from the two
attraction integrals, and the molecular orbital coefficients of the parent structures (ABA or CBC). If ABA, ABC, and CBC are
occupied MOs. Since we are interested in comparing Fock matrix not members of the same hemistructural set,I5 the Vi: for ABC
elements, it will be advantageous to evaluate the various integrals will not necessarily be transferable from ABA and CBC, and new
using a basis set which is mathematically complete16 and not information (Le., new e:)must be introduced to construct the
necessarily associated with particular nuclei. As long as the basis Fock matrix for ABC. Consequently, the properties of ABC will
set is comp1ete,l6 it is unnecessary to change basis functions when no lon er depend on the same parameters or information (Le.,
the nuclei are altered. The ith basis function can be represented Tij, V i ' , Vl:) as ABA and CBC, and the relationship between
as 6. the three structures will become more obscure. The hemistructural
The kinetic energy integrals are of the form: relationship is unique in the sense that all of the information (Le.,
Ti/,VLk', Vi:) necessary for constructing the Fock matrix and for
determining the HartreeFock wave function and energy of the
hemistructural molecule (ABC) can be transferred from the parent
structures (ABA and CBC)." This is also true for the exact
The kinetic energy operator, Vu2,contains coordinates of electron nonrelativistic energy and wave function since correlation effects
can be introduced through configuration interaction in terms of
(13) (a) P. J. Wheatley, Acta Crystallogr., 10, 182 (1957); (b) P. J. Slater determinants which are constructed from the HartreeFock
Wheatley, ibid., 13, 80 (1960); (c) B. Bak, L. HansenNygaard, and J. orbital^.^^*^^ The fact that the hemistructural molecule contains
RastrupAndersen, J . Mol. Spectrosc., 2, 361 (1958); (d) V. Schomaker and
only information which is common to the parents (Le., geometric
L. Pauling, J. A m . Chem. SOC.,61, 1769 (1939); (e) E. G. Cox, D. W. J.
Cruickshank, and J. A. S . Smith, Proc. R. Soc. London,Ser. A , 247, 1 (1958).
(14) (a) D. Chadwick and D. J. Millen, Trans. Faraday SOC.,67, 1539
coordinates, Tu, VLk', e:)places an important constraint on the
relationship of the hemistructural wave function and energy with
(1971); (b) C. C. Costain, J. Chem. Phys., 29, 864 (1958); (c) W. Gordy, the wave function and energy of each parent. In this sense, the
J. W. Simmons, and A. G. Smith, Phys. Rev., 74, 243 (1948).
(15) The examples cited above are not intended to lead the reader into hemistructural molecule contains no new information.
believing that the hemistructural relationship is limited to equilibrium geom One expected consequence is that properties of the hemi
etries. Note that each point on the ABC potential surface will correspond structural molecule may often be related in a simple manner (e.g.,
to a point on the ABA potential surface where the geometric coordinates additive or quadratic) to the properties of the two parents, but
of the A,B fragments are identical and to a point on the CBC potential
surface where the geometric coordinates of the B,C fragments are identical. this, of course, will not be general. Nonetheless, once the Fock
Each group of three corresponding points constitutes a hemistructural set, and matrix for ABC is defined, the question of how properties of the
there will be one hemistructural set for each point on the ABC potential hemistructural molecule depend on information transferred from
surface (is., infinite). The examples noted above (e.g., benzene, toluene, and the parent structure is solved in principle. In the next section,
xylene) are special cases where energy minima on three potential energy
surfaces are connected through a hemistructural relationship. See Appendix we will examine some generalizations which can be applied without
I1 for a further development of this idea. detailed computation.
(16) (a) Examples of complete basis sets include threedimensional
Cartesian polynomials and spherical Gaussians located at all possible points
in space with all possible exponents (also see: S. F. Boys, Proc. R. SOC.
London, Ser. A , 200, 542 (1950). (b) For more detailed discussion, see: B. (17) The transferability noted at the integral level translates into trans
Klahn and W. A. Bingel, Int. J . Quantum Chem., 11, 943 (1977). (c) ferability at the density matrix level. See eq 11, eq 110, and the discussion
Nonnuclearcentered basis sets are commonly used in numerical calculations in Appendix I. Note that the density matrix elements are not simply additive,
dealing with solidstate phenomena. For example, see: (d) G. P. Kerker, S. but can be constructed from transferable terms.
G. Louie, and M. L. Cohen,, Phys. Reu. B, 17, 706 (1978); (e) K. H. Lau (18) E. A. Hylleraas, Z . Phys., 48, 469 (1928).
and W. Kohn, Surf. Sci. 75, 69 (1978); (f) N. H. March and M. P. Tosi, (19) F. L. Pilar, "Elementary Quantum Chemistry", McGrawHill, New
Proc. R. SOC.London, Ser. A , 330, 373 (1972). York, 1968.
592 J . Am. Chem. SOC.,Vol. 104, No. 2, 1982 Murdoch
C. How Is the Energy of the Hemistructural Molecule Related the new kinetic and potential ( Vne,V,) energies:
to the Energies of the Parent Molecules? a. The Hemistructural
Fock Matrix. Since the large majority of ab initio calculations
on molecules are based on HartreeFock theory, it would be useful
to answer this question at the HartreeFock level. Extending the
occ
result to include correlation effects is straightforward and will be
presented later. V,, = 2 E x E ( a : j
v i J
+ a:,)(V!, + sv!,)(a:j+ &) (18)
The Fock matrix element, F,, for a closedshell system is given
by
F , = Hb + Pk/[(ukl)  y2(ikjl)] (9)
k /
The kinetic energy matrix elements, Tijl are not affected by the
where H; is the core matrix element which is constructed from perturbation so that the change in kinetic energy depends only
the sum of the corresponding kinetic energy matrix element on the change in coefficients, a,,,. The potential energies are a
h2 function of the corresponding matrix elements as well as the
Tu = Tij = ~(4i1Va214j) coefficients, a”,. The result is that the kinetic energy is governed
by a fundamentally simpler relationship than V,, or Vee, One
and the nuclearelectron attraction matrix element,9 consequence of this simpler relationship is that when changes in
+
a’ are additive (i.e., auj= uLj a;,), the kinetic energy may be
aiditive (to first order in a’”,) without V,, or V, being additive.
This disparity in behavior between T and V,, is particularly in
teresting since both are oneelectron properties.
Pklis an element of the density matrix and is given by The behavior of the kinetic energy is an important result since
OCC the total energy, including the nuclear repulsion energy (V,,), is
pkl = 2xaukav/ related to the kinetic energy through the virial theoremI9
Y
2. Geometry Nonadditivity and HOMO/LUMO Separations. fact that bond length additivity may fail for AB and BC dis
The extension of the theory to examples where deviations from tances in ABA, ABC, and CBC before it fails for the AC
geometry and coefficient additivity occur appears to be distance is an important result which will be developed in future
straightforward. One factor, related to the energy separation of work.
occupied and vacant orbitals,39is the contribution of higher order It is also shown that the additivity of the kinetic energy20 is
perturbation termsS9 This will affect the behavior of the MO equivalent to additivity of the total energy, but this additivity does
coefficients with respect to bV,, (eq 19) as well as the relationship not require constant electronic structure in any particular region
between the twoelectron repulsion terms in eq 16. The virial of space. Even in the limit of a small perturbation, equivalent
theorem (eq 20 and 111) and the HellmannFeynman theorem groups are not a prerequisite for additivity relationships.
(eq 112) also place important constraints on the dependence of This firstorder treatment of nuclear substitution has altered
the MO coefficients as a function of 6V,, (eq 1719) and its longheld views on the relationship between molecular structure
derivatives (eq 1179, 111922). Treating deviations from ge and empirical dissections of molecular properties into group
ometry additivity would have important applications in the pre contributions. The present work has also provided a firm theo
diction of transitionstate structure, structures of analogous stable retical foundation for several concepts which have been established
intermediates, geometries of metal complexes, and geometry empirically for years. Nonetheless, it would be unreal is ti^^^ to
changes due to acquisition or loss of an electron. Prediction of expect that all aspects of chemical bonding can be described as
force constants and isotope effects are other potential areas of firstorder effects. The extension of the present work to higher
investigation. order corrections and the elucidation of more general effects on
molecular properties, structure and dynamics is now underway.
IV. Summary and Conclusions
Appendix I
Some examples of bond energy additivity appear to be explicable
in terms of equivalent groups, but there are a number of cases The Hemistructural Wave Function: FirstOrder Corrections.
where bond energy additivity persists even after the equivalent From eq 12, it can be seen that the perturbed density matrix
group concept has broken down (e.g., benzene, pyridine, and element P k / is given bya
pyrazine). The failure of existing concepts to account for this occ
relatively simple phenomenon prompted the present approach for pkl = 2C(a!k + a:k)(a5 + 41) (11)
treating nuclear substitution. V

Bond length additivity has been demonstrated as a limiting case
when fragment transfer (AA + CC 2AC) is described by
firstorder corrections to the MO coefficients. Within this (16)
firstorder framework, energy changes due to fragment transfer
For the special case of a small perturbation, perturbation theory9
may be additive or nonadditive, and consequently bond length
(second order in energy; first order in wave function) can be used
additivity does not necessarily require bond energy additivity. The
to relate $,,(eq 14) to 6F. The coefficients (eq I4), b,, are given
by4’
$39) (a) Substituting eq 11into eq 16, it can be shown (see ref 9) that
6V, is approximated by 6V N 41FxFOEEb,,l x t & a O , , 8vtl +
2 1 ~ 1 1 ~ : a r b , , b , , 1 . t l a ~ p ~ , j k(b)l . Equation 17 gives a good descrip
tion of the changes to the M O coefficients when the b., terms are small (Le.,
b, C 1.0). In such a case, one could anticipate thatihe second term of eq
16, which contains the product, b,b,., may be smaller than the first term,
which contains only one b , coefficient. It is recognized that the size of b,, For small perturbations, only the first term of eq 16 makes a
may not be the only factor involved in regulating the relative magnitude of
the first and second terms of eq 16, but for one specific example of a per significant contribution to 6V$39b and on substitution into eq 17
turbation (a series of mononuclear atoms and ions where the nuclear charge
represents the perturbation) it can be shown analytically that the second term
of eq 16 vanishes (within the firstorder framework), even though individual
terms in the summations are nonzero. This has been verified by higher order
numerical calculations (D.E. Magnoli, Thesis, UCLA, 1980), which also show ( 4 0 ) When the relative order of perturbed and unperturbed orbitals is
that the first term of eq 16 dominates the second term until some of the b,, unchanged, application of eq 11 is straightforward. In other cases, proper
approach and exceed one. The generality of this result and the effect of numbering of the orbitals will ensure a correspondence. between apt and a!k
including higher order corrections to the M O coefficients are under exami
nation.
+ ait. All perturbations relevant to the present paper can be treated within
an isoelectronic and isonuclear framework (see ref 44 and 45).
596 J. Am. Chem. SOC.,Vol. 104, No. 2, 1982 Murdoch
gives42 The total change in MO coefficients, a:,,,, for the perturbation
1 OEC ABA to CBC is equal to the sum of the changes in MO coefficients
Eo,$ , CCUO
b,, = [X:Ca$j(4,X:Cb,
i j
Ukl, +
I p k~ ' 0 . 6Vie)~;j] V/ for the perturbation ABA to ABC and ABA to CBA.
(18) Appendix I1
which on rearrangement is equivalent to Forces in the Hemistructural Molecule. In the BornOppen
heimer approximation, the nuclear motions of a molecule can be
ba, = viewed as occurring in a potential field provided by the electrons
1 occ
and nuclei. Consequently, the forces acting on a particular nucleus
[4:CCb,, CCXXa$a:jaEka:Pijk/ + CCa$a;javie]
E:Eg v p i i k I i j
(19)
The unknowns in eq (19) are b,, on the righthand side and
b,, on the lefthand side. The energies E", and E$ as well as the (41) Although a full discussion of this application of perturbation theory
coefficients nzj, a&, &, and ufl and the integrals 0 j j k / are fixed will appear elsewhere, the highlights of some important points are covered
below.
and do not vary with the perturbation. The only variables are I. Materialization of Atoms into Empty Space. Since the basis set is
the nuclearelectron attraction matrix elements, SVie. Equation nonnuclear centered and independent of nuclear charges and positions, it is
19 permits a selfconsistent solution for b, within the perturbation worthwhile to address the question of whether or not the firstorder treatment
framework imposed by eq 17. The selfconsistent aspect of eq (Le., eq 17) is applicable to a problem where a nucleus moves from one point
in space to a region which originally did not contain any nuclei. At first
19 permits the recovery of a portion of the higher order terms glance, it may seem that when an atom materializes at a point which had low
omitted by the more common expression, eq 17. A full treatment electron density in the unperturbed system, all of the Fock matrix elements
will be presented el~ewhere.~'Alternative forms of selfconsistent involving basis functions in the nearby volume will change dramatically, and,
perturbation theory have been presented.43 as a result, firstorder treatments may break down. However, the situation
is not so simple. It is instructive to consider a complete basis set consisting
Equation 19 can be applied to three hemistructural molecules of spherical Gaussians with a continuous range of exponents located in each
(e.g., structures 35) by treating ABA as the unperturbed volume element of space (see ref 16). The unperturbed case can be taken to
reference. The two perturbations are represented by the change be an arbitrary molecule located at the origin in a defined, but arbitrary,
in structure from ABA to ABC (CBA) and from ABA orientation. In principle, a Fock matrix can be constructed and used to
generate a set of orbital energies and molecular orbitals. The perturbation
to CBC. Since C and A are generally not isonuclear or iso is a translation which moves the molecule an arbitrary distance from the origin
electronic, the associated energy changes could easily amount to (e& 50 A). A new Fock matrix can be constructed and used to produce a
thousands of kilocalories or more, and the applicability of per perturbed set of molecular orbitals and orbital energies. Since the molecule
turbation theory is not immediately obvious. This apparent has only been translated, it is clear that the orbital energies are unchanged.
However, the MO's have undergone a subtle modification: for example,
problem can be overcome by adding extra molecules or fragments suppose a particular core orbital (e.g., M O 1) of the unperturbed molecule
to each structure in order to achieve an isonuclear and isoelectronic is largely represented by some combination of basis functions, including 9,.
condition. As an example, the unperturbed reference becomes When the molecule is moved away by 50 A, it is clear that 4, will no longer
(ABA + 2C), the first perturbed structure becomes (ABC make a significant contribution to MO 1, which will now be represented by
some new combination of basis functions, which made negligible contributions
+ C + A), and the second perturbed structure is represented by to the MO's of the unperturbed molecule. This may appear to be a case of
(CBC + 2A). The energy differences are now reduced to the a large change in coefficients, but if we look further, it will be seen that it is
range of zero to tens of kilocalories and represent a small fraction not the numerical values of the coefficients which have changed, but only the
of the total molecular energies.44 Total energy differences, as basis functions assigned to the coefficients. If the numerical values of the
unperturbed coefficients are compared to the numerical values of the perturbed
well as relative energy differences, are substantially reduced, and coefficients, a onetoone correspondence will be found between the two sets
the addition of extra structures results in no loss of chemical of coefficients. The basis functions associated with each value of coefficient
~ignificance.~~ These extra structures will not be written out again will differ. Similarly, the Fock matrix for the perturbed problem will contain
and will be implicitly assumed hereafter. In a subsequent paper, numbers identical with those of the original Fock matrix but in different
positions. In fact, the perturbed Fock matrix differs from the unperturbed
an example is presented in which a 495 OOOkcal difference between Fock matrix by interchanges of appropriate rows and columns. The row and
ABA and CBC (which represents 75% of the total energy for column interchanges have no effect on the values of the orbital energies or
CBC) is reduced to 44 kcal by maintaining the perturbation within on the set of numerical values appearing as coefficients for each eigenvector.
an isoelectronic and isonuclear framework. The 44 kcal represents The coefficients will be associated with different basis functions, but will have
identical values. When the appropriate row and column interchanges are
less than 0.006% of the total energy of ABA + 2C or CBC + carried out, the perturbed Fock matrix corresponds, element by element, to
2A. The absolute and relative energy reductions reflect the fact the unperturbed Fock matrix, and application of eq 17 is straightforward and
that changes in individual orbital energies, Mulliken populations, trivial.
electron densities, and density matrix elements are relatively small Let us consider a second case where the unperturbed molecule is moved
into a region close to a positive charge. When the row and column inter
in going from ABA +
2C to ABC + C + A to CBC + changes are performed on the perturbed Fock matrix and the elements are
2A for at least one actual example. A more quantitative analysis compared with the corresponding elements of the original Fock matrix, it will
concerning the applicability of this form of perturbation theory be seen that the values are no longer equal. If the effect of the positive charge
is in progress.36 on the electronic structure of the molecule is small, then application of eq 17
is again straightforward. The point of these two examples is that simple
The change in V,, on going from ABA to CBC is given translation of a molecule to a new region of space has no effect on the
by the sum of the separate changes in V , , on perturbing ABA applicability of eq 17, as long as the appropriate row and column interchanges
to ABC and to CBA. The fact that eq 19 represents a set are carried out and the translation does not result in a large electronic re
of simultaneous linear equations and that changes in V,, are organization. The important point is not that a large change in coefficient
of a particular basis function takes place on translation, but the extent to which
additive and assignable to changes in individual nuclei is significant the electronic structure of the fragment is perturbed by the translation.
since changes in the coefficients (Le., b,J must also be additive The row and column interchanges are equivalent to 'moving" the unper
and assignable to changes in individual nuclei.46 From eq 15 turbed MO's to the new position of the fragment or the molecule. The
it can be seen that if the changes in b,, are additive, then changes interchanges avoid the difficulty of trying to represent the new MO's in terms
of orbitals centered some distance away. Note that after the appropriate row
in a:,,, will also be additive. If a:, is associated with the pertur and column interchanges (or after any linear transformation of the matrix
bation ABA to CBC, then ai, can be divided into two parts. One elements) are completed, the V,, matrix elements of the transformed Fock
term (ai,,,) is associated with changing nuclear positions and matrix will still be a sum of contributions from individual nuclei, the V, matrix
charges in the righthand fragment and corresponds to the per elements will be given by an equation of the form of eq 12, and the kinetic
energy matrix elements will still be transferable. Consequently, the application
turbation ABA to ABC. of linear transformations to the unperturbed and perturbed Fock matrices
The second term (a!,,,,) describes the change in coefficients for before application of first order perturbation theory will not alter the form
the perturbation ABA to CBA. The change in coefficient, ui,,,, of eq 110 or the basic conclusions concerning 'coefficient" additivity.
is given by For our present purposes, these row and column interchanges need not be
specified, but if the reader wishes to apply eq 17 to actual numerical examples,
a:, = a:, + a;, (110) the appropriate interchanges are necessary before attempting to calculate the
Nuclear Substitution and Hemistructural Relationship J . Am. Chem. Soc.. Vol. 104, No. 2, 1982 591
can be expressed as gradients or +he potential field which is electron densities), it would also be expected to produce certain
generated by the electrons and the other nuclei. Nuclear forces constraints on nuclear forces.
are of interest since the simple form of the virial theorem ( E = If these constraints act to produce zero net force on each nuc
 T = V/2, eq 20 ) can be applied when forces on the nuclei are leus, the hemistructural geometry will satisfy the simple form of
zero. This allows us to express the total molecular energy, in the virial theorem ( E = 7‘) and may correspond to an equilibrium
cluding nuclear repulsion, in terms of the electronic kinetic energy geometr~.~’While there are many experimental examples of this
given by eq 17. When the forces acting on the nuclei are not zero, situation,’ it is also known1 that net nuclear forces may exist at
the virial theorem assumes a slightly different formig the hemistructural geometry, so that the equilibrium geometry
of ABC is distorted away from the hemistructural geometry
3N aE
E=T EX,,, (111) defined by the equilibrium structures of ABA and CBC.
m=l ax,,, Consequently, forces on the nuclei at the hemistructural geometry
where N is the number of nuclei and the X,,, represent the nuclear assume fundamental importance, since they can be related to the
coordinates. Equation 111 permits us to express the total energy, total molecular energy through the generalized virial theorem (eq
E , in terms of the kinetic energy and the forces acting on the nuclei 111) and to geometry deviations from the hemistructural rela
(e.g., aE/aX,,,). Equation 111 is a useful expression since the tionship imposed by the equilibrium geometries of ABA and
geometry aspects of the hemistructural relationship apply at both CBC.
equilibrium and nonequilibrium geometries. Each point on the The force on a nucleus in the direction of nuclear coordinate
potential surface for ABC will be hemistructural with respect X,,,is given by the generalized HellmannFeynman theorem4*as
to corresponding points on the potential surfaces for ABA and
CBC. Since the geometry imposed by the hemistructural re (112)
lationship results in certain constraints on the wave function (and
where 9 is the total wave function (nuclear and electronic) and
~
A similar expression for a given nucleus in the lefthand "C" The force on a "B" nucleus in ABA is given by
fragment of CBC is given by occ
occ 2 C [aEV?eaE] + ZB(NA, + NA/ + NE) = 0 (1116)
2C[aEV$LaE + 2aLV:LaE + 2a;V:ia; + aLV:LaL + 2aLV:L a; + P
P
and eq 1117 gives the force (dE/dXm)Bon a "B" nucleus in CBC
a;V:;a;] + Zcl(Ncr + NB+ NAr+ 6NCJ = 0 (1112) occ
V$' is a function only of the coordinates of one specific nucleus +
~ C [ ~ E V : ~ ~2aLVFeaE
E + 2a;VgeaE + afiVteah+ 2a;V,B,a; +
P
in the left "C" fragment of CBC, while as, a;, and a; include a
functional dependence on the nuclear charges and positions of the a;V,!!ea;] + ZB(NA, + SNc, + NA/ + SNc, + NB) =
"B" nuclei. Consequently, eq 1112 can be separated into the (dE/dX,)B (1117)
analog of eq 117 Separating eq 1117 into terms based on I , r, and B dependence,
Fo~(l+ ) FdLr) = 0 (1113) (dE/dXm), = Fo(B) + F1(l,B) + F2(r,B) + F3(I,r,B) (1118)
where FoB(l)equals
where
FOB(0 =
occ
2C[aEV:LaE + 2aLV:LaE + aLV:LaL] + ZC~(NC/+ NB+ N A ~ ) 0 (1119)
P
(11 14)
and FIB(l,r)equals (1120)
occ
FIB(l,r) = 2 C [2a;V:LaE + 2ahV:La; + a;V:La;l + ZC/(SNC,)
P OCC
(1115) F2(r,B) = 2C[2a;Vfl,aE + a;VEea;] + ZB(6Ncr) (1121)
P
Using the p r ~ p e r t that
y ~ ~FoB(l)
~ ~ ~and FIB(I,r)vanish separately,
it is apparent that forces on the "C" nuclei are zero in CBA. OCC
Likewise, it can also be shown that the forces on "A" in CBA are F3(l,r,B) = 4 Z aLVgea; (1122)
zero by using CBC as the unperturbed reference and ABA as the P
double perturbation. In order for CBA to be an equilibrium (or At this point it would be useful to reflect on the significance
zero force) structure, it must also be shown that the forces on the of this force analysis. First, it has been shown that within the
"B" nuclei vanish.50 limitation of firstorder coefficient corrections, the force on a
particular nucleus in CC can be divided into two or more terms
(e.g., eq 117 through eq 119). If a zero force structure for CC
exists, then each separate force term49must vanish. One of these
terms is also the force on the corresponding nucleus in CA at
and from 11lob, a zero force condition with respect to F' requires the hemistructural geometry, and from this it follows that if CC
F E ( l , r ) = 0 = F, (11log) and AA are zero force structures, then CA will also be a zero
force structure at the hemistructural geometry. The separate
Again, this result is valid for any mononuclear fragment, E, which can pair vanishing of each force term represents a constraint on the behavior
with Fo to produce a zero force structure. Consequently, the separate van
ishing of the two force terms is required for any zero force structure containing of the coefficients a; and a;, and if the constraint cannot be met,
FO: no zero force structure is possible within the firstorder pertur
bation framework. Achieving a zero force structure may require
q(f)
= Fre(l,r)= Fl = 0 (11lOh)
more complicated electronic reorganization than allowed by
A zero force structure for FoEo requires satisfaction of both 11lOe and firstorder changes in the wave function. Higher level pertur
11lOh which are equivalent to the separate vanishing condition bations may eventually lead to a breakdown of coefficient ad
q(f)
= q"E'(l,r) = e ( r ) = qe'(r,/) = 0 (111Oi) ditivity (eq 16), and the simple transferability of the force terms
between the hemistructural molecule and the parent structures
This result establishes that the two force terms in eq 11lOc and 11lOf vanish
separately at any zero force geometry for arbitrary FOEO. (eq 11710) will not apply. As a result, the hemistructural ge
The force equations shown above involve displacements of the atomic ometry may no longer correspond to a zero force s t r ~ c t u r e . ' ~
fragments in any of the three Cartesian directions. The force can also be Similar remarks apply to the ABA, CBA, and CBC cases,
expressed in terms of the energy gradient with respect to any suitable coor and the circumstances which permit simultaneous realization of
dinate, and for polynuclear fragments it is useful to consider coordinates which
include movement of the fragment as a whole in the X,U,or 2 directions as conditions b and c (vide supra) will require further examination.
well as coordinates describing internal changes in bond lengths and bond The possibility that firstorder perturbations may not allow
angles. The treatment of the internal coordinates involves a number of subtle separate vanishing of Fl(l,B), F2(r,B), and F3(l,r,B) is worth
points and will require full development elsewhere, but displacements of the considering. In the case of FI(l,B) and F2(r,B), balance between
individual fragments as intact units can be handled like displacements of
individual atoms. Equations 11loa through 11lOi are still applicable for electronic and nuclear terms can be achieved by variations in the
f o r m associated with displacement of polynuclear E', E, F", and F fragments. coefficients as well as internuclear distances. However, F3(l,r,B)
It is useful to note that the separate vanishing condition is reference de contains only nuclearelectron attraction terms and lacks nuclear
pendent and requires a t least one zero force geometry for DEo and F'D. repulsion terms to cancel them out. Separate vanishing of Fl(I,B),
For the present application (AA, CA, CC), this is equivalent to the re
quirement that D C and AD have at least one zero force geometry. If this F2(r,B), and F3(Z,r,B) can occur on1 to the extent that the sec
condition is met, then zero force geometries for AA, AC, and CC require Y
ondorder electronic terms, 4CyaPVflea; (eq 1122) are zero.
the separate vanishing of the Fo and F , force terms. Note that if Fo and F, Consequently, we have the interesting result that the nuclear forces
vanish separately for CC and AA using DD as reference, then Fo and F, on the "A" and "C" fragments of CBA can be zero through the
also vanish separately for CC (AA) using AA (CC) as reference.
(50) Equations 11loa through 11lOi can be used to show that, using the full secondorder terms, while the forces on the "B" nuclei can
zero force structure DD as reference, the two force terms associated with be zero only through firstorder and part of the secondorder terms.
DI or D2 in the zero force structure D,D2 vanish separately. A similar result The fact that the hemistructural relationship may break down
holds for the two force terms associated with E, or E2 in the zero force for the "B" nuclei before it does for the "A" and "C" nuclei could
structure, E,E2. These results can be applied to the zero force structures
AEA (AB)A ElE2 and CBC (CB)C = DIDZ. Note that have important consequences for group transfer reactions such
it has been implicitly assumed that the nuclear coordinates of the 'B" frag as CB + A C + BA where ABA, CBA, and CBC are
ment are the same in ABA and CBC. transition states. If the CA distance is hemistructural, while B
600 J. Am. Chem. SOC.1982, 104, 600610
is shifted off of the hemistructural position toward C, for exam down of the hemistructural relationship is currently under ex
ple,s2the CB bond in CBA would be shorter (and stronger) than amination.
the CB bond in CBC. This decrease in length for CB would
come at the expense of the BA bond in CBA which would be Acknowledgment. The author would like to thank Professors
longer (and weaker) than in ABA. The total bond length, CB Arno Liberles, William Gelbart, Daniel Kivelson, William
plus BA, would be constant. The situation is somewhat analogous McMillan, E. R. Davidson, Norman March, R. A. Marcus, Lionel
to Johnston'ss1 proposal concerning the conservation of bond order Salem, Klaus Rudenberg, Bernard Kirtman, and James Muck
in transition states of atomtransfer reactions, where the bond order erman for extensive discussions and many helpful comments. The
of one bond may be greater than 1/2, while the bond order of the author would also like to thank Drs. Douglas Magnoli and Peter
other is less than 1/2. The total bond order is always conserved Ogilby for critical comments in the early stages of the work. This
at unity. The speculation that Johnston's empirical principle of research was supported in part by a grant from the donors of the
bondorder conservation may have its origins in a partial break Petroleum Research Fund, administered by the American
Chemical Society, by the Pennwalt Corporation Grant of Research
Corporation, by a USPHS Biomedical Research Grant (4
52135524739), by the University Research Committee (UCLA),
(51) H. S. Johnston and C. Parr, J. Am. Chem. Soc., 85, 2544 (1963).
and by the National Science Foundation. The author also ac
(52) Lateral displacements along the AC bond axis, as well as perpen knowledges a Regent's Junior Faculty Fellowship (19781979)
dicular displacements, may be possible. and a UCLA Faculty Career Development Award (19791980).
Abstract: The rates of protontransfer reactions between 9substituted fluorenes and 9substituted fluorenyllithium have been
examined in ether at 25 and 71 OC. A high primary isotope effect (kH/kD= 9.5) and substantial secondary kinetic (1.11
0.04) and equilibrium (1.19 h 0.04) isotope effects are observed for fluorene. Surprisingly, intermolecular steric effects
seem to play only a minor role in spite of the fact that the alkyl groups are located directly at the carbon involved in the proton
transfer. The barriers for the endergonic cross reactions (Le., those involving different alkyl groups in the anion and hydrocarbon)
are half of the sum of the barriers for the two corresponding identity reactions (Le., those involving the same alkyl groups
in the anion and hydrocarbon). This leads to Brmsted slopes which vary from 0.7 for reactions of fluorenyl anion to 1.8 for
reactions of 9(tertbutyl)fluorenyl anion. The rates of the identity and cross reactions give approximate linear correlations
with each other and with ApK and are dominated by an effect which correlates with u*. The substituent effect correlated
by u* is inconsistent with a classical field or repulsive steric effect and may originate from solvation effects. The thermodynamic
and kinetic relationships between the identity and cross reactions show that the transition states for the cross reactions are
only responding to half of the substituent effect on the identity reactions and that the substituent effect on the equilibria appears
absent from the crossreaction transition states. The results can be consistent with Marcus' theory only if the substituent effect
on the equilibria appears in steps separate from proton transfer. The results suggest that changes in solvation and proton
transfer occur as discrete kinetic steps.
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