Article

pubs.acs.org/JPCA

Singly Occupied MOs in Mono- and Diradical Conjugated

Hydrocarbons: Comparison between Variational Single-Reference,
Fully Correlated and Huckel Descriptions
Nicolas Suaud, Renaud Ruamps, Jean-Paul Malrieu, and Nathalie Guihery*
Laboratoire de Chimie et Physique Quantiques, UMR 5626 CNRS, IRSAMC, Universite de Toulouse III Paul Sabatier,
118 Rte de Narbonne, 31062 Toulouse Cedex, France

ABSTRACT: This work compares three descriptions of the unpaired electrons

distribution in conjugated monoradical and diradical hydrocarbons involving
one or two methylene groups attached to an aromatic skeleton. The rst one is
the simple Huckel topological Hamiltonian, the singly occupied molecular
orbitals (SOMO) of which may be analytically obtained. The second one is the
restricted open-shell self-consistent eld (ROHF-SCF) method. The so-
obtained distribution of the unpaired electrons on the skeleton appears deeply
dierent from that predicted by the Huckel Hamiltonian, being more strongly
localized on the external methylene groups. More elaborate methods treat all
electrons in the valence molecular orbitals (MOs) through a full valence
complete active space self-consistent eld (CASSCF) treatment. The
distributions of the unpaired electrons (given by the natural MOs of occupation
number close to 1) are surprisingly similar to those predicted by the Huckel
model. The spin density distributions, including spin polarization eects, can be improved by further conguration interactions
involving one holeone particle excitations and compared with the experimental hyperne coupling constant ratios. This
comparison conrms the lack of delocalization of the magnetic orbitals dened from the self-consistent single-reference
treatment. We show that, provided correct SOMO are used, a single excitation CI performed on top of a single reference gives
accurate spin densities. Finally, a rationalization of the role of the dynamic correlation in correcting the excessive localization of
the unpaired electron(s) at the ROHF level on the exocyclic methylene group(s) is given, attributing it to the dynamic charge
polarization of the charge transfer congurations between methylene and the aromatic frame.

I. INTRODUCTION of these simple pictures, compared to more sophisticated

Conjugated hydrocarbons were the rst and privileged training descriptions, may be found in reviews by Borden et al.5,6
ground of quantum chemistry until the mid sixties. The Among the successes of the Huckel model one must quote
the prediction7 of the spin-density distribution in radical
delocalized character of these systems led to some properties
conjugated hydrocarbons. The contact terms on the in-plane
that could not be understood from chemical intuition, for
protons responsible for the interaction between the electron
instance, the spacing between the ionization potentials, some
spin and the nuclear spins are observable by electron spin
spectroscopic features, and some specic reactivity prefer-
resonance (ESR) spectroscopy.8 These contact terms are due
ences.1 The quantum origin of these properties was not
to the spin-polarization7 of the electrons in the CH bonds
accessible to the dot-and-arrow models with which the chemists
and they depend on the spin density in the atomic orbital
used to interpret the properties of the molecules they handled.
(AO) of the carbon to which the hydrogen atom is attached.
The rather primitive monoelectronic model Hamiltonians
These radical systems possess an unpaired number of electrons
provided a rich harvest of results and rationalizations. The
(2n + 1), and the (n + 1)th MO is considered as being singly
simplest model is the topological Huckel Hamiltonian, which
occupied and is labeled SOMO (singly occupied MO). This
only deals with the system and only considers equal hopping
spin density was approximated by the square of the coecient
integrals between adjacent carbons. The considerable amount
of this SOMO, and the proportionality of the observed contact
of results obtained from this simple model has been, for
terms with these calculated quantities had led some
instance, nicely presented in Salems book.1 One should also
mention that beyond this model, the electronelectron
correlation problem was already considered through the Special Issue: Energetics and Dynamics of Molecules, Solids, and
introduction of the PariserParrPople (PPP) Hamiltonian,2,3 Surfaces - QUITEL 2012
a sophisticated version of the Hubbard Hamiltonian,4 proposed Received: December 10, 2013
in solid state physics a few years later, which remains a Revised: February 27, 2014
milestone and a reference model in this domain. The relevance

XXXX American Chemical Society A dx.doi.org/10.1021/jp4120892 | J. Phys. Chem. A XXXX, XXX, XXXXXX
The Journal of Physical Chemistry A
theoreticians to think that molecular orbitals could be
experimentally seen.9 The extension to diradicals, where
two electrons occupy two SOMOs, was straightforward.
Despite the simplicity of the Huckel model and in particular
the lack of negative spin densities (for a positive Ms total spin
component) in the systems, the results were in reasonable
agreement with those of the more sophisticated two-electron
PPP Hamiltonian. With the advances of ab initio quantum
chemistry, these elementary pictures were partially forgotten.
The present work will rst recall that the spatial distribution of
the unpaired electron given by the topological Huckel
Hamiltonian can be determined analytically. This study focuses
on a series of molecules in which one or two CH2 methylene
groups are attached to benzene or naphthalene skeletons.
Because these mono- and diradicals are supposed to bear one
or two unpaired electrons, the natural way to study them using
ab initio wave function theory (WFT) methods consists of
starting from a restricted open-shell HartreeFock (ROHF)
having one unpaired electron for monoradicals and two
unpaired electrons coupled in a triplet state for diradicals. As
already reported by Borden and Davidson,10 the resulting spin
distributions happen to be deeply dierent from those
predicted by the Huckel model, being much more concentrated
on the extra cyclic methylene groups. As shown by the same
authors, one may get an improved description of the electron
system by performing a full CASSCF treatment of all electrons
in optimized valence MOs.11 This description accounts for the
spin polarization of the electrons and therefore introduces
negative spin densities. However, the natural molecular orbitals
(NOs), which have an occupation number equal or close to 1
exhibit spin densities that happen to be surprisingly similar to
those predicted by the topological Huckel Hamiltonian. The
present paper will rst illustrate the unexpected quality of the
Huckel picture. Then it will exhibit an apparent contradiction
between the facts that the full CASSCF calculation denitely
conrms that only one or two MOs may be considered as singly
occupied, whereas the corresponding ROHF treatment provides a
completely biased description of the system. As a conrmation
of this paradox, we shall demonstrate that starting from the single
determinant built from the NOs of the full CASSCF calculation,
and introducing the excitations from doubly occupied to virtual
MOs (single reference + single excitations, SR+S) to account for
the spin polarization phenomenon, give the same spin density
distribution as a CAS(Full valence )+S calculation. These spin
distributions are in good agreement with the experimental
hyperne coupling constants and at variance with the ROHF+S
ones. An analytic derivation proposes a rationalization of the
defects of the ROHF or minimal CASSCF calculations as missing
the dynamic charge polarization eects brought by the one hole
(1h)one particle (1p) excitations on top of the charge transfer
congurations between methylene and the aromatic frame.
Although opened a long time ago, this domain is no longer
an academic one. Actually, the interest for magnetic properties of
conjugated hydrocarbons, and in particular fused polybenzenic
architectures, is rapidly increasing. Until recently, the attempts to
conceive and synthesize molecular or periodic materials presenting
challenging magnetic properties, such as ferromagnetism,
antiferromagnetism, spin crossover, and high magnetic anisotropy,
essentially involved transition metal ions or lanthanides as spin
carriers and belonged to coordination chemistry. It is nowadays
tempting to transfer these concepts to organic compounds.1220
Conjugated radical or polyradical conjugated hydrocarbons may
play the same role as magnetic ions12 and may be assembled in a
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rational way to generate ferromagnetic lattices12,13 or bistable
architectures. The possibility of starting from graphene patches or
carved graphenes attracts special interest,2125 especially in the
context of new materials for spintronics.18 For such large
architectures, tight-binding methods constitute natural computa-
tional approaches and their relevance is of course crucial.26,27
II. ANALYTICAL DERIVATION OF THE SOMO
COEFFICIENTS OF THE TOPOLOGICAL HU CKEL
HAMILTONIAN
The here-after considered conjugated hydrocarbons are
alternant (solid state physicists say bipartite). They do
not involve odd-membered rings, and consequently the carbon
atoms can be separated into two categories (starred or
nonstarred) in such a way that each starred atom is chemically
connected to nonstarred atoms and reciprocally. An illustration
of starred and nonstarred atoms is shown for the here-studied
compounds in Figure 1.
Figure 1. Representation of the methylenebenzene (compound 1),
two methylenenaphthalene isomers (compounds 2 and 3), meta-
xylylene (compound 4), and two dimethylenenaphthalene isomers
(compounds 5 and 6). The starred atoms (see text) are indicated as
well as the no-starred atoms for compounds 1, 2, and 4.
The expression of the Huckel Hamiltonian2830 is
H = tpq(ap+aq + aq+ap)
p,q
where the sum runs over all couples of chemically bonded
atoms. During the 1940s the mirror theorem has been
proposed by LonguettHiggins31 and Hall.32 For systems in
which the number (na) of starred atoms is larger than the
number (nb) of nonstarred ones, the mirror theorem says that
the Huckel Hamiltonian presents na nb eigenvalues of energy
zero. In other words, the SOMO satises the eigenequation
H a = 0a = 0
The theorem also says that the coecients of the SOMO on
the minor (nonstarred) sites are zero. Contrarily to what is
sometimes said,33 this property is also satised when the
hopping integrals tpq are dierent. If they are equal, it is easier
to establish the corresponding amplitudes of the nonzero
coecients of the SOMO of monoradicals. They are given by
projecting the eigenequation on the q AOs of the nonstarred
atoms, according to
q|H |a = tqp *cp * = 0
p*
The Journal of Physical Chemistry A
p and q being located on neighbor atoms. If all hopping
integrals are equal, the equation
cp * = 0
p*
is satised for all nonstarred sites q (p* and q being rst
neighbors). In practice, one may rst give a coecient 1 to the
AO of a starred atom that has only two second neighbor sites.
The coecient of the SOMO on the AO of these atoms will be
equal to 1. Progressing along the molecular graph, the
satisfaction of the above equation leads to integer coecients
either positive or negative on the starred atoms. The norm of
this vector is easily calculated and so is the spin density on the
starred atoms, which is obtained by dividing the square of the
coecient by the norm. This means that the spin densities are
necessarily rational numbers, a feature which, to our knowledge,
had not been noticed. Figure 2 presents the coecients of the
Figure 2. Huckel coecients of the SOMOs for compound 1 and 2
(top) and 4 (bottom). The norm (N) and spin densities (SP) on the
external atoms are N = 7 = (2)2 + (1)2 + (1)2 + 12, SP = 4/7 = 22/
N for 1, N = 20, SP = 9/20 for 2, and N = 3 (left MOs) and N = 4
(right MOs) whereas the total spin density is 7/12 for 4.
SOMO of the hereafter studied monoradicals and the
corresponding spin densities calculated on the external atom.
The same reasoning could be applied to diradicals and would
provide the spin density contribution of the two SOMOs.
Diradicals involve two SOMOs, which are degenerate and
not uniquely dened. When the geometry exhibits a symmetry
element for which the two SOMOs belong to a dierent
irreducible representation, as is the case for compounds 4 and
5, one may determine the coecients of the symmetry-adapted
SOMOs by xing in-phase and out-of-phase equal coecients
on the external carbons. In such cases, Huckel SOMOs may be
compared one by one to the symmetry-adapted SOMOs obtained
using the exact electronic Hamiltonian. In the absence of
symmetry, one may nd one SOMO identical to that of a parent
monoradical and dene the second one by orthogonality to the
rst one. The overall spin densities on the external methylene
groups are 7/12 in compound 4, and 17/32 in compound 5. For
compound 6 the spin densities are respectively 5/9 and 17/36 on
carbons numbered 1 and 12, respectively.
III. COMPUTATIONAL INFORMATION
Wave function theory and unrestricted density functional
theory (UDFT) calculations have been performed using the
Molcas7.2 package3436 version 7.2. The following cc-pVDZ
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Dunning basis sets37 were used: C, 9s4p1d contracted in
3s2p1d; H, 4s1p contracted 2s1p. In UDFT calculations the B3LYP
functional is used. In these calculations the dierence to the expected
values of S2 never exceeds 0.04 for monoradicals and 0.12 for
diradicals. Some BLYP calculations have also been performed.
All the geometries were optimized in an unrestricted
formalism, using the B3LYP functional for the Msmax solution.
First, the orbitals were optimized at the ROHF level for the
doublet ground state for monoradicals and triplet ground
state for diradicals. Second, the orbitals of the ground state
were optimized using a CAS(Full valence )SCF calculation.
The Huckel orbitals were analytically determined.
Although the spin population of the SOMOs is the most
important contribution to the spin density, the spin polarization
of both and other orbitals contributes quantitatively to the
whole spin density. To introduce the spin polarization, single-
excitations should be accounted for, and this can be achieved
using the restricted active space (RAS) program of the Molcas
package. Notice that these excitations act on all the
determinants of the active space, including those that, for
symmetry reasons, have a zero coecient in the CAS function.
Unfortunately, the total number of orbitals that can be
introduced in the RAS is limited to 50.
To compare the spin densities obtained from the ROHF
orbitals and those obtained from the CAS(Full valence )SCF
orbitals, we have technically proceeded as follows (Figure 3 for
the notation of the MO subspace):
(i) Using the ROHF orbitals, we have performed a RASCI
calculation involving all single excitations of an electron
from any of the singly or doubly occupied MOs (spaces 1
and 2) to either the SOMOs or any empty orbitals
(spaces 2, 3, and 4) (according to the Molcas conven-
tions, all doubly occupied orbitals belong to RAS1, the
SOMOs belong to RAS2, and the empty * orbitals
belong to RAS3). This calculation is noted SR+S(Full ) in
Table 2.
(ii) The same calculation has been performed using the
CAS(Full valence )SCF NOs: it only diers from (i) by
the set of MOs that is used. This SR+S calculation
is noted SR+S(Full ) with CAS(Full valence )SCF
NOs.
(iii) Using the CAS(Full valence )SCF orbitals and wave
function as reference, we have performed a RAS
calculation. All the valence MO belong to the CAS
(spaces 1, 2, and 3) and the single excitation toward the
nonvalence * MO (space 4) are considered (all the
valence orbitals belong to the RAS2 subspace whereas all
empty orbitals belong the RAS3 subspace). This
calculation is a multireference+Single excitations (MR+S)
and is noted CAS(Full valence )+S(Full ) with CAS(Full
valence )SCF NOs.
Because such calculations may be computationally expensive,
we have focused our study on the two smallest systems,
compounds 1 and 4, for which (i), (ii), and (iii) results are
reported in Table 2.
The results of unrestricted single determinant calculations
have also been reported. The spin densities in UDFT
calculations are known to be sensitive to the amount of Fock
exchange in the hybrid functional. We have therefore
performed UBLYP, UB3LYP, and UHF calculations. As already
noticed in the literature, the UHF results are absolutely
irrelevant, the spin density being exceedingly delocalized, with
The Journal of Physical Chemistry A
Figure 3. Division of the MOs into 4 subspaces: occupied MOs
(space 1), SOMO (space 2, one SOMO for monoradical, 2 SOMOs
for diradicals), and valence * MOs (space 3). Space 4 contains all the
other virtual * MOs.
enormous negative spin densities on the nonstarred atoms,
as if the wave function was a single spin wave. This description
will not receive further comments but has been included for
comparison in Table 3.
IV. RESULTS AND DISCUSSION
a. Spatial Extent of the Variational SOMOs and Their
Mulliken Spin Population. This section compares the spin
density contribution of the SOMOs and their spatial extent
optimized at several levels of calculation. The SOMOs of
compounds 1, 2, and 3 calculated using dierent methods are
represented in Figure 4. The Huckel, UDFT, and CAS(Full
valence )SCF orbitals are visibly more delocalized over the
molecules than the ROHF ones. The Mulliken spin population
of the SOMOs on each carbon provides another way to
appreciate the spatial extent of these orbitals (Table 1). One
should notice that the ROHF SOMOs do not have strictly zero
Figure 4. SOMO of the doublet ground state of compound 1 (left) and SOMOs of the triplet ground state of compound 4 (right) computed at
(from top to bottom) the ROHF, UDFT, CAS(Full valence )SCF and Huckel. All these MOs are drawn using the Molden default contour value
of 0.05.
D dx.doi.org/10.1021/jp4120892 | J. Phys. Chem. A XXXX, XXX, XXXXXX
Article
coecients on nonstarred (minor) atoms. Nevertheless, the
coecients on these sites are very small (<0.002). The spin
polarization of the system, incorporated in the CAS(Full
valence )SCF treatment, results in negative spin population on
these sites, and of course in an increase of the positive spin
population on the starred atoms. The Mulliken spin
populations of the SOMOs show that the spatial extent of
the SOMOs is enlarged at the CAS(Full valence )SCF level.
Despite the important dierence between the corresponding
orbitals, the occupation numbers of the CAS(Full valence
)SCF function clearly indicate that there is only one singly
occupied NO (occupation number equal to 1.0) for
monoradicals and two for diradicals. Indeed, the occupation
numbers of the least doubly occupied and most occupied
virtual type MOs are respectively 1.85 and 0.15 in the most
correlated system, compound 5. One may notice striking
similarities of the Mulliken populations of the SOMOs
calculated from the CAS(full valence )SCF with those
obtained from the simple topological Huckel model, also
reported in Table 1.
b. Impact of the Quality of the Orbitals on the Spin
Densities. This section will rst compare the spin densities
obtained from dierent computational schemes. Then,
concentrating on compound 1 (the well-studied benzyl
radical),3841 the results will be compared to the experimental
isotropic hyperne coupling constants.42
In comparison to the Mulliken spin population of the
SOMOs reported in Table 1, the previously almost zero values
of the spin densities on the nonstarred atoms become
negative, as expected, due to the spin polarization of the doubly
occupied MO. The spin densities in particular on the
methylene carbon have very dierent values when calculated
from the SR+S(Full ) using the ROHF MOs and MR+S(Full
) using the CAS(Full Valence )SCF NOs. At rst glance
this discrepancy could question obtaining the whole spin
The Journal of Physical Chemistry A Article

Table 1. Ground State Mulliken Spin Population on the Starred Atoms of the SOMO Optimized at the ROHF Level, Compared
with the Population of the Almost Singly Occupied Natural MO of the CAS(Full valence )SCFa
atom number
compd 1 3 5 7 9 11 12
1 Huckel 0.571 0.143 0.143
ROHF 0.803 0.062 0.050
CAS(7,7)SCF 0.591 0.117 0.142
2 Huckel 0.450 0.200 0.200 0.050 0.050 0.050
ROHF 0.760 0.112 0.063 0.033 0.008 0.003
CAS(11,11)SCF 0.457 0.221 0.198 0.050 0.023 0.015
3 Huckel 0.530 0.059 0.059 0.059 0.059 0.236
ROHF 0.791 0.026 0.027 0.016 0.012 0.110
CAS(11,11)SCF 0.529 0.033 0.070 0.053 0.036 0.242
4 Huckel 0.583 0.250 0.334
ROHF 0.777 0.123 0.150
CAS(8,8)SCF 0.560 0.251 0.312
5 Huckel 0.532 0.125 0.125 0.281
ROHF 0.773 0.047 0.061 0.128
CAS(12,12)SCF 0.489 0.104 0.175 0.282
6 Huckel 0.556 0.139 0.139 0.250 0.222 0.222 0.472
ROHF 0.779 0.039 0.071 0.113 0.128 0.080 0.747
CAS(12,12)SCF 0.512 0.082 0.173 0.233 0.237 0.233 0.456
a
The corresponding spin populations for the Huckel model are given for comparison.

Table 2. Ground State Mulliken Spin Densities Brought by the MOs for Compounds 1 and 4 Computed at SR+S and CAS+S
Levels and Using Either the ROHF MOs or the CAS(Full valence )SCF NOs and at the UDFT Level
atom number
compd 1 2 3 4 5
1 ROHF+S(Full ) 0.468 0.082 0.229 0.057 0.264
SR+S(Full ) with CAS(Full valence )SCF MOs 0.654 0.119 0.196 0.083 0.231
CAS(Full valence ) with CAS(Full valence )SCF MOs 0.665 0.150 0.214 0.100 0.246
CAS(Full valence )+S(Full ) with CAS(Full valence )SCF MOs 0.676 0.140 0.203 0.093 0.233
UB3LYP restricted to MOs 0.654 0.122 0.196 0.092 0.227
4 ROHF+S(Full ) 0.516 0.100 0.392 0.093 0.461
SR+S(Full ) with CAS(Full valence )SCF MOs 0.641 0.150 0.344 0.118 0.423
CAS(Full valence ) with CAS(Full valence )SCF MO 0.659 0.201 0.387 0.166 0.454
CAS(Full valence )+S(Full ) with CAS(Full valence )SCF MOs 0.672 0.190 0.370 0.158 0.429
UB3LYP restricted to MOs 0.649 0.159 0.351 0.153 0.409

polarization introducing single excitations only. However, the
SR+S(Full ) calculation using the CAS(Full valence )SCF
NOs provides spin densities in good agreement with those of
the MR+S(Full ) calculation. Taking this last correlated wave
function as the most reliable function, one may then conclude
that (i) single excitations suce to reproduce the main spin
polarization eect and (ii) the quality of the SOMOs is crucial
for obtaining reliable spin densities.
One should nally note that the spin densities obtained
from either SR+S(Full ) or CAS(Full valence )+S(Full )
using the CAS(Full valence )SCF NOs are in good agreement
with those of UB3LYP.
Comparing ROHF results of Table 2 with those of the SR
+S(Full ) it appears that, when starting from the ROHF MOs,
the spin polarization reduces dramatically the spin density on
the methylene carbon(s). On the contrary, when starting from
the NOs of the CAS(Full valence )SCF, the spin density on
this atom is enhanced in the SR+S(Full ) calculation. The
analysis of the SR+S(Full ) and MR+S(Full ) wave functions
shows that the coecients of the singly excited determinants
in which either an electron is promoted from the magnetic
spinorbital a to virtual one i* (i.e., 1 particle) or an electron is
E dx.doi.org/10.1021/jp4120892 | J. Phys. Chem. A XXXX, XXX, XXXXXX
promoted from doubly occupied spin orbitals i to the magnetic
one a (i.e., 1 hole) are almost zero when the CAS(Full valence
)SCF NOs are used and signicant when the ROHF MOs
are used. These excitations actually result in a delocalization of
the spin density. This observation can be rationalized: the
amplitude of these coecients are respectively proportional to
the integrals i*|Ka|a and i|Ka|a, where Ka is the exchange
operator relative to the magnetic orbital, the magnitude of
which increases with the localization of the orbital. As a result,
due to the exceeding localization of the magnetic ROHF
orbital, the decrease of the spin density is exaggerated in the
corresponding SR+S calculation.
The spin densities can be compared to the a (H)
experimental hyperne coupling constants provided by the
ESR spectroscopy, if one accepts the McConnell relationship,
i.e., the proportionality of the contact term on a proton to the
spin density of the carbon to which it is bound. This
experimental information is only available for the benzyl
compound 1. Table 3 gives the ratios of the calculated Mulliken
spin densities, taking that of the C of the methylene group as 1,
compared to the corresponding ratios of the experimental
hyperne constants. All the calculated ratios are in good
The Journal of Physical Chemistry A Article

Table 3. Carbon Atom Mulliken Spin Density Ratios and Mulliken Spin Density Ratios of the H Atoms Bound to the C
Atoms, for Compound 1a
atom number
2 3 4 5
spin densities ROHF+S(Full ) 0.20 0.49 0.14 0.57
SR+S(Full ) with CAS(Full valence )SCF MOs 0.21 0.30 0.14 0.36
CAS(Full valence )SCF 0.25 0.32 0.16 0.37
CAS(Full valence )+S(Full ) with CAS(Full valence )SCF MOs 0.21 0.30 0.14 0.36
BLYP 0.12 0.27 0.09 0.33
B3LYP 0.19 0.30 0.14 0.35
UHF 0.59 0.69 0.61 0.69
spin densities SR+S(Full valence ) 0.09 0.01 0.00
CAS(Full valence )+S(Full valence )SCF 0.32 0.14 0.32
BLYP 0.31 0.10 0.40
B3LYP 0.33 0.15 0.40
UHF 0.69 0.61 0.71
exp aH/aH1 0.31 0.10 0.38
a
The references are the spin density of C1 and the spin density of the H bound to C1. C2 is not bound to any H atom.

agreement with the experimental ones, except the ROHF electron distribution in benzyl. Let us start from a strongly
+S(Full ) and the UHF ones. This shows that the crucial point localized picture
is the quality of the magnetic MOs, which is not achieved at the
ROHF level and is not restored by the single excitations. 0 = |i i j j kka |
Regarding the DFT results, B3LYP that has 20% of HF where i, j, and k are the occupied MOs of the benzene ring
exchange shows larger negative spin densities than BLYP, and and a is the orbital of the exocyclic carbon. Let us call Fii, Fjj,
this is in line with those of UHF, where they become Fkk, Faa the energies of these MOs, dened from the Fock
enormous. The introduction of a fraction of Fock exchange operator relative to 0.
increases the spin polarization of the system.
One may gain access to spin densities on the H atoms, F=h+ (2Jj K j) + Ja Ka/2
which are in closer relationship with the hyperne coupling j
constants. These densities are directly accessible from UHF and
for the inactive orbitals, so that
DFT calculations. We have performed SR+S(Full valence )
and MR+S calculations. In the former, the ROHF MOs are Fii = h ii + (2Jji K ji) + Jii + Jai Kai/2
used and all the valence * excitations are allowed on top ji
of the SR determinant (one electron in the SOMO). In the
latter calculations, all valence MOs are active and all single For the magnetic orbital a one may dene
excitations involving valence MOs are considered in an SCF
procedure. For each type of treatment the ratios are the same Faa = haa + (2Jja K ja)
as for the corresponding spin densities, as shown in Table 3 ji

(SR+S(Full valence ) results cannot be directly compared to
the ROHF+S(Full ) ones as the CI spaces are dierent). SR
+S(Full valence ) spin densities on H that do not belong to
the methylene group are almost zero, evidencing the excessive
localization of the SOMO on the MO of the external C atom.
V. ANALYTIC RATIONALIZATION: THE CRUCIAL ROLE
OF DYNAMIC CHARGE POLARIZATION
As already mentioned, the defect of the ROHF description of
radicals and diradicals has been noticed a long time ago by
Borden and Davidson.10,11 Regarding the radicals, one may
refer to the elementary problem of allyl, which suers a
spurious symmetry breaking at this level, as observed by Paldus
and Veillard.43 Two electrons tend to localize in a double bond
whereas the unpaired electron localizes on one of the terminal
carbon atoms. The same tendency to strong bond pairing is
observed in the p-dimethylene cyclobutadiene, the two
extracyclic bonds being very short. Going beyond the 2-active
MO picture, including the correlation between the active and
inactive ( only or and ) electrons reduces this exceedingly
localized description. It may be useful to analyze the dierence
between the Huckel and the HF descriptions of the unpaired
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The delocalization between the benzene ring and the exocyclic
atom will rst proceed through a+a ai excitations, which lead to
the determinant ia = |iajj a|. The orbital mixing between
kk
the orbitals i and a, which takes place in the SCF process, may
be considered in a perturbative approach as due to the
interaction between 0 and ia . To the rst order
i a |H |0
C i a =
0|H |0 i a |H | i a
One may calculate the energy dierence appearing in the
denominator
0|H |0 i a |H | i a = Fii Faa + Jia K ia /2 Jaa
Due to the concentration of a and the spatial localization of
the orbitals, Jaa is very large, whereas Kia is negligible and Jia is
much smaller than Jaa. The two-electron part of the energy
denominator increases its amplitude (in absolute value). The
Huckel model ignores that two-electron contribution and will
give signicantly larger delocalization mixings between the
orbitals of the rings and the exocyclic orbital than does the
ROHF treatment. One may check that the same conclusions
are valid for the mixings between the orbital a and the virtual
The Journal of Physical Chemistry A
MOs i* of the ring, governed by the a+i*aa excitations. Now one
may explain why the correlation increases the delocalization
between the exocyclic center and the ring. This increase is due
to the so-called dynamical polarization eect. When the
electron transfer between the ring MO i and the singly
occupied MO a has taken place, the other electrons of the
doubly occupied MOs m (either or ) feel a modied electric
eld, deviating from the mean eld by the operator Ja Ji. This
uctuation of the electric eld will create a dynamical
polarization eect, i.e., an excitation from m to a virtual MO
n*. The interaction between the doubly excited determinant
a+n*a+a aia m0 and ia
is
an+*a a+ a i a m0|H | i a = n*|Ja Ji |m
which may be large, due to the large dipolar character of the Ja
Ji operator. This leads to a third-order perturbative correction
to the coecient Cia
i a |H |0
C i a =
(0|H |0 i a |H | i a )2
n*|Ja Ji |m2
. calculation. Even if of lesser extent, a similar defect has also
0|H |0 i a |H | i a + Fmm Fn * n *
This correction (and higher order corrections) may be
expressed as a change of the eective energy of ia
,
i a |H eff | i a = i a |H | i a the SOMOs and the other electrons, leads to a delocalization
n*|Ja Ji |m2
+ words, although the density matrix diagonalization clearly
m,n * 0|H |0 i a |H | i a + Fmm Fn * n *
and writing
i a |H |0
C eff
i a =
0|H |0 i a |H eff | i a ROHF treatment introduces a bias in the physical content of
The dynamical polarization eect stabilizes the eective energy
of the charge transfer congurations between the exocyclic
carbon and the ring and therefore diminishes the absolute value
of the energy denominator, hence increasing the delocalization
of the orbitals between the exocyclic atom and the ring to
which it is attached. The same remark would apply on the Cai*
coecients relative to the a+i*aa excitations.
This derivation is valid as well for the diradicals. Moreover, it
is relevant for coordination chemistry of open-shell systems. In
this domain too it has been observed that the magnetic orbitals,
centered on the transition metal ions, are exceedingly localized,
when compared to the natural MOs obtained from an extensive
CI calculation.44,45 It has been observed that the delocalization
between the ligand and the metal is brought by the so-called
2h1p and 1h2p excitations, i.e., by the determinants of the
type a+n*a+a aia m0 or a+n*a+n*aaam0, which are responsible for the
energy lowering of the charge transfer congurations between
the magnetic site and the ligands.46
Actually, this remark is even more general because it also
concerns the closed shell systems. It has been observed for
instance that the SCF calculations predict an exceedingly large
bond length alternation in linear polyenes.4751 This
phenomenon is due to an underestimation of the delocalization
between the MOs localized on the double bonds. The
delocalization proceeds through charge transfer excitations
between adjacent bonds, i.e., a+i*aj excitations. These excitations
induce a uctuation of the electric eld felt by the other
Article
electrons. Their response to this uctuation results in a
stabilization of the eective energy of the CT congurations,
and therefore to an increase of the interbond charge transfer
components of the wave function. This correlation process
reduces the bond alternation. In this precise problem dynamic
polarization of the CT components a+i*aj 0 between the
adjacent bonds I and J proceeds through the doubly excited
determinants a+r*a+i*ajam0 and involves the interaction r*|Ji*
Jj|m. The orbitals r* and m may be not only MOs neighbors
to bonds I and J but also MOs of the bonds involving the four
carbon atoms of bonds I and J. The contribution to the
reduction of the bond alternation is expected to be important
because the operator Ji* Jj has a strong eect on the *
distributions relative to these bonds. This remark rationalizes
the observed limits of full CASSCF calculations52,53 in the
reduction of CC bond alternations.
VI. CONCLUSION
The SOMOs optimized at the ROHF level of calculation in
radical conjugated hydrocarbons are exceedingly localized in
comparison to those obtained at the CAS(Full valence )SCF
been observed in transition metal complexes.54 As analytically
demonstrated and numerically conrmed, going from the
ROHF or minimal CASSCF solution to more sophisticated
methods, which introduce correlations between the electrons of
of the corresponding SOMOs55 (see also ref 54). In other
indicates that these systems have only one or two essentially
singly occupied MOs and may therefore be considered as of
essentially single-determinantal character (for the high spin
state), the magnetic MOs are poorly described when obtained
from a priori single reference self-consistent treatment. This
the magnetic MOs. As a consequence, the contribution of these
orbitals to the spin density is very dierent from that obtained
at the most sophisticated level. But replacing the ROHF single
determinant by the determinant built from the natural orbitals
of a CAS(Full valence )SCF allows one to produce a reliable
single reference expansion of the wave function. Despite its
simplicity, the Huckel model provides much more accurate
SOMOs and, consequently, much better spin population
contributions of the SOMOs to the total spin density than
the ROHF treatment. This qualitative success can hardly be
formalized and cannot be computationally exploited because
the basis set in which the Huckel Hamiltonian works is implicit
and we recommend using the method proposed in ref 55 to
optimize the magnetic orbitals of organic systems. The spatial
extent of the SOMOs may have important consequences on the
magnitude of the magnetic couplings in polyradical hydro-
carbons and therefore on the calculated magnetic properties.
The quality of the MOs happens to be of major importance in
the calculation of the magnetic couplings of diradicals.54,55
AUTHOR INFORMATION
Corresponding Author
*N. Guihery: e-mail, nathalie.guihery@irsamc.ups-tlse.fr; tel,
+330561556098.
Notes
The authors declare no competing nancial interest.
G dx.doi.org/10.1021/jp4120892 | J. Phys. Chem. A XXXX, XXX, XXXXXX
The Journal of Physical Chemistry A
ACKNOWLEDGMENTS
The authors thank F. Neese for helpful discussions regarding a
similar problem in transition metal complexes.
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