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CHAPTER
1
Bond Differentiation and
Orbital Decoupling in the
Orbital-Communication Theory
of the Chemical Bond
Roman F. Nalewajski
a
, Dariusz Szczepanik
b
,
and Janusz Mrozek
b
Contents 1. Introduction 3
2. Molecular Information Channels in Orbital Resolution 6
3. Decoupled (Localized) Bonds in Hydrides Revisited 11
4. Flexible-Input Generalization 15
5. Populational Decoupling of Atomic Orbitals 21
6. Bond Differentiation in OCT 29
7. Localized σ Bonds in Coordination Compounds 34
8. Restricted Hartree–Fock Calculations 36
8.1. Orbital and condensed atom probabilities of
diatomic fragments in molecules 37
8.2. Average entropic descriptors of diatomic
chemical interactions 40
9. Conclusion 44
References 45
Abstract Information-theoretic (IT) probe of molecular electronic structure, within the
orbital-communication theory (OCT) of the chemical bond, uses the standard
entropy/information descriptors of the Shannon theory of communication
a
Department of Theoretical Chemistry, Jagiellonian University, Cracow, Poland
b
Department of Computational Methods in Chemistry, Jagiellonian University, Cracow, Poland
Advances in Quantum Chemistry, Volume 61 c _2011 Elsevier Inc.
ISSN 0065-3276, DOI: 10.1016/B978-0-12-386013-2.00001-2 All rights reserved.
1
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2 Roman F. Nalewajski, Dariusz Szczepanik, and Janusz Mrozek
to characterize the scattering of electron probabilities and their information
content throughout the system network of chemical bonds generated by
the occupied molecular orbitals (MOs). Thus, the molecule is treated as
information network, which propagates the “signals” of the electron alloca-
tion to constituent atomic orbitals (AOs) or general basis functions between
the channel AO “inputs” and “outputs.” These orbital “communications” are
determined by the two-orbital conditional probabilities of the output AO
events given the input AO events. It is argued, using the quantum-mechanical
superposition principle, that these conditional probabilities are proportional
to the squares of corresponding elements of the first-order density matrix
of the AO charges and bond orders (CBO) in the standard self-consistent
field (SCF) theory using linear combinations of AO (LCAO) to represent MO.
Therefore, the probability of the interorbital connections in the molecu-
lar communication system is directly related to the Wiberg-type quadratic
indices of the chemical bond multiplicity. Such probability propagation in
molecules exhibits the communication “noise” due to electron delocaliza-
tion via the system chemical bonds, which effectively lowers the information
content in the output signal distribution, compared with that contained in
probabilities determining its input signal, molecular or promolecular. The
orbital information systems are used to generate the entropic measures of
the chemical bond multiplicity and their covalent/ionic composition. The
average conditional-entropy (communication noise, electron delocalization)
and mutual-information (information capacity, electron localization) descrip-
tors of these molecular channels generate the IT covalent and IT ionic bond
components, respectively. A qualitative discussion of the mutually decou-
pled, localized bonds in hydrides indicates the need for the flexible-input
generalization of the previous fixed-input approach, in order to achieve a
better agreement among the OCT predictions and the accepted chemi-
cal estimates and quantum-mechanical bond orders. In this extension, the
input probability distribution for the specified AO event is determined by
the molecular conditional probabilities, given the occurrence of this event.
These modified input probabilities reflect the participation of the selected
AO in all chemical bonds (AO communications) and are capable of the con-
tinuous description of its decoupling limit, when this orbital does not form
effective combinations with the remaining basis functions. The occupational
aspect of the AO decoupling has been shown to be properly represented
only when the separate communication systems for each occupied MO are
used, and their occupation-weighted entropy/information contributions are
classified as bonding (positive) or antibonding (negative) using the extra-
neous information about the signs of the corresponding contributions to
the CBO matrix. This information is lost in the purely probabilistic model
since the channel communications are determined by the squares of such
matrix elements. The performance of this MO-resolved approach is then
compared with that of the previous, overall (fixed-input) formulation of OCT
for illustrative π-electron systems, in the H¨ uckel approximation. A qualita-
tive description of chemical bonds in octahedral complexes is also given. The
bond differentiation trends in OCT have been shown to agree with both the
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Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 3
chemical intuition and the quantum-mechanical description. The numerical
Restricted Hartree–Fock (RHF) applications to diatomic bonds in representa-
tive molecular systems are reported and discussed. The probability weighted
scheme for diatomic molecular fragments is shown to provide an excellent
agreement with both the Wiberg bond orders and the intuitive chemical
bond multiplicities.
1. INTRODUCTION
The techniques and concepts of information theory (IT) [1–8] have been shown
to provide efficient tools for tackling diverse problems in the theory of
molecular electronic structure [9]. For example, the IT definition of Atoms-
in-Molecules (AIM) [9–13] has been reexamined and the information content
of electronic distributions in molecules and the entropic origins of the chem-
ical bond has been approached anew [9–18]. Moreover, the Shannon theory
of communication [4–6] has been applied to probe the bonding patterns
in molecules within the communication theory of the chemical bond (CTCB)
[9, 19–28] and thermodynamic-like description of the electronic “gas” in
molecular systems has been explored [9, 29–31]. The CTCB bonding patterns
in both the ground and excited electron configurations have been tackled
and the valence-state promotion of atoms due to the orbital hybridization
has been characterized [28]. This development has widely explored the use
of the average communication noise (delocalization, indeterminacy) and
information-flow (localization, determinacy) indices as novel descriptors of
the overall IT covalency and ionicity, respectively, of all chemical bonds in
the molecular system as a whole, as well as the internal bonds present in its
constituent subsystems and the external interfragment bonds.
The electron localization function [32] has been shown to explore the
nonadditive part of the Fisher information [1–3] in the molecular orbital
(MO) resolution [9, 33], whereas a similar approach in the atomic orbital
(AO) representation generates the so-called contragradience (CG) descrip-
tors of chemical bonds, which are related to the matrix representation of the
electronic kinetic energy [34–38]. It should be recalled that the molecular
quantum mechanics and IT are related through the Fisher (locality) mea-
sure of information [34–41], which represents the gradient content of the
system wavefunction, thus being proportional to the average kinetic energy
of electrons. The stationary Schr¨ odinger equation indeed marks the optimum
probability amplitude of the associated Fisher information principle, includ-
ing the additional constraint of the fixed value of the system potential energy
[34, 39–41]. Several strategies for molecular subsystems have been designed
[9, 22, 25, 26] and the atomic resolution of bond descriptors has been pro-
posed [24]. The relation between CTCB and the Valence Bond (VB) theory has
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4 Roman F. Nalewajski, Dariusz Szczepanik, and Janusz Mrozek
been examined [23, 27] and the molecular similarities have been explored
[9, 42]. Moreover, the orbital resolution of the “stockholder” atoms and
the configuration-projected channels for excited states have been developed
[43–45].
The key concept of CTCB is the molecular information system, which
can be constructed at alternative levels of resolving the electron probabili-
ties into the underlying elementary “events” determining the channel inputs
a={a
i
] and outputs b ={b
j
], for example, of finding an electron on the basis
set orbital, AIM, molecular fragment, etc. They can be generated within
both the local and the condensed descriptions of electronic probabilities in
a molecule. Such molecular information networks describe the probability/
information propagation in a molecule and can be characterized by the stan-
dard quantities developed in IT for real communication devices. Because of
the electron delocalization throughout the network of chemical bonds in a
molecule the transmission of “signals” from the electron assignment to the
underlying events of the resolution in question becomes randomly disturbed,
thus exhibiting the communication “noise.” Indeed, an electron initially
attributed to the given atom/orbital in the channel “input” a (molecular
or promolecular) can be later found with a nonzero probability at several
locations in the molecular “output” b. This feature of the electron delocaliza-
tion is embodied in the conditional probabilities of the outputs given inputs,
P(b[a) ={P(b
j
[a
i
)], which define the molecular information network.
Both one- and two-electron approaches have been devised to construct
this matrix. The latter [9] have used the simultaneous probabilities of two
electrons in a molecule, assigned to the AIM input and output, respec-
tively, to determine the network conditional probabilities, whereas the for-
mer [38, 46–48] constructs the orbital-pair probabilities using the projected
superposition-principle of quantum mechanics. The two-electron (correla-
tion) treatment has been found [9] to give rise to rather poor representation
of the bond differentiation in molecules, which is decisively improved in the
one-electron approach in the AO resolution, called the orbital-communication
theory (OCT) [38, 46–48]. The latter scheme complements its earlier orbital
implementation using the effective AO-promotion channel generated from
the sequential cascade of the elementary orbital-transformation stages
[43–45, 49, 50]. Such consecutive cascades of elementary information sys-
tems have been used to represent the underlying orbital transformations
and electron excitations in the resultant propagations of the electron prob-
abilities, determining the orbital promotions in molecules. The information
cascade approach also provides the probability scattering perspective on
atomic promotion due to the orbital hybridization [28].
In OCT the conditional probabilities determining the molecular commu-
nication channel in the basis-function resolution follow from the quantum-
mechanical superposition principle [51] supplemented by the “physical”
projection onto the subspace of the system-occupied MOs, which determines
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Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 5
the molecular network of chemical bonds. Both the molecule as a whole and
its constituent subsystems can be adequately described using the OCT bond
indices. The internal and external indices of molecular fragments (groups
of AO) can be efficiently generated using the appropriate reduction of the
molecular channel [9, 25, 46, 48] by combining selected outputs and larger
constituent fragment(s).
In this formulation of CTCB the off-diagonal orbital communications have
been shown to be proportional to the corresponding Wiberg [52] or related
quadratic indices of the chemical bond [53–63]. Several illustrative model
applications of OCT have been presented recently [38, 46–48], covering both
the localized bonds in hydrides and multiple bonds in CO and CO
2
, as well
as the conjugated π bonds in simple hydrocarbons (allyl, butadiene, and
benzene), for which predictions from the one- and two-electron approaches
have been compared; in these studies the IT bond descriptors have been
generated for both the molecule as whole and its constituent fragments.
After a brief summary of the molecular and MO-communication sys-
tems and their entropy/information descriptors in OCT (Section 2) the
mutually decoupled, localized chemical bonds in simple hydrides will be
qualitatively examined in Section 3, in order to establish the input proba-
bility requirements, which properly account for the nonbonding status of
the lone-pair electrons and the mutually decoupled (noncommunicating,
closed) character of these localized σ bonds. It will be argued that each such
subsystem defines the separate (externally closed) communication channel,
which requires the individual, unity-normalized probability distribution of
the input signal. This calls for the variable-input revision of the original and
fixed-input formulation of OCT, which will be presented in Section 4. This
extension will be shown to be capable of the continuous description of the
orbital(s) decoupling limit, when AO subspace does not mix with (exhibit no
communications with) the remaining basis functions.
Additional, occupational aspect of the orbital decoupling in the OCT
description of a diatomic molecule will be described in Section 5. It intro-
duces the separate communication channels for each occupied MO and
establishes the relevant weighting factors and the crucial sign convention
of their entropic bond increments, which reflects the bonding or antibonding
character of the MO in question, in accordance with the signs of the asso-
ciated off-diagonal matrix elements of the CBO matrix. This procedure will
be applied to determine the π-bond alternation trends in simple hydrocar-
bons (Section 6) and the localized bonds in octahedral complexes (Section 7).
Finally, the weighted-input approach for diatomic fragments in molecules
will be formulated (Section 8). It will be shown that this new AO-resolved
description using the flexible-input (bond) probabilities as weighting fac-
tors generates bond descriptors exhibiting excellent agreement with both the
chemical intuition and the quantum-mechanical bond orders formulated in
the standard SCF-LCAO-MO theory.
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6 Roman F. Nalewajski, Dariusz Szczepanik, and Janusz Mrozek
Throughout this article, the bold symbol X represents a square or rectan-
gular matrix, the bold-italic X denotes the row vector, and italic X stands
for the scalar quantity. The entropy/information descriptors are measured
in bits, which correspond to the base 2 in the logarithmic (Shannon) measure
of information.
2. MOLECULAR INFORMATION CHANNELS IN ORBITAL
RESOLUTION
In the standard MO theory of molecular electronic structure the network of
chemical bonds is determined by the system-occupied MO in the electron
configuration in question. For simplicity, let us first assume the closed-
shell (cs) ground state of the N=2n electronic system in the Restricted
Hartree–Fock (RHF) description, involving the n lowest (real and orthonor-
mal), doubly occupied MO. In the LCAO-MO approach, they are given
as linear combinations of the appropriate (orthogonalized) basis functions
χ =(χ
1
, χ
2
, . . . , χ
m
) ={χ
i
], ¸χ[χ) ={δ
i, j
] ≡ I, for example, L¨ owdin’s symmetri-
cally orthogonalized AO, ϕ =(ϕ
1
, ϕ
2
, . . . , ϕ
n
) ={ϕ
s
] =χC, where the rectangu-
lar matrix C={C
i,s
] groups the relevant LCAO-expansion coefficients.
The system electron density ρ(r) and hence the one-electron probabil-
ity distribution p(r) =ρ(r)/N, that is, the density per electron or the shape
factor of ρ, are determined by the first-order density matrix γ in the AO
representation, also called the charge and bond order (CBO) matrix,
ρ(r) =2ϕ(r)ϕ

(r) = χ(r)[2CC



(r) ≡ χ(r)γχ

(r) = Np(r). (1)
The latter represents the projection operator
ˆ
P
ϕ
=[ϕ)¸ϕ[ =

s

s
)¸ϕ
s
[ ≡

s
ˆ
P
s
onto the subspace of all doubly occupied MO,
γ=2¸χ[ϕ)¸ϕ[χ) = 2CC

≡ 2¸χ[
ˆ
P
ϕ
[χ) = {γ
i, j
= 2¸χ
i
[
ˆ
P
ϕ

j
) ≡ 2¸i[
ˆ
P
ϕ
[j)], (2a)
thus, satisfying the appropriate idempotency relation
(γ)
2
= 4¸χ[
ˆ
P
ϕ
[χ)¸χ[
ˆ
P
ϕ
[χ) = 4¸χ[
ˆ
P
2
ϕ
[χ) = 4¸χ[
ˆ
P
ϕ
[χ) = 2γ. (3)
The CBOmatrix reflects the promoted, valence state of AOin the molecule,
with the diagonal elements measuring the effective electron occupations of
the basis functions, {γ
i,i
=N
i
=Np
i
]. The AO-probability vector in this state,
p={p
i
=N
i
/N], groups the probabilities of the basis functions being occupied
in the molecule.
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Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 7
The information system in the (condensed) orbital resolution involves
the AO events χ in its input a={χ
i
] and output b ={χ
j
]. It represents
the effective promotion of these basis functions in the molecule via the
probability/information scattering described by the conditional probabil-
ities of AO outputs given AO inputs, with the input (row) and output
(column) indices, respectively. In the one-electron approach [46–48], these
AO-communication connections {P(χ
j

i
) ≡ P(j[i)] result from the appropri-
ately generalized superposition principle of quantum mechanics [51],
P(b[a) =
_
P(j[i) = N
i
[¸i[
ˆ
P
ϕ
[j)[
2
= (2γ
i,i
)
−1
γ
i, j
γ
j,i
_
,

j
P(j[i) = 1, (4)
where the closed-shell normalization constant N
i
= (2γ
i,i
)
−1
follows directly
Eq. (3). These (physical) one-electron probabilities explore the dependen-
cies between AOs resulting from their participation in the system-occupied
MO, that is, their involvement in the entire network of chemical bonds in a
molecule. This molecular channel can be probed using both the promolecu-
lar (p
0
={p
0
i
]) and molecular (p) input probabilities, in order to extract the IT
multiplicities of the ionic and covalent bond components, respectively.
In the open-shell (os) case [48] one partitions the CBO matrix into contri-
butions originating from the closed-shell (doubly occupied) MO ϕ
cs
and the
open-shell (singly occupied) MO ϕ
os
, ϕ =(ϕ
cs
, ϕ
os
):
γ=¸χ[ϕ
os
)¸ϕ
os
[χ) ÷2¸χ[ϕ
cs
)¸ϕ
cs
[χ) ≡ ¸χ[
ˆ
P
os
ϕ
[χ) ÷2¸χ[
ˆ
P
cs
ϕ
[χ) ≡ γ
os
÷γ
cs
. (5)
They satisfy separate idempotency relations,

os
)
2
=
_
χ
¸
¸ ˆ
P
os
ϕ
¸
¸
χ
__
χ
¸
¸ ˆ
P
os
ϕ
¸
¸
χ
_
=
_
χ
¸
¸
(
ˆ
P
os
ϕ
)
2
_
χ
_
=
_
χ
¸
¸ ˆ
P
os
ϕ
¸
¸
χ
_
= γ
os
, (6)
and (γ
cs
)
2
=2γ
cs
(Eq. [3]). Hence,
P(j[i) = N
i
[¸i[
ˆ
P
ϕ
[j)[
2
= (γ
os
i,i
÷2γ
cs
i,i
)
−1
γ
i,j
γ
j,i
, (7a)
The conditional probabilities of Eqs. (4 and 7a) define the probability scat-
tering in the AO-promotion channel of the molecule, in which the “signals”
of the molecular (or promolecular) electron allocations to basis functions are
transmitted between the AO inputs and outputs. Such information system
constitutes the basis of OCT [46–48]. The off-diagonal conditional probabil-
ity of jth AO output given ith AO input is thus proportional to the squared
element of the CBO matrix linking the two AOs, γ
j,i

i, j
. Therefore, it is also
proportional to the corresponding AO contribution M
i, j

2
i, j
to the Wiberg
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8 Roman F. Nalewajski, Dariusz Szczepanik, and Janusz Mrozek
index [52] of the chemical bond covalency between two atoms A and B,
M(A,B) =

i∈A

j∈B
M
i, j
, or to generalized quadratic descriptors of molecular
bond multiplicities [53–63].
By separating the CBO contributions due to each occupied MO one
similarly defines the information system for each orbital. For example, in
the closed-shell system, each doubly occupied MO ϕ ={ϕ
s
] generates the
corresponding contributions to the CBO matrix of Eq. (2):
γ = 2

s
¸χ[ϕ
s
)¸ϕ
s
[χ) ≡

s
γ
cs
s
, γ
cs
s
=
_
γ
cs
i, j
(s) = 2¸i[
ˆ
P
s
[j)
_
, (2b)
In the open-shell configuration, one separately partitions the contri-
bution of γ
cs
=

cs
s
γ
cs
s
, due to the doubly occupied MO ϕ
cs
, and the
remaining part γ
os
=

os
s
γ
os
s
, γ
os
s
={γ
os
i, j
(s) =¸i[
ˆ
P
s
[j)], generated by the singly
occupied MO ϕ
os
. They satisfy the corresponding idempotency relations
(see Eqs. [3 and 6]): (γ
cs
s
)
2
=2γ
cs
s
and (γ
os
s
)
2

os
s
. One then determines the
corresponding communication connections for each occupied MO,
P
os
s
(b[a) =
_
P
os
s
(j[i) =
γ
os
i, j
(s)γ
os
j,i
(s)
γ
os
i,i
(s)
_
and P
cs
s
(b[a) =
_
P
cs
s
(j [i ) =
γ
cs
i, j
(s)γ
cs
j,i
(s)

cs
i,i
(s)
_
,
(7b)
were obtained using Eqs. (4a and 7a) with the normalization constants
appropriately modified to satisfy the normalization condition for the con-
ditional probabilities:

j
P
cs
s
(j[i) =

j
P
os
s
(j[i) = 1. (7c)
In OCT, the entropy/information indices of the covalent/ionic compo-
nents of all chemical bonds in a molecule represent the complementary
descriptors of the average communication noise and the amount of informa-
tion flowin the molecular information channel. The molecular input p(a) ≡ p
generates the same distribution in the output of the molecular channel,
pP(b[a) =
_

i
p
i
P(j[i) ≡

i
P(i, j) = p
j
_
= p (8)
and thus identifying p as the stationary probability vector for the molecu-
lar state in question. In the preceding equation we have used the partial
normalization of the molecular joint, two-orbital probabilities P(a, b) =
{P(i, j) =p
i
P(j[i)] to the corresponding one-orbital probabilities. It should be
observed at this point that the promolecular input p(a
0
) ≡ p
0
in general
produces different output probability p
0
P(b[a) =p

(a
0
) ={p

j
] =p

,= p.
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Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 9
The purely molecular communication channel [9, 38, 46–48], with p defin-
ing its input signal, is devoid of any reference (history) of the chemical
bond formation and generates the average noise index of the molecular IT
bond covalency, measured by the conditional entropy S(b[a) ≡ S of the system
outputs given inputs:
S(b[a) = −

i

j
P(i, j)log
2
[P(i, j)/p
i
]
= −

i
p
i

j
P(j[i)log
2
P(j[i) ≡ S[p[p] ≡ S[P(b[a)] ≡ S. (9a)
Thus, this average noise descriptor expresses the difference between the
Shannon entropies of the molecular one- and two-orbital probabilities,
S = H[P(a, b)] −H[p];
H[p] = −

i
p
i
log
2
p
i
,
H[P(a, b)] = −

i

j
P(i, j)log
2
P(i, j). (9b)
For the independent input and output events, when P
ind.
(a, b) ={p
i
p
j
],
H[P
ind.
(a, b)] =2H[p] and hence S
ind.
=H[p].
The molecular channel with p
0
determining its input signal refers to the
initial state in the bond formation process, for example, the atomic pro-
molecule—a collection of nonbonded free atoms in their respective positions
in a molecule or the AO basis functions with the atomic ground-state occu-
pations, before their mixing into MO [9, 38, 46–48]. The AO occupations
in this reference state are fractional in general. However, in view of the
exploratory character of the present analysis, we shall often refer to the
simplest description of the promolecular reference by a single (ground-
state) electron configuration, which exhibits the integral occupations of AO.
It gives rise to the average information-flow descriptor of the system IT
bond ionicity, given by the mutual information in the channel inputs and
outputs:
I(a
0
: b) =

i

j
P(i, j)log
2
[P(i, j)/(p
j
p
0
i
)] = H[p] ÷H[p
0
] −H[P(a, b)]
= H[p
0
] −S = I[p
0
: p] ≡ I[P(b[a)] = I, (10)
This quantity reflects the fraction of the initial (promolecular) information
content H[p
0
], which has not been dissipated as noise in the molecular
communication system. In particular, for the molecular input, when p
0
=p,
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10 Roman F. Nalewajski, Dariusz Szczepanik, and Janusz Mrozek
I(a: b) =

i

j
P(i, j)log
2
[P(i, j)/(p
j
p
i
)] =H[p] −S=I[p: p]. Thus, for the ind-
ependent input and output events, I
ind.
(a: b) =0.
Finally, the sum of these two bond components,
N(a
0
; b) = S ÷I ≡ N[p
0
; p] ≡ N[P(b[a)] ≡ N = H[p
0
], (11)
measures the overall IT bond multiplicity of all bonds in the molecular
system under consideration. It is seen to be conserved at the promolecular-
entropy level, which marks the initial information content of orbital proba-
bilities. Again, for the molecular input, when p
0
=p, this quantity preserves
the Shannon entropy of the molecular input probabilities: N(a; b) =S(b[a) ÷
I(a: b) =H[p].
It should be emphasized that these entropy/information descriptors and
the underlying probabilities depend on the selected basis set, for exam-
ple, the canonical AO of the isolated atoms or the hybrid orbitals (HOs) of
their promoted (valence) states, the localized MO (LMO), etc. In what fol-
lows we shall examine these IT descriptors of chemical bonds in illustrative
model systems. The emphasis will be placed on the orbital decoupling in the
molecular communication channels and the need for appropriate changes
in their input probabilities, which weigh the contributions to the average
information descriptors from each input.
There are two aspects of the orbital decoupling in chemical bonds. On one
side, the two chemically interacting AOs becomes decoupled, when they do
not mix into MO, for example, in the extreme MO-polarization limit of the
electronic lone pair, when two bonding electrons occupy a single AO. On the
other side, the two AOs are also effectively decoupled, no matter how strong
is their mutual mixing, when the bonding and antibonding MO combina-
tions are completely occupied by electrons, since such MO configuration is
physically equivalent to the Slater determinant of the doubly occupied (orig-
inal) AO. We shall call these two facets the mixing (shape) and occupation
(population) decouplings, respectively.
It is of vital interest for a wider applicability of CTCB to examine howthese
two mechanisms can be accommodated in OCT. In Section 3, we shall argue
that the mutual decoupling status of several subsets of basis functions, mani-
festing itself by the absence of any external communications (bond orders) in
the whole system, calls for the separate unit normalization of its input prob-
abilities since such fragments constitute the mutually nonbonded (closed)
building blocks of the molecular electronic structure. It will be demonstrated,
using simple hydrides as an illustrative example, that the fulfillment of this
requirement dramatically improves the agreement with the accepted chemi-
cal intuition and the alternative bond multiplicity concepts formulated in the
MO theory.
To conclude this section, we observe that by propagating the AO prob-
abilities through the information channels of the separate MO, defined by
the conditional probabilities of Eq. (7b), one could similarly determine the
Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 11 #11
Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 11
IT bond increments for each occupied MO. We shall implement this idea in
Section 5, when tackling the populational decoupling of atomic orbitals, as a
result of an increased occupation of the antibonding MO.
3. DECOUPLED (LOCALIZED) BONDS IN HYDRIDES REVISITED
In the ground-state the chemical interaction between two (singly occupied)
orthonormal AOs χ =(a, b) originating from atoms A and B, respectively,
gives rise to the doubly occupied, bonding MO ϕ
bond.
and the unoccupied
antibonding MO ϕ
anti.
,
ϕ
bond.
=

Pa ÷
_
Qb, ϕ
anti.
= −
_
Qa ÷

Pb, P ÷Q = 1. (12)
Their shapes are determined by the complementary (conditional) proba-
bilities: P(a[ϕ
bond.
) =P(b[ϕ
anti.
) =P and P(b[ϕ
bond.
) =P(a[ϕ
anti.
) =Q, which con-
trol the bond polarization, covering the symmetrical bond combination
for P=Q=1/2 and the limiting lone-pair (nonbonding) configurations for
P=(0, 1). The associated model CBO matrix,
γ=2
_
P
_
PQ
_
PQ Q
_
, (13)
then generates the information system for such a two-AO model, shown in
Scheme 1.1a.
In this diagram one adopts the molecular input p=(P, Q=1 −P), to
extract the bond IT covalency index measuring the channel average com-
munication noise, and the promolecular input p
0
=(1/2, 1/2), to calculate the
IT ionicity relative to this covalent promolecule, in which each basis func-
tion contributes a single electron to form the chemical bond. The bond IT
covalency S(P) is then determined by the binary entropy function H(P) = −
Plog
2
P −Qlog
2
Q=H[p]. It reaches the maximum value H(P=1/2) =1 for
the symmetric bond P=Q=1/2 and vanishes for the lone-pair configura-
tions, when P=(0, 1), H(P=0) =H(P=1) =0, marking the alternative ion-
pair configurations A
÷
B

and A

B
÷
, respectively, relative to the initial AO
occupations N
0
=(1, 1) in the assumed promolecular reference. The comple-
mentary descriptor of the IT ionicity, determining the channel (mutual) infor-
mation capacity I(P) =H[p
0
] −H(P) =1 −H(P), reaches the highest value for
these two limiting electron-transfer configurations P=(0, 1): I(P=0, 1) =1.
Thus, this ionicity descriptor is seen to identically vanish for the purely
covalent, symmetric bond, I(P=1/2) =0.
Both components yield the conserved overall bond index N(P) =1 in the
whole range of bond polarizations P ∈ [0, 1]. Therefore, this model properly
accounts for the competition between the bond covalency and ionicity, while
Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 12 #12
12 Roman F. Nalewajski, Dariusz Szczepanik, and Janusz Mrozek
P(b|a) p p
P a a P
(a)
(b)
P
Q b b Q
P
Q
Q
1 h
0
n
h
0
n
1 1
S = −Plog
2
P −Qlog
2
Q = H(P)
I = H[ p
0
] −H(P)
N = I ÷S = H[ p
0
]
S = I = N = 0
Scheme 1.1 The molecular information system modeling the chemical bond between two
basis functions χ =(a, b) and its entropy/information descriptors. In Panel b, the corre-
sponding nonbonding (deterministic) channel due to the lone-pair hybrid h
0
n
is shown. For the
molecular input p =(P, Q), the orbital channel of Panel a gives the bond entropy-covalency
represented by the binary entropy function H(P). For the promolecular input p
0
=(1/2, 1/2),
when both basis functions contribute a single electron each to form the chemical bond,
one thus predicts H[p
0
] =1 and the bond information ionicity I =1 −H(P). Hence, these two
bond components give rise to the conserved (P-independent) value of the single overall bond
multiplicity N =I ÷S =1.
preserving the single measure of the overall IT multiplicity of the chemi-
cal bond. Similar effects transpire from the two-electron CTCB [9] and the
quadratic bond indices formulated in the MO theory [53–63].
This localized bond model can be straightforwardly extended to the sys-
tem of r localized bonds in simple hydrides XH
r
[49], for example, CH
4
, NH
3
,
or H
2
O, for r =4, 3, 2, respectively. Indeed, a single σ bond X–H
α
, for X=C,
N, O and α =1, . . . , r, can then be approximately regarded as resulting from
the chemical interaction of a pair of two orthonormal orbitals: the bonding
sp
3
hybrid h
α
of the central atom, directed towards the hydrogen ligand H
α
,
and the 1s
α
≡ σ
α
orbital of the latter. The localized bond X–H
α
then originates
from the double occupation of the corresponding bonding MOϕ
bond.
(α), with
the antibonding MO ϕ
anti.
(α) remaining empty:
ϕ
bond.
(α) =

Ph
α
÷
_

α
, ϕ
anti.
(α) = −
_
Qh
α
÷


α
P ÷Q = 1. (14)
In the χ
α
=(h
α
, σ
α
) representation, the corresponding CBO matrix γ
α
for a
single σ bond X–H
α

α,β
] then includes the following nonvanishing elements:
γ
h
α
,h
α
=2P, γ
σ
α

α
=2Q, γ
h
α

α

σ
α
,h
α
= 2
_
PQ, (15)
while for each of 4 −r nonbonded hybrids {h
n
], describing the system lone-
electronic pairs,
γ
h
n
,h
n
= 2 and γ
h
n
, j
= 0, j ,= h
n
. (16)
Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 13 #13
Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 13
The corresponding conditional probabilities (see Eq. [4]), which determine
the nonvanishing communication connections, then read:
P(h
α
[h
α
) = P, P(σ
α

α
) = Q, P(h
α

α
) = Q, P(σ
α
[h
α
) = P, P(h
n
[h
n
) = 1.
(17)
Therefore, the electron probability is not scattered by the lone-pair hybrids.
As a result such decoupled subchannels {h
n
=h
0
n
] representing two lone
pairs of oxygen atom in H
2
O or a single nonbonding electron pair of
nitrogen in NH
3
, introduce the exactly vanishing contributions to both
bond components and hence to the overall bond index of these molecules
in OCT.
It follows from these expressions that each localized bond X–H
α
in this HO
representation defines the separate communication system of Scheme 1.1a,
consisting of inputs and outputs χ
α
=(h
α
, σ
α
), which does not exhibit any
external communications with AO involved in the system remaining bonds.
Therefore, such orbital pairs constitute the externally closed (nonbond-
ing) subsystems, determining the mutually decoupled information systems
defined by the diagonal blocks
P
α
(b
α
[a
α
) ≡P
α

α

α
] =
_
P Q
P Q
_
, P
α
(a
α
, b
α
) ≡P
α

α
, χ
α
] =
_
P
2
PQ
QP Q
2
_
,
(18)
of the associated overall probability matrices in the χ ={χ
α
] basis set:
P(b[a) ={P
α
(b
α
[a
α

α,β
] and P(a, b) ={P
α
(a
α
, b
α

α,β
]. Such mutually closed
(isolated) subchannels correspond to the separate input/output probability
distributions, p
0
α
=(1/2, 1/2) or p
α
=p

α
=(P, Q), each satisfying the unit nor-
malization [9, 26]. These separate molecular subsystems give rise to the
additive bond contributions S
α
(b
α
[a
α
) ≡ S
α
, I
α
(a
0
α
: b
α
) ≡ I
α
and N
α
(a
0
α
: b
α
) =
S
α
÷I
α
≡ N
α
to the system overall bond descriptors in OCT:
S(P) =

α
S
α
= rH(P), I(P) =

α
I
α
=r[1 −H(P)], N =

α
N
α
=r. (19)
We have recognized in these expressions that each lone-pair (dou-
bly occupied) hybrid h
n
of the central atom, which does not form any
chemical bonds (communications) with the hydrogen ligands, generates
the decoupled deterministic subchannel of Scheme 1.1b, thus exhibit-
ing the unit input probability. Therefore, it does not contribute to
the resultant entropy/information index of all chemical bonds in the
molecule.
Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 14 #14
14 Roman F. Nalewajski, Dariusz Szczepanik, and Janusz Mrozek
The same result follows from another, delocalized representation of chem-
ical bonds in these prototype systems. Consider, as an illustration, the
canonical valence-shell MO in CH
4
, with four hydrogen ligands in the alter-
nating corners of the cube placed in such a way, that the three axes of the
Cartesian coordinate system pass through the middle of its opposite walls.
In such an arrangement, the four delocalized bonds are described by the four
(mutually decoupled) orbital-pair interactions between the specified canon-
ical AO of carbon atom and the corresponding symmetry combination of
four hydrogen orbitals. Again, the net result is the four decoupled bonds in
the system giving rise to overall IT bond index N = 4, with S = 4H(P) and
I = 4[1 −H(P)].
One observes, however, a change in the bond covalent/ionic composition
resulting from this transformation from the localized MO description to the
canonical MO perspective [48]. As an illustration of this entropic effect, let
us briefly examine the bonding pattern in the linear BeH
2
. In the localized
bond representation, the two bonding MOs result from the mutually decou-
pled interactions between two-orbital pairs, each including one sp hybrid of
Be and 1s orbital of the corresponding hydrogen. This localized approach
thus gives N = 2, with S = 2H(P) and I = 2[1 −H(P)], and hence for the
maximum orbital mixing (P = 1/2), the IT bond composition reads S
max.
= 2
and I
max.
= 0. In the delocalized description, the two doubly occupied canon-
ical MO, expressed in the basis set χ = (h
1
, h
2
, σ
1
, σ
2
) used to generate the
localized MO of Eq. (12), read as follows:
ψ
1
=

Us ÷
_
V
2

1
÷σ
2
) =
_
U
2
(h
1
÷h
2
) ÷
_
V
2

1
÷σ
2
), U ÷V = 1,
ψ
2
=

Tp ÷
_
W
2

1
−σ
2
) =
_
T
2
(h
1
−h
2
) ÷
_
W
2

1
−σ
2
), T ÷W = 1.
(20)
The associated CBO matrix,
γ =
_
_
_
_
_
_
U ÷T U −T

UV ÷

TW

UV −

TW
U −T U ÷T

UV −

TW

UV ÷

TW

UV ÷

TW

UV −

TW V ÷W V −W

UV −

TW

UV ÷

TW V −W V ÷W
_
¸
¸
¸
¸
_
,
(21)
indicates that all these basis orbitals in fact exhibit the nonvanishing com-
munications to all outputs in this delocalized representation of the system
electronic structure. In the maximum mixing limit of U = V = T = W = 1/2
Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 15 #15
Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 15
it is only partly decoupled,
γ
max.
=
_
_
_
_
1 0 1 0
0 1 0 1
1 0 1 0
0 1 0 1
_
¸
¸
_
, (22)
and so is the associated matrix P(b[a) = 1/2γ
max.
of molecular communica-
tions (see Eq. [4]). Thus, this delocalized channel is characterized by the
input distributions p = p
0
= {1/4], which give rise to the overall unit normal-
ization. The associated entropy/information indices for this channel read as
follows: S
max.
= I
max.
= 1 and hence N
max.
= 2.
The variable-input norm description of the decoupled chemical bonds
gives the full agreement with the chemical intuition, of r bonds in XH
r
,
with changing covalent/ionic composition in accordance with the actual MO
polarization and the adopted basis set representation. The more the probabil-
ity parameter P deviates from the symmetrical bond (maximum covalency)
value P = 1/2, due to the electronegativity difference between the central
atom and hydrogen, the lower is the covalency (the higher ionicity) of this
localized, diatomic bond. Therefore, in this IT description the total bond
multiplicity N = r bits is conserved for changing proportions between the
overall covalency and ionicity of all chemical bonds in the system under
consideration.
In the orbital-communication theory, this “rivalry” between bond compo-
nents reflects a subtle interplay between the electron delocalization (S
α
=
H(P)) and localization (I
α
= 1 −H(P)) aspects of the molecular scattering of
electron probabilities in the information channel of a separated single chem-
ical bond, decoupled from the molecular remainder. The more deterministic
is this probability propagation, the higher the ionic component. Accordingly,
the more delocalized is this scattering, the higher the “noise” descriptor of
the underlying information system.
4. FLEXIBLE-INPUT GENERALIZATION
Thus, it follows from the analysis of the preceding section that a gen-
eral agreement of IT descriptors with the intuitive chemical estimates fol-
lows only when each externally decoupled fragment of a molecule exhibits
the separate unit normalization of its input probabilities; this requirement
expresses its externally closed status relative to the molecular remainder.
It modifies the overall norm of the molecular input to the number of
such mutually closed, noncommunicating fragments of the whole molecular
system. This requirement was hitherto missing in all previous applications
of CTCB and OCT to polyatomic systems.
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16 Roman F. Nalewajski, Dariusz Szczepanik, and Janusz Mrozek
In the generalized approach the probabilities p
0
α
={p
α
a
] of the constituent
inputs in the given externally decoupled (noncommunicating and non-
bonded) subchannel α
0
of the system “promolecular” reference M
0
=

0

0
[ . . .) should thus exhibit the internal (intrasubsystem) normalization,

a∈α
p
α
a
= 1; we have denoted the externally closed status of each fragment in
M
0
by separating it with the vertical solid lines from the rest of the molecule.
Therefore, these subsystem probabilities are, in fact, conditional in character;
p
α
a
= P(a[α) = p
a
/P
α
, calculated per unit input probability P
α
= 1 of the whole
subsystem α in the collection of the mutually nonbonded subsystems in the
reference M
0
, that is, when this molecular fragment is not considered to be a
part of a larger system. Indeed, the above summation over the internal orbital
events then expresses the normalization of all such conditional probabilities
in the separate (or isolated) subsystem α
0
:

a∈α
P(a[α) = 1.
This situation changes discontinuously in the externally coupled (commu-
nicating and bonded) case, when the same subsystemexhibits non-vanishing
(no matter how small) communications with the remainder of the molecule
M = (α β . . .). Such bonded fragments of the molecule are mutually open,
as symbolically denoted by the vertical broken lines separating them. They
are characterized by the fractional condensed probabilities P = {P
M
α
< 1],
which measure the probabilities of the constituent subsystems in M as a
whole. Therefore, the input probabilities of the bonded fragment α in M,
p
M
α
= {p
M
a
= P
M
α
p
α
a
], are then subject to the molecular normalization:

a∈α
p
α
a
=
P
M
α

a∈α
p
α
a
= P
M
α
. The need for using the molecular input probabilities then
causes a discontinuous change in the system covalent/ionic bond compo-
nents compared with the corresponding decoupled (promolecular) values.
Indeed, the former corresponds to the unit norm of input probabilities for
all molecular subsystems, whereas in the latter, each decoupled fragment
appears as a separate system, thus alone exhibiting the unit probability
normalization.
In the previous, fixed-input determination of the IT bond indices this
discontinuity in the transition from the decoupled to the coupled descrip-
tions of the molecular fragments prevents an interpretation of the former
as the limiting case of the latter, when all external communications of the
subsystem in question become infinitely small. In other words, the fixed-
and flexible-input approaches generate the mutually exclusive sets of bond
indices, which cannot describe this transition in a continuous (“causal”)
fashion. As we have demonstrated in the decoupled approach of the pre-
ceding section, only the overall input normalization equal to the number of
the decoupled orbital subsystems gives rise to the full agreement with the
accepted chemical intuition.
Therefore, in this section we shall attempt to remove this discontinuity
in the unifying, flexible-input generalization of the use of the molecular
information systems. We shall demonstrate that in such an extension the
above limiting transition in the communication description of the subsystem
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Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 17
decoupling in the molecule finds the continuous (causal) representation. In
order to make this transition continuous, the separate input-dependent dis-
tributions, tailored for each ith input event, have to explicitly depend on the
structure of its molecular communications, which is embodied in the ith row
of the system two-orbital conditional probabilities. Indeed, they have to con-
tinuously increase the overall norm of the distribution for the given input
orbital with increasing localization of the molecular scattering of this input
signal to reach the unit input norm in the limit of this orbital being totally
decoupled from the rest of the molecule.
The essence of the new proposition lies in a separate determination of
the entropy/information contributions due to each AO input in the molec-
ular channel specified by the conditional probabilities P(b[a). This goal can
be tackled by using the separate probability distributions tailored for each
input. The hitherto single molecular propagation of the overall molecular
input probabilities p of the previous approach, carried out to extract the IT
covalent bond descriptor, will now be replaced by the series of m molec-
ular propagations of the separate probability distributions {p(i) = {p(k; i)]
for each molecular input i = 1, 2, . . . , m, which generate the associated cova-
lencies: {S(i) = S[p(i)]]. The reference promolecular probabilities, also input
dependent {p(i
0
) = {p(k; i
0
)], will be used to estimate the corresponding
ionic contributions due to each input: {I(i) = I[p(i
0
)]]. Together, these input-
dependent contributions generate the corresponding total indices {N(i) =
I(i) ÷S(i) = N[p(i
0
), p(i)]]. Finally, the overall IT bond descriptor of M as
a whole will be generated by the summation of all such additive con-
tributions determined in the separate propagations of the input-tailored
molecular/promolecular distributions: N =

i
N(i). In the average molec-
ular quantities, these contributions must be weighted with the appropriate
ensemble probabilities of each input, for example, the molecular probabilities
p = {p
i
].
There are obvious normalization (sum) rules to be satisfied by these input-
dependent probabilities. Consider first the completely coupled molecular
channel, in which all orbitals interact chemically, thus exhibiting nonvan-
ishing direct and/or indirect communications with the system remainder. In
this case all molecular inputs have to be effectively probed to the full extent
of the unit condensed probability of the molecule as a whole:

k
p(k; i)] =

k
p(k; i
0
)] = 1. (23)
This condition recognizes a general category of these input-dependent
probabilities {p(k; i)] and {p(k; i
0
)] as conditional probabilities of two-orbital
events, that is, the joint probabilities per unit probability of the specified
input: p(k; i) ≡ p(k[i) and p(k; i
0
) ≡ p(k[i
0
). However, it should be emphasized
that these probabilities are also conditional on the molecule as a whole, since
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18 Roman F. Nalewajski, Dariusz Szczepanik, and Janusz Mrozek
they correspond to the unit input probability in M or M
0
,

i
p
i
=

i
p
0
i
= 1,
p(k[i) = p(k[i|M) = P(k[i), p(k[i
0
) = p(k[i
0
|M
0
) = P(k[i
0
) ≡ P(k[i). (24)
In case of the decoupled single-orbital subsystem χ
0
i
, only the diagonal
probability scattering P
i
(i[i) = 1 is observed in the molecule (Scheme 1.1b).
The input-tailored conditional probabilities then refer to the unit input
probability of the input i(i
0
) alone:
p(k[i) = p(i[i|i) = p(i[i)δ
i,k
= p(k[i
0
) = p(i[i
0
|i
0
) = p(i
0
[i
0

i,k
= δ
i,k
. (25)
In order to make the fragment decoupling continuous in this general-
ized description, the input probabilities {p(i), p
0
(i)] have to be replaced by
the separate distributions reflecting the actual participation of ith AO in
the chemical bonds (communications) of the molecule. Therefore, they both
have to be related explicitly to the ith row in the conditional probability
matrix P(b[a) = {P(j[i)], which reflects all communications (bonds) between
this orbital input and all orbital outputs {j] (columns in P(b[a)). This link
must generate the separate subsystem probabilities p
0
α
, when the fragment
becomes decoupled from the rest of the molecular system, α → α
0
, when
P(b[a
α
) → {P(b
α
[a
α

α,β
], where P(b
α
[a
α
) = {P(a
/
[a)]. Indeed, for the decou-
pled subsystemα
0
= (a, a
/
, . . .) only the internal communications of the corre-
sponding block of the molecular conditional probabilities P(b
α
[a
α
) = {P(a
/
[a)]
are allowed. They also characterize the internal conditional probabilities in
α
0
since
p(j[i|α
0
) = p(i, j|α
0
)/p(i|α
0
) = P(i, j|M)/p(i|M) = p(j[i|M) = P(j[i). (26)
Hence, {p(k[a|α
0
) =p
α
(a
/
[a)δ
α,β
=p(k[a
0

0
) =p
α
(a
/
[a
0

α,β
=P(a
/
[a)δ
α,β
]; again,
the AO inputs in α are to be probed with an overall unit condensed
probability:

a
/
∈α
P(a
/
[a) = 1.
In the input-dependent molecular channels, all these requirements can
be shown to be automatically satisfied when one selects the input-tailored
probabilities, we seek, as the corresponding rows of the molecular condi-
tional probability matrix P(b[a) = {P(j[i)]. Consider the conditional-entropy
contribution from ith channel:
S(i) = −

k

j
P(k, j; i)log
2
[P(j, k)/p
k
] = −

k
P(k[i)
_

j
P(j[k)log
2
P(j[k)
_
.
(27)
Since this entropy-covalency corresponds to the overall unit norm of
probability distribution associated with ith input, in the average molecu-
lar quantity, corresponding to all mutually open basis functions, it has to
be weighted by the actual probability p
i
of this input in the molecule as a
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Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 19
whole. It can be directly verified that such averaging indeed reproduces the
molecular index of Eq. (9):
S
av.
=

i
p
i
S(i) ≡

i
S
i
= −

i

k

j
[p
i
P(k[i)]P(j[k)log
2
P(j[k)
= −

k

j
_

i
P(k, i)
_
P(j[k)log
2
P(j[k) = −

k

j
p
k
P(j[k)log
2
P(j[k)
= −

k

j
P(j, k)log
2
P(j[k) = S. (28)
A similar demonstration can be carried out for the mutual-information
(ionic) contributions:
I(i) =

k

j
P(k
0
, j[i)log
2
[P(j, k)/(p
j
p
0
k
)] = −S(i) −

k

j
P(j, k
0
)log
2
p
0
k
= −S(i) −

k
p
0
k
log
2
p
0
k
= −S(i) ÷H[p
0
],
I
av.
=

i
p
i
I(i) ≡

i
I
i
= −S ÷H[p
0
], (29)
Thus, it follows from these contributions that they also reproduce the
overall molecular bond index as the mean value of the partial, input AO
contributions:
N(i) =S(i) ÷I(i) = −

k

j
P(k
0
, j)log
2
p
0
k
,
N
av.
=

i
p
i
N(i) ≡

i
N
i
= N = H[p
0
]. (30)
To summarize, in the flexible-input extension of OCT the consistent use
of the molecular channel is proposed, with only the molecular inputs being
used in probability propagation. However, the promolecular reference dis-
tribution is seen to enter the final determination of the ionic (difference)
components relative to the initial distribution of electrons before the bond
formation.
As an illustration (see Scheme 1.2a), let us again consider the two-AO
channel of Scheme 1.1a. We first observe that the input-dependent distribu-
tions in this model are identical with the molecular distribution (see Eq. [18]).
The partial and average IT descriptors are also reported in this diagram, rela-
tive to the reference distribution p
0
= (1/2, 1/2) of the covalent promolecule,
when two AOs contribute a single electron each to form the chemical bond.
Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 20 #20
20 Roman F. Nalewajski, Dariusz Szczepanik, and Janusz Mrozek
p(a), p(b)
p(a
0
), p(b
0
)
p(a), p(b)
p(a
0
), p(b
0
)
P
a
P
a
P
Q
P
Q b Q b Q
P(b|a)
S
a
= PH(P) S
b
=QH(P)
I
a
= P[1 −H(P)] I
b
= Q[1 −H(P)]
N
a
= S
a
÷I
a
= P N
b
= S
b
÷I
b
= Q
S
av.
= S
a
÷S
b
= H(P) = S I
av.
= I
a
÷I
b
= 1 −H(P) = I N
av.
= N
a
÷N
b
= 1 = N
Scheme 1.2 The flexible-input generalization of the two-AO channel of Scheme 1.1a for the
promolecular reference distribution p
0
= (1/2, 1/2). The corresponding partial and average
entropy/information descriptors of the chemical bond are also reported.
The flexible-normgeneralization of the previous OCT completely reproduces
the overall IT bond order and its components reported in Scheme 1.1.
It follows from the input probabilities in Scheme 1.2 that in the limit of the
decoupled (lone-pair) orbital ϕ
bond.
= a(P = 1) or ϕ
bond.
= b(Q = 1) its input
probability becomes 1, while that of the other (empty) orbital identically van-
ishes, as required. The unit input probability of the doubly occupied AO in
the channel input is then deterministically transmitted to the same AO in
the channel output, with the other (unoccupied) AO not participating in the
channel communications, so that both orbitals do not contribute to the resul-
tant bond indices. Therefore, the flexible-input approach correctly accounts
for the MO shape decoupling in the chemical bond, which was missing in the
previous, fixed-input scheme.
It is also of interest to examine the dissociation of this model molecule
A–B into (one-electron) atoms A and B, which determine the promolecule.
Such decoupled AO corresponds to the molecular configuration [ϕ
1
bond.
ϕ
1
anti.
]
since the Slater determinant [ϕ
bond.
ϕ
anti.
[ = [ab[. Indeed, using the orthogonal
transformations between χ = (a, b) and ϕ = (ϕ
bond.
, ϕ
anti.
),
χ = ϕ
_ √
P
_
Q

_
Q

P
_
≡ ϕC
T
and ϕ = χC, C
T
C = CC
T
=I,
one can directly verify that γ[ϕ
1
bond.
ϕ
1
anti.
] = CC
T
= I = P(b[a), so that the
decoupled AO inputs become p(a) = p(a
0
) = (1, 0) and p(b) = p(b
0
) = (0, 1),
each is separately unity normalized.
Therefore, while still retaining the essence of the previous approach,
the new proposition introduces in OCT of the chemical bond that is the
desired input flexibility generating the continuity in the IT description of
the fragment decoupling process. This generalization covers in a common
framework both the completely coupled AO in the molecule and the limiting
cases of its subsystems being effectively decoupled in the molecular chan-
nel. In the former case, the resultant input signal corresponds to the unit
norm of the condensed probability distribution. In the case of n-mutually
separated fragments, this flexible normalization is automatically increased
Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 21 #21
Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 21
to n by the choice of the flexible probabilities for each input represented by
the conditional two-orbital probabilities. As we have shown in the previ-
ous section, such an approach dramatically improves the agreement with
the accepted chemical intuition. It also has the conceptual and interpretative
advantages by providing a unifying description capable of tacking both the
coupled and decoupled molecular fragments in a single theoretical frame-
work and generating the continuous description of the shape-decoupling
limit, so that the decoupled subsystems appear naturally as those exhibiting
infinitely small communications with the molecular remainder.
It should be emphasized that in calculating the “ensemble” average
bond components of Eq. (28), the product

k
p
i
P(k[i)P(j[k) =

k
P(i, k)
P(j[k) ≡ P
ens.
(i, j) represents an effective joint probability of orbitals χ
i
and χ
j
in a molecule. Indeed, the amplitude interpretation of Eq. (4) gives

k
p
i
P(j[k)
P(k[i) ∝p
i

k
¸j[ϕ)¸ϕ[k)¸k[ϕ)¸ϕ[i) = p
i
¸j[
ˆ
P
ϕ
ˆ
P
χ
ˆ
P
ϕ
[i) = p
i
¸j[
ˆ
P
ϕ
[i) ∝ p
i
P(j[i), since
ˆ
P
χ
ˆ
P
ϕ
=
ˆ
P
ϕ
and
ˆ
P
ϕ
ˆ
P
ϕ
=
ˆ
P
ϕ
. Therefore, this probability product in fact mea-
sures an ensemble probability of simultaneously finding an electron on
orbitals χ
i
and χ
j
. In Section 8, we shall use such diatomic (bonding) probabil-
ity weights, when χ
i∈A
and χ
j∈B
, in determining the effective IT descriptors of
chemical interactions in diatomic fragments of the molecule.
5. POPULATIONAL DECOUPLING OF ATOMIC ORBITALS
The previous formulation of CTCB in atomic resolution was shown to fail to
predict a steady decrease in the resultant bond order with increasing occu-
pation of the antibonding MO [9, 43–45]. The same shortcoming is observed
in the fixed-input OCT. For example, in the N = 3, electron system described
by the two-AO model, [M(3)] = [ϕ
2
bond.
ϕ
1
anti.
], one obtains S = 0.47, I = 0.48,
and N = 0.95. Therefore, despite a half occupation of ϕ
anti.
, MO the overall
bond multiplicity remains almost the same as in the completely bonding
configuration of the two-electron system [M(2)] = [ϕ
2
bond.
]. Moreover, this
probabilistic approach cannot distinguish between the two bonding config-
urations for N = 1, [M(1)] = [ϕ
1
bond.
], and N = 2, [M] = [ϕ
2
bond.
], predicting the
same bond indices, reported in Scheme 1.1a. Similarly, for the total popu-
lation decoupling in the N = 4 electron system, [M(4)] = [ϕ
2
bond.
ϕ
2
anti.
], one
predicts S = 0, I = N = 1. This is because the probabilistic models loose the
“memory” about the relative phases of AO in MO [43–45], which is retained
by the elements of the quantum-mechanical CBO matrix and density of the
nonadditive Fisher information [34–38]. Therefore, in this approach only
the covalent index reflects the nonbonding (noncommunicating) status of
AO in this limit. This diagnosis indicates a need for introducing into the
MO-resolved scheme the information about the bonding/antibonding char-
acter of specific (occupied) MO, which is not reflected by their condensed
electron probabilities in atomic resolution.
Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 22 #22
22 Roman F. Nalewajski, Dariusz Szczepanik, and Janusz Mrozek
Let us now put to the test the performance of the flexible-input chan-
nels, which were shown to properly account for the MO shape decoupling.
In the limiting case of the complete population decoupling in the two-AO
model, when both doubly occupied basis functions remain effectively non-
bonding in the molecule, γ = 2I and hence P(b[a) = I. Therefore, the two
completely occupied AOs remain effectively closed (noncommunicating and
decoupled) for any level of their mixing measured by the AO-probability
parameter P. Again, the input-dependent probabilities separately exhibit
the unit probability norm, completely localized on a single orbital: p(a) =
p(a
0
) = (1, 0) and p(b) = p(b
0
) = (0, 1). Thus, this scheme correctly predicts
the nonbonding (nb) character of such a hypothetical electronic structure:
S
nb
= I
nb
= N
nb
= 0. Obviously, the same result follows from the flexible-
input contributions to the system average entropy/information descriptors.
However, the problem of distinguishing between the two bonding cases, a
half-bond for N = 1 and the full single bond for N = 2, still remains, and
the descriptors of the N = 3 channel also grossly contradict the chemical
intuition.
This failure to properly reflect the intuitive MO-population trends by the
IT bond indices calls for a thorough revision of the hitherto used overall
communication channel in AO resolution, which combines the contributions
from all occupied MOs in the electron configuration in question. Instead, one
could envisage a use of the separate MO channels introduced in Section 2
(Eq. [7b]). As an illustration, let us assume for simplicity the two-AO model
of the chemical bond A–B originating from the quantum-mechanical interac-
tion between two AOs: χ =(a ∈ A, b ∈ B). The bond contributions between
this pair of AO in the information system of sth MO,
S
a,b

s
) = S[P
s
(b [a)],
I
a,b

s
) = H[p
0
s
] −S(ϕ
s
),
N
a,b

s
) = S
a,b

s
) ÷I
a,b

s
) = H[p
0
s
], (31)
would then be straightforwardly recognized as bonding (positive), when
γ
a,b

s
) > 0, or antibonding (negative), when γ
a,b

s
) < 0, and nonbonding
(zero), when γ
a,b

s
) = 0. Here, p
0
s
denotes the input probability in the ϕ
s
infor-
mation channel. Alternatively, the purely molecular estimate of the mutual
information I
s
[p
s
: p
s
] can be used to index the localized bond ionicity.
In combining such MO contributions into the corresponding resultant
bond indices for the specified pair (i, j) of AO, these increments should
be subsequently multiplied by the MO-occupation factor f
MO
={ f
s
= n
s
/2],
which recognizes that the full bonding/antibonding potential of the given
MO is realized only when it is completely occupied, and by the correspond-
ing MO probability P
MO
={P
s
=n
s
/N]. The resultant A–B descriptors would
then be obtained by summation of such occupation/probability-weighted
bonding or antibonding contributions from all occupied MOs, which
Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 23 #23
Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 23
determine the system chemical bonds:
S(i, j) =

s
sign[γ
i, j

s
)]P
s
f
s
S
i, j

s
), I(i, j) =

s
sign[γ
i, j

s
)]P
s
f
s
I
i, j

s
),
N(i, j) =

s
sign[γ
i, j

s
)]P
s
f
s
N
i, j

s
). (32)
As shown in Scheme 1.3, these resultant IT indices from the MO-resolved
OCT do indeed represent adequately the population-decoupling trends for
N=1 4 electrons in the two-AO model.
Consider now another model system of the π electrons in allyl, with the
consecutive numbering of 2p
z
= z orbitals in the carbon chain. In the H¨ uckel
approximation, it is described by two occupied (canonical) MOs:
ϕ
1
=
1

2
_
1

2
(z
1
÷z
3
) ÷z
2
_
(doubly occupied) and
ϕ
2
=
1

2
(z
1
−z
3
) (singly occupied), (33)
which generate the corresponding MO and molecular CBO matrices,
γ
1
=
1
2
_
_
1

2 1

2 2

2
1

2 1
_
_
, γ
2
=
1
2
_
_
1 0 −1
0 0 0
−1 0 1
_
_
,
γ = γ
1
÷γ
2
=
1
2
_
_
2

2 0

2 2

2
0

2 2
_
_
, (34)
and the molecular information systemshown in Scheme 1.4. The correspond-
ing MO information systems, generated by the partial CBO matrices {γ
s
],
using the MO-input probabilities of AO, p
s
= {p(i[s) = γ
ij
(s)/n
s
], are reported
in Scheme 1.5; their normalization requires that

i
p(i[s) = 1.
It follows from Eqs. (2b, 7a, and 7a) that there are no analytical combina-
tion formulas [9] for grouping the partial MObond indices of Scheme 1.5 into
their overall analogs of Scheme 1.4. Indeed, the MO channels are determined
by their own CBOstructure, and a variety of their nonvanishing communica-
tion connections between AOs generally differ from that for the system as a
whole. Moreover, the input (conditional) probabilities used in Scheme 1.5 do
not reflect the two MO channels being a part of the whole molecular channel.
The latter requirement is only satisfied when the two networks are paral-
lely coupled [42] into the combined information system, in which the input
probabilities are given by the corresponding products { ¨ p
s
= P
s
p
s
], where
the MO probabilities P
MO
= {P
s
] = (2/3, 1/3). In allyl such molecular inputs
give the following IT descriptors of the two MO channels:
¨
S
1
= P
1
S
1
= 1,
Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 24 #24
24 Roman F. Nalewajski, Dariusz Szczepanik, and Janusz Mrozek
(a)
γ
b
= n
b
_
P

PQ

PQ Q
_
S(ϕ
b
) = H(P)
P a P
a
P
Q
P
Q b Q b Q
I(ϕ
b
) =H
_
1
2
_
−H(P) = 1 −H(P)
I(ϕ
b
) = S(ϕ
b
) ÷I(ϕ
b
) = 1
(b)
γ
a
= n
a
_
Q −

PQ


PQ P
_
S(ϕ
a
) = H(P)
Q
a
Q a Q
P
Q
P b P b P
I(ϕ
a
) =H
_
1
2
_
−H(P) = 1 −H(P)
N(ϕ
a
) = S(ϕ
a
) ÷I(ϕ
a
) = 1
(c)
ϕ
a
γ =
_
P

PQ

PQ Q
_
P(b[a) =
_
P Q
P Q
_
P
MO
= (1, 0)
ϕ
b
S =
1
2
S(ϕ
b
) =
_
1
2
_
H(P) I =
1
2
I(ϕ
b
) =
_
1
2
_
[1 −H(P)] N =
1
2
N(ϕ
b
) =
1
2
ϕ
a
γ = 2
_
P

PQ

PQ Q
_
P(b[a) =
_
P Q
P Q
_
P
MO
= (1, 0)
ϕ
b
S =S(ϕ
b
) =H(P) I =I(ϕ
b
) =[1 −H(P)] N = N(ϕ
b
) = 1
j
a
γ =
_
2P ÷Q

PQ

PQ 2Q÷P
_
P(b[a) =
_
(P ÷1)
2
/(3P ÷1) PQ/(3P ÷1)
QP/(3Q÷1) (Q÷1)
2
/(3Q÷1)
_
P
MO
=
_
2
3
,
1
3
_
j
b
S =
_
2
3
_
S(ϕ
b
) −
_
1
6
_
S(ϕ
a
) =
1
2
H(P) I =
_
2
3
_
I(ϕ
b
) −
_
1
6
_
I(a) =
_
1
2
_
[1 −H(P)]
N=
_
2
3
_
N(ϕ
b
) −
_
1
6
_
N(ϕ
a
) =
1
2
j
a
γ =
_
2 0
0 2
_
P(b[a) =
_
1 0
0 1
_
P
MO
=
_
1
2
,
1
2
_
j
b
S =
_
1
2
_
S(ϕ
b
) −
_
1
2
_
S(ϕ
a
) =0 I =
_
1
2
_
I(ϕ
b
) −
_
1
2
_
I(ϕ
a
) =0
N=
_
1
2
_
N(ϕ
b
) −
_
1
2
_
N(ϕ
a
) = 0
Scheme 1.3 Decoupling of atomic orbitals in the MO-resolved OCT (2-AO model) with
increasing occupation of the antibonding combination of AO. Panels a and b sum-
marize the bonding and antibonding channels, while Panel c reports the associated
probability/occupation-weighted indices.
Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 25 #25
Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 25
p, p
0
p*
1/3
1/3
1/3
1/4
1/4
1/3
2/3
z
1
z
1
1/2 z
2
z
2
11/36
1/3 2/3
z
3
z
3
11/36
7/18 S = 1.11 I = 0.46 N = 1.58
Scheme 1.4 The molecular information channel of π electrons in allyl and its overall IT
bond indices.
j
2
:
1/2
z
1
z
1
1/2 1/2
1/2
1/2
1/2 1/2 1/2 z
3
z
3
I
2
=0 S
2
=
2
=1
p
2
p
2
P
2
(b|a)
p
1
p
1
1/4 z
1
z
1
1/4 1/4
j
1
:
1/2
1/4
1/4
1/4
1/4
1/4
z
2
z
2
1/2
1/2
1/2
1/2
z
3
z
3
1/4
1/4
S
1
=
1
=3/2 I
1
=0
P
1
(b|a)
Scheme 1.5 The molecular π-electron information systems for two occupied MOs in allyl
(Eq. [33]). The corresponding MO bond indices (in bits) are also reported.
¨
I
1
= −P
1
log
2
P
1
= 0.39;
¨
S
2
= P
2
S
2
=
1
3
,
¨
I
2
= −P
2
log
2
P
2
= 0.53. Such molecular
inputs thus generate the nonvanishing IT ionicities, which sum up to the
group entropy
¨
I =
¨
I
1
÷
¨
I
2
= H[P
MO
] = −

s
P
s
log
2
P
s
= 0.92.
One then observes that the overall index of Scheme 1.4, N = 1.58 = H[p
0
],
predicting about 3/2 π-bond multiplicity in allyl, can be reconstructed by
adding to this additive-ionicity measure, the sum of the bonding (posi-
tive) entropy-covalency
¨
S
1
of the first MO and the antibonding (negative)
contribution (−
¨
S
2
) due to the second MO:
¨
S
1
÷(−
¨
S
2
) ÷
¨
I = N. (35)
One also notices that the population-weighting procedure of Scheme 1.3,
with f
1
= 1 and f
2
= 1/2, gives a diminished bond multiplicity:
¨
N = f
1
P
1
S
1
−f
2
P
2
S
2
÷( f
1
¨
I
1
−f
2
¨
I
2
) = f
1
(
¨
S
1
÷
¨
I
1
) −f
2
(
¨
S
2
÷
¨
I
2
)
≡ f
1
¨
N
1
−f
2
¨
N
2
= 0.96, (36)
thus predicting roughly a single π bond in allyl. The latter result reflects
the fact that only a single-bonding MO, ϕ
1
, is completely occupied, whereas
the antibonding combination ϕ
2
of AO on peripheral carbon atoms remains
practically nonbonding.
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26 Roman F. Nalewajski, Dariusz Szczepanik, and Janusz Mrozek
In the same H¨ uckel approximation the delocalized π bonds in butadiene
are determined by two doubly occupied canonical MOs with P
MO
=
_
1
2
,
1
2
_
and f
MO
=(1, 1),
ϕ
1
= a(z
1
÷z
4
) ÷b(z
2
÷z
3
), ϕ
2
= b(z
1
−z
4
) ÷a(z
2
−z
3
), 2(a
2
÷b
2
) = 1;
a =
1
2
_
1 −
1

5
= 0.3717, b =
1
2
_
1 ÷
1

5
= 0.6015. (37)
The corresponding CBO matrices,
γ
1
=2
_
_
_
_
a
2
ab ab a
2
ab b
2
b
2
ab
ab b
2
b
2
ab
a
2
ab ab a
2
_
¸
¸
_
, γ
2
=2
_
_
_
_
b
2
ab −ab −b
2
ab a
2
−a
2
−ab
−ab −a
2
a
2
ab
−b
2
−ab ab b
2
_
¸
¸
_
,
γ=
1

5
_
_
_
_

5 2 0 −1
2

5 1 0
0 1

5 2
−1 0 2

5
_
¸
¸
_
, (38)
generate the associated AO-information channels as shown in Schemes 1.6
and 1.7.
1/4
1/4
1/4
1/4
1/4
1/4
1/4
1/4
2/5
2/5
2/5
2/5
1/10
1/10
1/10
1/10
1/2
1/2
1/2
1/2
z
1
z
2
z
3
z
4
z
1
z
2
z
3
z
4
S=1.36 I =0.64 =2
Scheme 1.6 The overall π-electron channel in OCT for butadiene derived from the H¨ uckel
MO.
Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 27 #27
Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 27
j
1
:
z
1
a
2
a
2
p(i|1)
b
2
b
2
z
i
z
2
z
3
z
4
p
1
= {p(i[1)] = (a
2
, b
2
, b
2
, a
2
)
a
2
= 0.1382, b
2
= 0.3818
S
1
= N
1
= 1.85, I
1
= 0
j
2
:
z
1
b
2
b
2
p(i|2)
a
2
a
2
z
i
z
2
z
3
z
4
p
2
= {p(i[2)] = (b
2
, a
2
, a
2
, b
2
)
S
2
= N
2
= 1.85, I
2
= 0
Scheme 1.7 Probability scattering in the H¨ uckel π-MO channels of butadiene for the
representative input orbital z
i
= 2p
z,i
and the associated MO entropies.
The overall data correctly predict the resultant double multiplicity of
all π bonds in butadiene. In the one-electron OCT treatment, they exhibit
rather substantial IT ionicity [48], which indicates a high degree of deter-
minism (localization) in the orbital probability scattering, compared with the
previous two-electron approach [9]. A reference to the preceding equation
indicates that a half of the reported entropy for ϕ
2
is associated with the
antibonding interactions between AOs, as reflected by the negative values of
the corresponding elements in the MO CBO matrix. Therefore, the bonding
and antibonding components in S
2
cancel each other, when one attributes
different signs to these AO contributions. The group ionicity
¨
I =
¨
I
1
÷
¨
I
2
=
H[P
MO
] = 1 and hence Eq. (35) nowreads
¨
S
1
÷
_
1
2
¨
S
2

1
2
¨
S
2
_
÷
¨
I = 1.925, where
¨
S
s
= P
s
S
s
, thus again predicting roughly two π bonds in the system.
In the H¨ uckel theory the three occupied MO, which determine the π bonds
in benzene, P
MO
=
1
3
1, where 1 stands for the unit row matrix, read
ϕ
1
=
1

6
(z
1
÷z
2
÷z
3
÷z
4
÷z
5
÷z
6
),
ϕ
2
=
1
2
(z
1
÷z
2
−z
4
−z
5
),
ϕ
3
=
1

12
(z
1
−z
2
−2z
3
−z
4
÷z
5
÷2z
6
). (39)
They give rise to the overall CBO matrix elements reflecting the π-electron
population on orbital χ
i
= z
i
, γ
i,i
= z
1
, γ
i,i
= 1, and the chemical coupling
between χ
i
and its counterparts on carbon atoms in the relative ortho-, meta-,
and para-positions, respectively, γ
i,i÷1
= 2/3, γ
i,i÷2
= 0, γ
i,i÷3
= −1/3. The resul-
tant scattering of AO probabilities for the π electrons in benzene is shown in
Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 28 #28
28 Roman F. Nalewajski, Dariusz Szczepanik, and Janusz Mrozek
z
i
1/2
2/9
z
i +1
1/6
z
i
0
z
i +2
1/18
z
i +3
S = 1.70 I
2
= 0.89 N = 2.58
Scheme 1.8 The probability scattering in benzene (H¨ uckel theory) for the representative
input orbital z
i
=2p
z,i
and the associated OCT entropy/information descriptors.
Scheme 1.8. The overall bond multiplicity is somewhat lower that N = 3 pre-
dicted for the three localized π bonds in cyclohexatriene since in benzene, the
π-bond alternation is prevented by the stronger σ bonds, which assume the
maximum strength in the regular hexagon structure [64–67].
All matrix elements in γ
1
=2¸χ[
ˆ
P
1
[χ) =(
1
3
)1, where χ =(z
1
, z
2
, z
3
, z
4
, z
5
, z
6
)
and all elements in the square matrix 1 are equal to 1, are positive (bonding),
whereas half of themin γ
2
and γ
3
is negative, thus representing the antibond-
ing interactions between AOs. The nonvanishing elements in γ
2
are limited
to the subset χ
/
= (z
1
, z
2
, z
4
, z
5
):
γ
2
=2¸χ

[
ˆ
P
2

/
) =
1
2
_
_
_
_
1 1 −1 −1
1 1 −1 −1
−1 −1 1 1
−1 −1 1 1
_
¸
¸
_
, (40)
while γ
3
explores the whole basis set χ:
γ
3
= 2 ¸χ[
ˆ
P
3
[χ) =
1
6
_
_
_
_
_
_
_
_
1 −1 −2 −1 1 2
−1 1 2 1 −1 −2
−2 2 4 2 −2 −4
−1 1 2 1 −1 −2
1 −1 −2 −1 1 2
2 −2 −4 −2 2 4
_
¸
¸
¸
¸
¸
¸
_
. (41)
These CBO matrices of the occupied MO give rise to the following
communications and input probabilities in the associated MO channels:
P
1
(b[a) =
1
6
1, p
1
=
1
6
1; P
2
(b[a) =
1
4
_
_
_
_
_
_
_
_
1 1 0 1 1 0
1 1 0 1 1 0
0 0 0 0 0 0
1 1 0 1 1 0
1 1 0 1 1 0
0 0 0 0 0 0
_
¸
¸
¸
¸
¸
¸
_
,
Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 29 #29
Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 29
p
2
=
1
4
(1, 1, 0, 1, 1, 0); P
3
(b[a) =
1
12
_
_
_
_
_
_
_
_
1 1 4 1 1 4
1 1 4 1 1 4
1 1 4 1 1 4
1 1 4 1 1 4
1 1 4 1 1 4
1 1 4 1 1 4
_
¸
¸
¸
¸
¸
¸
_
,
p
3
=
1
12
(1, 1, 4, 1, 1, 4). (42)
The corresponding entropy/information descriptors then read as follows:
S
1
= N
1
= 2.58, I
1
= 0; S
2
= N
2
= 2, I
2
= 0; S
3
= N
3
= 2.25, I
3
= 0. (43)
The group ionicity
¨
I =
¨
I
1
÷
¨
I
2
÷
¨
I
3
= H[P
MO
] = 1.58 and
¨
S
1
= S
1
/3 then also
gives rise to roughly (2.5)-bond multiplicity, with the bonding (positive) and
antibonding (negative) contributions in
¨
S
2
and
¨
S
3
approximately canceling
each other.
6. BOND DIFFERENTIATION IN OCT
It has been demonstrated elsewhere that the bond alternation effects are
poorly represented in both the CTCB formulated in atomic resolution [9]
and in its OCT (fixed-input) extension [48]. The OCT indices from the alter-
native output reduction schemes have been shown to give more realistic
but still far from satisfactory description of the bond alternation trends in
these molecular systems [48]. This is because in purely probabilistic models,
the bonding and antibonding interactions are not distinguished since con-
ditional probabilities (squares of the MO-CBO matrix elements) loose the
information about the relative phases of AOin MO. However, this distinction
is retained in the off-diagonal CBO matrix elements, particularly in the sepa-
rate CBO contributions {γ
s
] from each occupied MO. Since the OCT analysis
of the bonding patterns in molecules provides the supplementary, a posteriori
description to the standard MOscheme in this section we shall attempt to use
this extra information, directly available from the standard SCF MO calcula-
tions, to generate more realistic “chemical” trends of the π-bond alternation
patterns in the three illustrative systems of the preceding section.
The problem can be best illustrated using the simplest allyl case. As dis-
cussed elsewhere [9, 22], the entropy/information indices for the given pair
of atomic orbitals can be extracted from the relevant partial channel, which
includes all AO inputs (sources of the system chemical bonds) and the two-
orbital outputs in question, defining the localized chemical interaction of
interest. In Scheme 1.9, two examples of such partial information systems are
Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 30 #30
30 Roman F. Nalewajski, Dariusz Szczepanik, and Janusz Mrozek
1/3
1/3
(a)
1/3
1/3
2/3
1/2
11/36
7/18
z
1
z
2
z
1
z
2
z
3
1/4
1/3
1/4
1/4
11/36
11/36
2/3
2/3
1/3
1/3
1/3
z
1
z
2
z
3
z
1
z
3
(b)
S(1, 2) = 0.82 I(1, 2) = 0.24 N(1, 2) = 1.05
S(1, 3) = 0.59 I(1, 3) = 0.45 N(1, 3) = 1.05
Scheme 1.9 The molecular partial information channels and their entropy/information
descriptors of the chemical interaction between the adjacent (Panel a) and terminal (Panel b)
AO in the π-electron system of allyl.
displayed for the nearest neighbor (z
1
, z
2
) and terminal (z
1
, z
3
) chemical inter-
actions. They have been obtained from the molecular channel of Scheme 1.4,
by removing communications involving the third, remaining AOof this min-
imum basis set of π AO. It follows from these illustrative sets of indices that
the two partial channels give rise to identical overall index N, with only
the IT-covalent/ionic components differentiating the two bonds: the nearest
neighbor interaction exhibits a higher “noise” (covalency) component and
hence the lower information-flow (ionicity) content. In the H¨ uckel theory
the corresponding partial information systems in the butadiene π-electron
system predict identical indices for all pairs of orbitals, S(i, j) = 0.68, I(i, j) =
0.25, and N(i, j) = 0.93, thus failing completely to account for the π-bond
alternation.
To remedy this shortcoming of the communication theory, one has to
bring into play the known signs of interactions between the specified pair
(i, j) of AO in the given MO ϕ
s
, in order to recognize them as bonding
(exhibiting a “constructive” interference), γ
i, j
(s) > 0, or antibonding (involv-
ing a “destructive” interference), γ
i, j
(s) < 0, with γ
i, j
(s) = 0 corresponding
to the nonbonding (zero communication) case. The MO-resolved channels
are vital for the success of such an approach since the bonding interaction
between the given pair of AOs in one MO can be accompanied by the anti-
bonding interaction between these basis functions in another occupied MO.
This extraneous information determines the signs of contributions in the
weighted contributions of Eqs. (31 and 32) from the partial MO channels,
including the two specified orbitals in their input and output, and using
the fragment-renormalized MO probabilities [9, 26]. It should be observed
that in the flexible-input approach of Section 4 the nonbonding AOs, which
Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 31 #31
Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 31
1/3 1/4 1/4
1/2
1/4
z
1
z
1
2/3 1/2 1/2 z
2
z
2
(a) z
1
–z
2
:
ϕ
1
: γ
1, 2

1
) > 0
S
1,2

1
) = 1 I
1,2

1
) = 0 N
1,2

1
) = 1
S(1, 2) = 2/3 I(1, 2) = 0 N(1, 2) = 2/3
1/2
1/2
1/2
1/4
1/4
1/4
1/4
1/2
1/2
1/2
1/4
1/4
1/4
z
3
z
3
z
1
z
1
z
1
z
1
1/2 1/2 1/2
z
3
z
3
(b) z
1
–z
3
:
ϕ
1
: γ
1, 3

1
) > 0
S
1,3

1
) = 1 I
1,3

1
) = 1 N
1,3

1
) = 1
ϕ
2
: γ
1, 3

2
) < 0
S
1,3

2
) = 1 I
1,3

2
) = 0 N
1,3

2
) = 1
S(1, 3) = 2/3 −1/6 = 1/2 I(1, 3) = 0 N(1, 3) = 1/2
Scheme 1.10 The partial MO-information channels and their entropy/information descrip-
tors of the chemical interactions between the nearest neighbor (Panel a) and terminal
(Panel b) AO in the π-electron system of allyl.
communicate only with themselves, gives rise to the separate AO channels
of Scheme 1.1b, thus not contributing to the resultant bond descriptors.
An illustrative application of such scheme to π electrons in allyl, for
which P
MO
=
_
2
3
,
1
3
_
, f
MO
=
_
1,
1
2
_
, p
1
=
_
1
4
,
1
2
,
1
4
_
, and p
2
=
_
1
2
, 0,
1
2
_
, is reported
in Scheme 1.10. One observes that z
1
–z
2
interaction has only the bonding con-
tribution from ϕ
1
, while the effective z
1
–z
3
interaction combines the bonding
contribution due to ϕ
1
and the antibonding increment originating from ϕ
2
.
This scheme is seen to generate (2/3)-bond multiplicity between the near-
est neighbors and a weaker half-bond between the terminal carbon atoms.
This somewhat contradicts the Wiberg’s covalency indices predicting a half
z
1
–z
2
bond and a vanishing z
1
–z
3
interaction. The reason for a finite value of
this bond index in OCT is the dominating delocalization of electrons in ϕ
1
throughout the whole π system.
Let us similarly examine the localized π interactions in butadiene, for
which P
MO
=
_
1
2
,
1
2
_
, f
MO
= (1, 1), p
1
= (a
2
, b
2
, b
2
, a
2
), and p
2
= (b
2
, a
2
, a
2
, b
2
). A
reference to Eq. (38) indicates that the equivalent terminal pairs of AO,
z
1
–z
2
and z
3
–z
4
, exhibit only the bonding interactions in ϕ
1
and ϕ
2
, while
the remaining AO combinations involve the bonding contribution from ϕ
1
and the antibonding from ϕ
2
. These MO increments are summarized in
Scheme 1.11 (see also Scheme 1.7).
These diatomic IT indices predict the strongest terminal (1–2) or (3–4) π
bonds, which exhibit somewhat diminished bond multiplicity to about 92%
Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 32 #32
32 Roman F. Nalewajski, Dariusz Szczepanik, and Janusz Mrozek
of the unit value in ethylene, and the vanishing bond orders of the (1–3)
and (2–4) interactions. The middle (2–3) π bond measures about 14% of the
ethylene reference value, while the chemical interaction between terminal
carbons (1–4) is diagnosed as being antibonding in character, in full confor-
mity with the negative value of the corresponding off-diagonal element in
the overall CBO matrix (Eq. [38]). These predictions should be compared
with the associated quadratic indices M
i, j

2
i, j
of Wiberg, M
1,2
=M
3,4
=0.8,
M
1,3
=M
2,4
=0, and M
1,4
=M
2,3
=0.2, which unrealistically equates the partial
bonding (2–3) and antibonding (1–4) interactions.
As final example let us reexamine from the present perspective a differ-
entiation of the localized π-bonds between the two carbon atoms in the
relative ortho-, meta- and para-positions in benzene [9, 48]. This weighted
MO approach makes a separate use of the diatomic parts of the canonical
MO channels, with the bonding and antibonding contributions identified by
the signs of the corresponding coupling elements in the MO density matri-
ces {γ
s
]. It should be realized that while the canonical (delocalized) MO
completely reflect the molecular symmetry, its diatomic fragments do not.
Therefore, the bond indices generated in this scheme must exhibit some dis-
persions so that they have to be appropriately averaged with respect to the
admissible choices of the corresponding orbital pairs to ultimately generate
the invariant entropy/information descriptors of the ortho-, meta-, and para
π bonds in benzene. We further observe that in this π system, P
MO
=
_
1
3
,
1
3
,
1
3
_
and f
MO
= (1, 1, 1).
Scheme 1.12 summarizes the elementary entropy/information increments
of the diatomic bond indices generated by the MO channels of Eq. (42). They
give rise to the corresponding diatomic descriptors, which are obtained from
Eq. (32). For example, by selecting i =1 of the diatomic fragment consisting
additionally the j =2, 3, 4 carbon, one finds the following IT bond indices:
S(1, 2) =N(1, 2) =0.42, S(1, 3) =N(1, 3) =0.01,
S(1, 4) =N(1, 4) = −0.25.
These predictions correctly identify the bonding, a practically nonbonding,
and the antibonding characters of π bonds between two carbons of the ben-
zene ring in the relative ortho-, meta-, and para-positions, respectively, as
indeed reflected by the overall CBO matrix elements. However, due to a
nonsymmetrical (fragment) use of the symmetrical MO channels, these pre-
dictions exhibit some dispersions when one explores other pairs of carbon
atoms in the ring, giving rise to the following average descriptors:
S(ortho) =N(ortho) =0.52, S(meta) =N(meta) =0.06,
S(para) =N(para) = −0.19.
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Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 33
2a
2
2b
2
2b
2
2a
2
z
1
z
1
z
2(3)
z
2(3)
z
1
z
1
z
2(3)
z
2(3)
(a) z
1
–z
2
, z
1
–z
3
:
b
2
b
2
b
2
b
2
a
2
a
2
a
2
b
2
b
2
a
2
a
2
a
2
ϕ
1
: γ
1,2

1
) > 0, γ
1,3

1
) > 0
S
1,2

1
) = N
1,2

1
) = 0.925 I
1,2

1
) = 0
S
1,3

1
) = N
1,3

1
) = 0.925 I
1,3

1
) = 0
ϕ
2
: γ
1,2

2
) > 0, γ
1,3

2
) < 0
S
1,2

2
) = N
1,2

2
) = 0.925 I
1,2

2
) = 0
S
1,3

2
) = N
1,3

2
) = 0.925 I
1,3

2
) = 0
S(1, 2) =N(1, 2) =0.925, I(1, 2) = 0 S(1, 3) = N(1, 3) = 0, I(1, 3) = 0;
1/2
1/2
1/2
1/2
z
1
z
1
z
4
z
4
z
1
z
1
z
4
z
4
(b) z
1
–z
4
:
a
2
a
2
b
2
b
2
a
2
a
2
b
2
a
2
b
2
a
2
b
2
b
2
ϕ
1
: γ
1, 4

1
) > 0
S
1,4

1
) = N
1,2

1
) = 0.789 I
1,4

1
) = 0
ϕ
2
: γ
1, 4

2
) < 0
S
1,4

2
) = N
1,4

2
) = 1.061 I
1,4

2
) = 0
S(1, 4) = N(1, 4) = −0.136, I(1, 2) = 0
1/2
1/2
1/2
1/2
z
2
z
2
z
3
z
3
z
2
z
2
z
3
z
3
(c) z
2
–z
3
:
b
2
b
2
a
2
a
2
b
2
b
2
a
2
b
2
a
2
b
2
a
2
a
2
ϕ
1
: γ
2, 3

1
) > 0
S
2,3

1
) = N
2,3

1
) = 1.061 I
2,3

1
) = 0
ϕ
2
: γ
2, 3

2
) < 0
S
2,3

2
) = N
2,3

2
) = 0.789 I
2,3

2
) = 0
S(2, 3) = N(2, 3) = 0.136, I(2, 3) = 0
Scheme 1.11 The partial MO-information channels and their entropy/information descrip-
tors for the two-orbital interactions in the π-electron system of butadiene.
The above ortho result shows that the overall IT bond multiplicity between
the nearest neighbors N(ortho) ∼ 0.5 is indeed compromised in benzene,
compared with N =1 in ethylene, due to the effect of the prohibited bond
alternation, enforced by the stronger σ bonds [64–67]. Again, the magnitudes
of these IT indices generally agree with the corresponding Wiberg indices:
M
ortho
=0.44, M
meta
=0, and M
para
=0.11. Note, however, that OCT properly
recognizes the para interactions in benzene as antibonding, whereas in the
Wiberg scheme, this distinction is lost.
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34 Roman F. Nalewajski, Dariusz Szczepanik, and Janusz Mrozek
z
i
z
i
1/6
1/6
1/6
1/6
1/6 1/2
z
j
z
j
1/6 1/2
(z
i
≠z
j
) ∈(z
1
,

z
2
, z
3
, z
4
, z
5
, z
6
)
(a) j
1
:
γ
i, j

1
) > 0
S
i, j

1
) = N
i, j

1
) = 0.862 I
i, j

1
) = 0
z
i
z
i
1/4
1/4
1/4
1/4
1/4
1/2
z
j
z
j
1/4
1/2
(z
i
≠z
j
) ∈(z
1
,

z
2
, z
4
, z
5
)
(b) j
2
:
γ
1, 2

2
) = γ
4,5

2
) > 0
γ
1,4

2
) = γ
1,5

2
) = γ
2,4

2
) = γ
2,5

2
) < 0
S
i, j

2
) = N
i, j

2
) = 1 I
i, j

2
) = 0
z
3
z
3
1/3
1/3
1/3
1/3
1/3 1/2
z
6
z
6
1/3 1/2
(z
i
≠z
j
) ∈(z
3
,

z
6
)
(c) j
3
:
z
i
z
i
1/12
1/12
1/12
1/12
1/12 1/2
z
j
z
j
1/12 1/2
(z
i
≠z
j
) ∈(z
1
,

z
2
, z
3
, z
4
, z
5
)
z
i
z
i
1/12
1/3
1/12
1/3
1/12 1/5
z
j
z
j
1/3 4/5
z
i
∈(z
3
,

z
6
), z
j
∈(z
1
,

z
2
, z
4
, z
5
)
γ
3,6

3
) < 0
S
3,6

3
) = N
3,6

3
) = 1.057 I
3,6

3
) = 0
γ
1,2

3
) = γ
1,4

3
) = γ
2,5

3
) = γ
4,5

3
) < 0
γ
1,5

3
) = γ
2,4

3
) > 0
S
i, j

3
) = N
i, j

3
) = 0.597 I
i,j

3
) = 0
γ
1,3

3
) = γ
2,6

3
) = γ
3,5

3
) = γ
4,6

3
) < 0
γ
1,6

3
) = γ
2,3

3
) = γ
3,4

3
) = γ
5,6

3
) > 0
S
i, j

3
) = N
i, j
ϕ
3
) = 0.827 I
i, j

3
) = 0
Scheme 1.12 The elementary entropy/information contributions to chemical interactions
between two different AOs in the minimum basis set {z
i
= 2p
z,i
] of the π-electron system in
benzene.
7. LOCALIZED σ BONDS IN COORDINATION COMPOUNDS
The decoupled description of hydrides (Section 3) can be naturally extended
into the localized σ bonds between the central atom/ion X and the coordi-
nated ligands {L
α
], for example, in the coordination compounds of transition
metal ions or in SF
6
. Consider, for example, the octahedral complex XL
6
with
the ligands placed along the axes of the Cartesian coordinate system: {L
1
(e),
L
2
(e)], e =x, y, z. The X–L
α
bond then results from the chemical interaction
Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 35 #35
Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 35
between six acceptor (partially occupied) d
2
sp
3
hybrids {H
α
] of X and the
corresponding donor (doubly occupied) {σ
α
] orbitals of ligands. The corre-
sponding localized MO, which determines the communication channel of
the separate bond M–L
α
, α =1, 2, . . . , 6, now include the (doubly occupied)
bonding MO ϕ
b
(α), with the two electrons originating from the donor σ
α
orbital, n
b
=N
σ
(α) =2, and the antibonding MOϕ
a
(α), in general partly occu-
pied with n
a
=N
X
(α) electrons originating from X, which result from the two
basis functions χ
α
=(H
α
, σ
α
):
ϕ
b
(α) =

PH
α
÷
_

α
, ϕ
a
(α) = −
_
QH
α
÷


α
, P ÷Q=1. (44)
The associated CBO matrix elements and the corresponding conditional
probabilities they generate now depend on the initial number of electrons n
a
on H
α
, which are contributed by X to the αth σ bond (see also Scheme 1.3),
γ
H
α
,H
α
=2P ÷n
a
Q, γ
σ
α

α
=2Q÷n
a
P, γ
H
α

α

σ
α
,H
α
=(2 −n
a
)
_
PQ. (45)
Indeed, n
a
=0, for example, in SF
6
, determines the maximum value of the
magnitude of the coupling CBO element γ
H
α
, σ
α

σ
α
, H
α
=2
_
PQ, and n
a
=1
diminishes it by a factor of 2, while the double occupation of ϕ
a
(α) gives
rise to the nonbonding state corresponding to the separate, decoupled
subchannels for each orbital,
γ
H
α
,H
α

σ
α

α
=2 and γ
H
α

α

σ
α
,H
α
=0, (46)
which do not contribute to the entropy/information indices of the localized
chemical bond.
For n
a
=0, that is, the empty antibonding MO, when X–L
α
channel is
given by Scheme 1.1a, the IT bond indices correctly predict the overall IT
multiplicity reflecting the six decoupled bonds in this molecular system:
S(P) =

α
S
α
(b
α
[a
α
) =6H(P),
I(P) =

α
I
α
(a
0
α
: b
α
) =6[1 −H(P)], N=6. (47)
The highest IT covalency of the σ bond M–L
α
, S
max.
=1, predicted for
the strongest mixing of orbitals P=Q=1/2, is thus accompanied by the
vanishing IT ionicity, I
max.
=0.
The corresponding conditional probabilities P
α
(b
α
[a
α
) ≡ P
α

α

α
] for the
single and double occupations of ϕ
a
(α) are reported in the corresponding dia-
grams of Scheme 1.3c. It follows from these expressions that in the latter case
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36 Roman F. Nalewajski, Dariusz Szczepanik, and Janusz Mrozek
0.9 H H
(a)
(b)
0.1
σ σ
1
2
0.1
0.9
1
2
1
2
1
2
0.9 H H
0.1
σ σ
1
3
0.1
0.9
2
3
11/30
19/30
P(b|a) p p
P(b|a) p

p
0
S
max.
=0.469
I
max.
=0.479
N
max.
=0.948
Scheme 1.13 The orbital-communication channels for the localized M–L
α
bond in the
fixed-input approach, for P =Q=1/2, and the singly occupied antibonding MO: covalent
(molecular input; Panel a) and ionic (promolecular input; Panel b).
the off-diagonal elements identically vanish, γ
H
α

α

σ
α
,H
α
=0, thus giving
rise to the decoupled pair of orbitals and hence to the deterministic chan-
nel of Scheme 1.1b for each of them (see the fourth diagram in Scheme 1.3c).
Therefore, such separate channels do not contribute to the overall IT bond
descriptors.
For the partly bonding, open-shell configuration n
a
=1 (the third dia-
gram in Scheme 1.3c) and the maximum covalency combination P=Q=1/2,
one obtains a strongly deterministic information system as shown in
Scheme 1.13. It follows from these diagrams that the fixed-input approach
predicts a practically conserved overall bond order compared with the n
a
=0
case (the second diagram in Scheme 1.3c), with the bond weakening being
reflected only in the bond composition with now roughly equal (half-bond)
covalent and ionic components.
As already discussed in Scheme 1.3, the populational decoupling trends of
AO in the coordination bond are properly reflected only in the flexible-input
(MO-resolved) description, which recognizes the bonding and antibonding
contributions to the resultant bond multiplicity from the signs of the cor-
responding CBO matrix elements of the system-occupied MO. It should be
emphasized, however, that such treatment ceases to be purely probabilistic
in character since it uses the extraneous piece of the CBO information, which
is lost in the conditional probabilities.
8. RESTRICTED HARTREE–FOCK CALCULATIONS
In typical SCF-LCAO-MO calculations the lone pairs of the valence and/or
inner shell electrons can strongly affect the IT descriptors of the chemi-
cal bond. Therefore, the contributions due to each AO input should be
Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 37 #37
Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 37
appropriately weighted (see Eqs. [28 and 29] in Section 4) using the joint,
two-orbital probabilities that reflect the actual participation of each AO in
the system chemical bonds. In this section we describe such an approach to
diatomic chemical interactions in molecules and present numerical results
from standard RHF calculations for a selection of representative molecular
systems.
8.1. Orbital and condensed atom probabilities of
diatomic fragments in molecules
The molecular probability scattering in the specified diatomic fragment
(A, B), involving AO contributed by these two bonded atoms, χ
AB
=(χ
A
, χ
B
),
to the overall basis set χ ={χ
X
], is completely characterized by the corre-
sponding P(χ
AB

AB
) block [22, 26] of the molecular conditional probability
matrix of Eq. (4), which determines the molecular communication system in
OCT [46–48] of the chemical bond:
P(χ
AB

AB
) ≡ [P(χ
Y

X
); (X, Y) ∈(A, B)]
≡ {P(j[χ
AB
); χ
j
∈χ
AB
] ≡ {P(j[i); (χ
i
, χ
j
) ∈χ
AB
)]. (48)
Thus, the square matrix P(χ
AB

AB
) contains only the intrafragment commu-
nications, which miss the probability propagations originating from AO of
the remaining constituent atoms χ
Z
/ ∈χ
AB
.
The atomic output reduction of P(χ
AB

AB
) [9] gives the associated con-
densed conditional probabilities of the associated molecular information
system,
P(X
AB

AB
) =[P(A[χ
AB
), P(B[χ
AB
)]
=
_
P(X[χ
AB
) ≡ {P(X[i)]=

j∈X
P(j
¸
¸
χ
AB
); χ
i
∈ χ
AB
, X=A, B
_
, (49)
where P(Y[i) measures the conditional probability that an electron on χ
i
will
be found on atom Y in the molecule. The sum of these conditional prob-
abilities over all AOs contributed by the two atoms then determines the
communication connections {P(A, B[i)], linking the condensed atomic output
(A, B) and the given AO input χ
i
in the associated communication system of
the diatomic fragment:
P(A[χ
AB
) ÷P(B[χ
AB
) =P(A, B[χ
AB
)
=
_
P(A,B[i) =P(A[i) ÷P(B[i) =

j∈(A,B)
P( j
¸
¸
i) ≤ 1
_
. (50)
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38 Roman F. Nalewajski, Dariusz Szczepanik, and Janusz Mrozek
In other words, P(A,B[i) measures the probability that the electron occu-
pying χ
i
will be detected in the diatomic fragment AB of the molecule.
The inequality in the preceding equation reflects the fact that the atomic
basis functions participate in chemical bonds with all constituent atoms,
with the equality sign corresponding only to a diatomic molecule,
when χ
AB
=χ.
The fragment-normalized AO probabilities
˜ p(AB) ={˜ p
i
(AB) =γ
i,i
/N
AB
], N
AB
=

i∈(A,B)
γ
i,i
,

i∈(A,B)
˜ p
i
(AB) =1, (51)
where N
AB
stands for the number of electrons in the specified diatomic frag-
ment of the molecule and ˜ p
i
(AB) denotes the probability that one of them
occupies χ
i∈(A,B)
, then determine the simultaneous probabilities of the joint
two-orbital events [47]:
P
AB

AB
, χ
AB
) ={P
AB
(i, j) = ˜ p
i
(AB)P(j[i) =γ
i,j
γ
j,i
/(2N
AB
)]. (52)
They generate, via relevant partial summations, the joint atom-orbital prob-
abilities in AB, {P
AB
(X, i)]:
P
AB
(X
AB
, χ
AB
) =[P
AB
(A, χ
AB
), P
AB
(B, χ
AB
)]
=
_
P
AB
(X, i) =

j∈X
P
AB
(i, j) ≡ ˜ p
i
(AB)P(X[i), X=A, B
_
. (53)
For the closed-shell molecular systems one thus finds
P
AB
(X, χ
AB
) =
_
P
AB
(X, i) = ˜ p
i
(AB)

j∈X
P( j
¸
¸
i) =

j∈X
γ
i,j
γ
j,i
2N
AB
_
, X=A, B. (54)
These vectors of AO probabilities in diatomic fragment AB subsequently
define the condensed probabilities {P
X
(AB)] of both bonded atoms in sub-
system AB:
P
X
(AB) =
N
X
(AB)
N
AB
=

i∈(A,B)
P
AB
(X, i) =

i∈(A,B)

j∈X
γ
i,j
γ
j,i
2N
AB
, X=A, B, (55)
where the effective number of electrons N
X
(AB) on atom X=A, B reads:
N
X
(AB) =

i∈(A,B)

j∈X
γ
i,j
γ
j,i
2
. (56)
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Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 39
Therefore, in diatomic molecules, for which χ
AB
=χ, one finds using the
idempotency relations of Eq. (3),
P
X
(AB) =

j∈X
_

i
γ
j,i
γ
i,j
2N
AB
_
=

j∈X
γ
j,j
N
AB
=

j∈X
˜ p
j
(AB), X=A, B, (57)
and hence P
A
(AB) ÷P
B
(AB) =1. Clearly, the last relation does not hold for
diatomic fragments in larger molecular systems, when χ
AB
,= χ, so that in
general P
X
(AB) ,=

j∈X
˜ p
j
and
P
A
(AB) ÷P
B
(AB) ,= 1. (58)
We finally observe that the effective orbital probabilities of Eqs. (52–54)
and the associated condensed probabilities of bonded atoms (Eq. 55) do not
reflect the actual AO participation in all chemical bonds in AB, giving rise
to comparable values for the bonding and nonbonding (lone-pair) AO in the
valence and inner shells. The relative importance of basis functions of one
atom in forming the chemical bonds with the other atom of the specified
diatomic fragment is reflected by the (nonnormalized) joint bond probabilities
of the two atoms, defined by the diatomic components of the simultaneous
probabilities of Eqs. (52 and 53):
P
b
(A, B) ≡

i∈B
P
AB
(A, i) =

i∈A
P
AB
(B, i) =P
b
(B,A) =

i∈A

j∈B
γ
i,j
γ
j,i
2N
AB
. (59)
The underlying joint atom-orbital probabilities, {P
AB
(A, i), i ∈ B] and
{P
AB
(B, i), i ∈ A], to be used as weighting factors in the average conditional-
entropy (covalency) and mutual-information (ionicity) descriptors of the AB
chemical bond(s), indeed assume appreciable magnitudes only when the
electron occupying the atomic orbital χ
i
of one atom is simultaneously found
with a significant probability on the other atom, thus effectively excluding
the contributions to the entropy/information bond descriptors due to the
lone-pair electrons. Thus, such joint bond probabilities emphasize of AOs
have both atoms are simultaneously involved in the occupied MOs.
The reference bonding probabilities of AO have to be normalized to the
corresponding sums P(A, B[χ
AB
) ={P(A, B[i)] of Eq. (50). Since the bond
probability concept of Eq. (59) involves symmetrically the two bonded
atoms, we apply the same principle to determine the associated reference
bond probabilities of AO to be used to calculate the mutual-information
bond index:
{p
b
(i) =P(A, B[i)/2; i ∈ (A, B)], (60)
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40 Roman F. Nalewajski, Dariusz Szczepanik, and Janusz Mrozek
where P(A,B[i) denotes the probability that an electron originating from
orbital χ
i
will be found on atom A or B in the molecule.
8.2. Average entropic descriptors of diatomic
chemical interactions
As we have already mentioned in Section 2, in OCT the complementary
quantities characterizing the average noise (conditional entropy of the chan-
nel output given input) and the information flow (mutual information in the
channel output and input) in the diatomic communication systemdefined by
the conditional AO probabilities of Eq. (48) provide the overall descriptors of
the fragment bond covalency and ionicity, respectively. Both molecular and
promolecular reference (input) probability distributions have been used in
the past to determine the information index characterizing the displacement
(ionicity) aspect of the system chemical bonds [9, 46–48].
In the A–B fragment development we similarly define the following
average contributions of both constituent atoms to the diatomic covalency
(delocalization) entropy:
H
AB
(B[χ
A
) =

i∈A
P
AB
(B, i) H(χ
AB
[i), H
AB
(A[χ
B
) =

i∈B
P
AB
(A, i) H(χ
AB
[i),
(61)
where the Shannon entropy of the conditional probabilities for the given AO
input χ
i
∈ χ
AB
=(χ
A
, χ
B
) in the diatomic channel:
H(χ
AB
[i) = −

j∈(A,B)
P(j[i)log
2
P(j[i). (62)
In Eq. (61) the conditional entropy S
AB
(Y[χ
X
) quantifies (in bits) the delocal-
ization X→Y per electron so that the total covalency in the diatomic fragment
A–B reads as follows:
S
AB
=N
AB
[H
AB
(B[χ
A
) ÷H
AB
(A[χ
B
)]. (63)
Again, it should be emphasized that the simultaneous (diatomic) proba-
bilities {P
AB
(X, i ∈ Y), Y ,= X], used in Eq. (61) as weighting factors of the
corresponding contributions due to the specified input AO, effectively elim-
inate contributions due to the inner- and valence-shell lone pairs, since
these weighting factors reflect the actual orbital participation in the fragment
chemical bonds.
Accordingly, the probability-weighted contributions to the average
mutual-information quantities of bonded atoms are defined in reference to
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Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 41
the unbiased bond probabilities of AO (Eq. [60]):
I
AB

A
: B) =

i∈A
P
AB
(B, i)I(χ
AB
: i), I
AB

B
: A) =

i∈B
P
AB
(A, i)I(χ
AB
: i),
I(χ
AB
: i) =

j∈(A,B)
P(j[i)log
2
_
P(j[i)
p
b
(i)
_
. (64)
They generate the total information ionicity of all chemical bonds in the
diatomic fragment:
I
AB
=N
AB
[I
AB

A
: B) ÷I
AB

B
: A)]. (65)
Finally, the sum of the above total (diatomic) entropy-covalency and
information-ionicity indices determines the overall information-theoretic
bond multiplicity in the molecular fragment in question:
N
AB
=S
AB
÷ I
AB
. (66)
They can be compared with the diatomic (covalent) bond order of Wiberg
[52] formulated in the standard SCF-LCAO-MO theory,
M
AB
=

i∈A

j∈B
γ
2
i,j
=

i∈A

j∈B
M
i,j
, (67)
which has been previously shown to adequately reflect the chemical intu-
ition in the ground state of typical molecular systems. Such a comparison is
performed in Tables 1.1 and 1.2, reporting the numerical RHF data of bond
orders in diatomic fragments of representative molecules for their equilib-
rium geometries in the minimum (STO-3G) and extended (6-31G*) basis sets,
respectively.
It follows from both these tables that the applied weighting procedure
gives rise to an excellent agreement with both the Wiberg bond orders
and the chemical intuition. A comparison between corresponding entries
in Table 1.1 and the upper part of Table 1.2 also reveals generally weak
dependence on the adopted AO representation, with the extended basis set
predictions being slightly closer to the familiar chemical estimates of the
localized bond multiplicities in these typical molecules. In a series of related
compounds, for example, in hydrides or halides, the trends exhibited by the
entropic covalent and ionic components of a roughly conserved overall bond
order also agree with intuitive expectations. For example, the single chemical
bond between two “hard” atoms in HF appears predominantly covalent,
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42 Roman F. Nalewajski, Dariusz Szczepanik, and Janusz Mrozek
Table 1.1 Comparison of the diatomic Wiberg and entropy/information bond
multiplicity descriptors in selected molecules: the RHF results obtained in the
minimum (STO-3G) basis set
Molecule A–B M
AB
N
AB
S
AB
I
AB
H
2
H–H 1.000 1.000 1.000 0.000
F
2
F–F 1.000 1.000 0.947 0.053
HF H–F 0.980 0.980 0.887 0.093
LiH Li–H 1.000 1.000 0.997 0.003
LiF Li–F 1.592 1.592 0.973 0.619
CO C–O 2.605 2.605 2.094 0.511
H
2
O O–H 0.986 1.009 0.859 0.151
AlF
3
Al–F 1.071 1.093 0.781 0.311
CH
4
C–H 0.998 1.025 0.934 0.091
C
2
H
6
C–C 1.023 1.069 0.998 0.071
C–H 0.991 1.018 0.939 0.079
C
2
H
4
C–C 2.028 2.086 1.999 0.087
C–H 0.984 1.013 0.947 0.066
C
2
H
2
C–C 3.003 3.063 2.980 0.062
C–H 0.991 1.021 0.976 0.045
C
6
H
1
6
C
1
–C
2
1.444 1.526 1.412 0.144
C
1
–C
3
0.000 0.000 0.000 0.000
C
1
–C
4
0.116 0.119 0.084 0.035
1
For the sequential numbering of carbon atoms in the benzene ring.
although a substantial ionicity is detected for LiF, for which both Wiberg and
information-theoretic results predict roughly (3/2)-bond in the minimum
basis set, consisting of approximately one covalent and 1/2 ionic contri-
butions; in the extended basis set, both approaches give approximately a
single-bond estimate, with the information theory predicting the ionic dom-
inance of the overall bond multiplicity. The significant information-ionicity
contribution is also detected for all halides in the lower part of Table 1.2. One
also finds that all carbon–carbon interactions in the benzene ring are prop-
erly differentiated. The chemical orders of the single and multiple bonds in
ethane, ethylene, and acetylene are also properly reproduced, and the triple
bond in CO is accurately accounted. Even more subtle bond differentiation
effects are adequately reflected by the present information-theoretic results.
The differentiation of the “equatorial” and “axial” S–F bonds in the irregu-
lar tetrahedron of SF
4
is reproduced, and the increase in the strength of the
central bond in propellanes with increase of sizes of the bridges is correctly
predicted [9].
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Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 43
Table 1.2 The same as in Table 1.1 for the extended 6-31G* basis set
Molecule A–B M
AB
N
AB
S
AB
I
AB
F
2
F–F 1.228 1.228 1.014 0.273
HF H–F 0.816 0.816 0.598 0.218
LiH Li–H 1.005 1.005 1.002 0.004
LiF Li–F 1.121 1.121 0.494 0.627
CO C–O 2.904 2.904 2.371 0.533
H
2
O O–H 0.878 0.896 0.662 0.234
AlF
3
Al–F 1.147 1.154 0.748 0.406
CH
4
C–H 0.976 1.002 0.921 0.081
C
2
H
6
C–C 1.129 1.184 1.078 0.106
C–H 0.955 0.985 0.879 0.106
C
2
H
4
C–C 2.162 2.226 2.118 0.108
C–H 0.935 0.967 0.878 0.089
C
2
H
2
C–C 3.128 3.192 3.095 0.097
C–H 0.908 0.943 0.878 0.065
C
6
H
1
6
C
1
–C
2
1.507 1.592 1.473 0.119
C
1
–C
3
0.061 0.059 0.035 0.024
C
1
–C
4
0.114 0.117 0.081 0.035
LiCl Li–Cl 1.391 1.391 0.729 0.662
LiBr Li–Br 1.394 1.394 0.732 0.662
NaF Na–F 0.906 0.906 0.429 0.476
KF K–F 0.834 0.834 0.371 0.463
SF
2
S–F 1.060 1.085 0.681 0.404
SF
4
S–F
a
1.055 1.064 0.670 0.394
S–F
b
0.912 0.926 0.603 0.323
SF
6
S–F 0.978 0.979 0.726 0.254
B
2
H
2
6
B–B 0.823 0.851 0.787 0.063
B–H
t
0.967 0.995 0.938 0.057
B–H
b
0.476 0.490 0.462 0.028
Propellanes
3
[1.1.1] C
b
–C
b
0.797 0.829 0.757 0.072
[2.1.1] C
b
–C
b
0.827 0.860 0.794 0.066
[2.2.1] C
b
–C
b
0.946 0.986 0.874 0.112
[2.2.2] C
b
–C
b
1.009 1.049 0.986 0.063
1
For the sequential numbering of carbon atoms in the benzene ring.
2
H
t
and H
b
denote the terminal and bridge hydrogen atoms, respectively.
3
Central bonds between the bridgehead carbon atoms C
b
.
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44 Roman F. Nalewajski, Dariusz Szczepanik, and Janusz Mrozek
Moreover, as intuitively expected, the C–H bonds are seen to slightly
increase their information ionicity when the number of these terminal bonds
increases in a series: acetylene, ethylene, and ethane. In B
2
H
6
, the correct ≈
(1/2)-bond order of the bridging B–H bond is predicted, and approximately
single terminal bond multiplicity is detected. For the alkali metal fluorides
the increase in the bond entropy-covalency (decrease in information ionic-
ity) with increasing size (softness) of the metal is also observed. For the fixed
alkali metal in halides, for example, in a series consisting LiF, LiCl, and LiBr
(Table 1.2), the overall bond order is increased for larger (softer) halogen
atoms, mainly due to a higher entropy-covalency (delocalization) and noise
component of the molecular communication channel in AO resolution.
9. CONCLUSION
Until recently, a wider use of CTCB in probing the molecular electronic
structure has been hindered by the originally adopted two-electron con-
ditional probabilities, which blur a diversity of chemical bonds. We have
demonstrated in the present work that the MO-resolved OCT using the
flexible-input probabilities and recognizing the bonding/antibonding char-
acter of the orbital interactions in a molecule, which is reflected by the signs
of the underlying CBO matrix elements, to a large extent remedies this prob-
lem. The off-diagonal conditional probabilities it generates are proportional
to the quadratic bond indices of the MO theory; hence, the strong interorbital
communications correspond to strong Wiberg bond multiplicities. It also
covers the orbital decoupling limit and properly accounts for the increas-
ing populational decoupling of AO when the antibonding MOs are more
occupied. It should be also emphasized that the extra-computation effort of
this IT analysis of the molecular bonding patterns is negligible compared
with the standard computations of the molecular electronic structure, since
all quantum-mechanical computations in the orbital approximation already
determine the CBO data required by this generalized formulation of OCT.
We have also demonstrated that a dramatic improvement of the over-
all entropy/information descriptors of chemical bonds and a differentiation
of diatomic bond multiplicities is obtained when one recognizes the mutu-
ally decoupled groups of orbitals as the separate information systems. Such
decoupling process can be satisfactorily described only within the flexible-
input approach, which links the specified AO-input distribution to its
involvement in communicating (bonding) with the remaining orbitals. The
other improvement of the IT description of the bond diversity in molecules
and their weakening with the nonzero occupation of antibonding MO has
been gained by applying the MO-resolved channels supplemented with
the extra sign convention of their entropy/information bond contributions,
which is linked to those of the associated MO bond orders. Indeed, the
Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 45 #45
Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 45
bonding/antibonding classification, although lost in the conditional prob-
abilities, is directly available from the corresponding CBO matrix elements,
routinely generated in all LCAO-MO calculations and required to generate
the information channels themselves.
This orbital IT development extends our understanding of the chem-
ical bond from the complementary viewpoint of the information/
communication theory. The purely probabilistic models have been previ-
ously shown to be unable to completely reproduce the bond differentiation
patterns observed in alternative bond order measures formulated in the stan-
dard MO theory. However, as convincingly demonstrated in Section 8, the
bond probability weighting of contributions due to separate AO inputs gives
excellent results, which completely reproduce the bond differentiation in
diatomic fragments of the molecule implied by the quadratic criterion of
Wiberg. In excited states, only the recognition of the bonding/antibonding
character of the orbital interactions, which is reflected by the signs of the cor-
responding elements of the CBO matrix, allows one to bring the IT overall
descriptors to a semi-quantitative agreement with the alternative measures
formulated in the SCF-LCAO-MO theory.
The OCT has recently been extended to cover many orbital effects in the
chemical bond and reactivity phenomena [38, 68–70]. The orbital communi-
cations have also been used to study the bridge bond order components [71,
72] and the multiple probability scattering phenomena in the framework of
the probability-amplitude channel [73]. The implicit bond-dependency ori-
gins of the indirect (bridge) interactions between atomic orbitals in molecules
have also been investigated [74].
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2

Roman F. Nalewajski, Dariusz Szczepanik, and Janusz Mrozek

to characterize the scattering of electron probabilities and their information content throughout the system network of chemical bonds generated by the occupied molecular orbitals (MOs). Thus, the molecule is treated as information network, which propagates the “signals” of the electron allocation to constituent atomic orbitals (AOs) or general basis functions between the channel AO “inputs” and “outputs.” These orbital “communications” are determined by the two-orbital conditional probabilities of the output AO events given the input AO events. It is argued, using the quantum-mechanical superposition principle, that these conditional probabilities are proportional to the squares of corresponding elements of the first-order density matrix of the AO charges and bond orders (CBO) in the standard self-consistent field (SCF) theory using linear combinations of AO (LCAO) to represent MO. Therefore, the probability of the interorbital connections in the molecular communication system is directly related to the Wiberg-type quadratic indices of the chemical bond multiplicity. Such probability propagation in molecules exhibits the communication “noise” due to electron delocalization via the system chemical bonds, which effectively lowers the information content in the output signal distribution, compared with that contained in probabilities determining its input signal, molecular or promolecular. The orbital information systems are used to generate the entropic measures of the chemical bond multiplicity and their covalent/ionic composition. The average conditional-entropy (communication noise, electron delocalization) and mutual-information (information capacity, electron localization) descriptors of these molecular channels generate the IT covalent and IT ionic bond components, respectively. A qualitative discussion of the mutually decoupled, localized bonds in hydrides indicates the need for the flexible-input generalization of the previous fixed-input approach, in order to achieve a better agreement among the OCT predictions and the accepted chemical estimates and quantum-mechanical bond orders. In this extension, the input probability distribution for the specified AO event is determined by the molecular conditional probabilities, given the occurrence of this event. These modified input probabilities reflect the participation of the selected AO in all chemical bonds (AO communications) and are capable of the continuous description of its decoupling limit, when this orbital does not form effective combinations with the remaining basis functions. The occupational aspect of the AO decoupling has been shown to be properly represented only when the separate communication systems for each occupied MO are used, and their occupation-weighted entropy/information contributions are classified as bonding (positive) or antibonding (negative) using the extraneous information about the signs of the corresponding contributions to the CBO matrix. This information is lost in the purely probabilistic model since the channel communications are determined by the squares of such matrix elements. The performance of this MO-resolved approach is then compared with that of the previous, overall (fixed-input) formulation of OCT for illustrative π -electron systems, in the H¨ ckel approximation. A qualitau tive description of chemical bonds in octahedral complexes is also given. The bond differentiation trends in OCT have been shown to agree with both the

Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory

3

chemical intuition and the quantum-mechanical description. The numerical Restricted Hartree–Fock (RHF) applications to diatomic bonds in representative molecular systems are reported and discussed. The probability weighted scheme for diatomic molecular fragments is shown to provide an excellent agreement with both the Wiberg bond orders and the intuitive chemical bond multiplicities.

1. INTRODUCTION
The techniques and concepts of information theory (IT) [1–8] have been shown to provide efficient tools for tackling diverse problems in the theory of molecular electronic structure [9]. For example, the IT definition of Atomsin-Molecules (AIM) [9–13] has been reexamined and the information content of electronic distributions in molecules and the entropic origins of the chemical bond has been approached anew [9–18]. Moreover, the Shannon theory of communication [4–6] has been applied to probe the bonding patterns in molecules within the communication theory of the chemical bond (CTCB) [9, 19–28] and thermodynamic-like description of the electronic “gas” in molecular systems has been explored [9, 29–31]. The CTCB bonding patterns in both the ground and excited electron configurations have been tackled and the valence-state promotion of atoms due to the orbital hybridization has been characterized [28]. This development has widely explored the use of the average communication noise (delocalization, indeterminacy) and information-flow (localization, determinacy) indices as novel descriptors of the overall IT covalency and ionicity, respectively, of all chemical bonds in the molecular system as a whole, as well as the internal bonds present in its constituent subsystems and the external interfragment bonds. The electron localization function [32] has been shown to explore the nonadditive part of the Fisher information [1–3] in the molecular orbital (MO) resolution [9, 33], whereas a similar approach in the atomic orbital (AO) representation generates the so-called contragradience (CG) descriptors of chemical bonds, which are related to the matrix representation of the electronic kinetic energy [34–38]. It should be recalled that the molecular quantum mechanics and IT are related through the Fisher (locality) measure of information [34–41], which represents the gradient content of the system wavefunction, thus being proportional to the average kinetic energy ¨ of electrons. The stationary Schrodinger equation indeed marks the optimum probability amplitude of the associated Fisher information principle, including the additional constraint of the fixed value of the system potential energy [34, 39–41]. Several strategies for molecular subsystems have been designed [9, 22, 25, 26] and the atomic resolution of bond descriptors has been proposed [24]. The relation between CTCB and the Valence Bond (VB) theory has

4

Roman F. Nalewajski, Dariusz Szczepanik, and Janusz Mrozek

been examined [23, 27] and the molecular similarities have been explored [9, 42]. Moreover, the orbital resolution of the “stockholder” atoms and the configuration-projected channels for excited states have been developed [43–45]. The key concept of CTCB is the molecular information system, which can be constructed at alternative levels of resolving the electron probabilities into the underlying elementary “events” determining the channel inputs a = {ai } and outputs b = {bj }, for example, of finding an electron on the basis set orbital, AIM, molecular fragment, etc. They can be generated within both the local and the condensed descriptions of electronic probabilities in a molecule. Such molecular information networks describe the probability/ information propagation in a molecule and can be characterized by the standard quantities developed in IT for real communication devices. Because of the electron delocalization throughout the network of chemical bonds in a molecule the transmission of “signals” from the electron assignment to the underlying events of the resolution in question becomes randomly disturbed, thus exhibiting the communication “noise.” Indeed, an electron initially attributed to the given atom/orbital in the channel “input” a (molecular or promolecular) can be later found with a nonzero probability at several locations in the molecular “output” b. This feature of the electron delocalization is embodied in the conditional probabilities of the outputs given inputs, P(b|a) = {P(bj |ai )}, which define the molecular information network. Both one- and two-electron approaches have been devised to construct this matrix. The latter [9] have used the simultaneous probabilities of two electrons in a molecule, assigned to the AIM input and output, respectively, to determine the network conditional probabilities, whereas the former [38, 46–48] constructs the orbital-pair probabilities using the projected superposition-principle of quantum mechanics. The two-electron (correlation) treatment has been found [9] to give rise to rather poor representation of the bond differentiation in molecules, which is decisively improved in the one-electron approach in the AO resolution, called the orbital-communication theory (OCT) [38, 46–48]. The latter scheme complements its earlier orbital implementation using the effective AO-promotion channel generated from the sequential cascade of the elementary orbital-transformation stages [43–45, 49, 50]. Such consecutive cascades of elementary information systems have been used to represent the underlying orbital transformations and electron excitations in the resultant propagations of the electron probabilities, determining the orbital promotions in molecules. The information cascade approach also provides the probability scattering perspective on atomic promotion due to the orbital hybridization [28]. In OCT the conditional probabilities determining the molecular communication channel in the basis-function resolution follow from the quantummechanical superposition principle [51] supplemented by the “physical” projection onto the subspace of the system-occupied MOs, which determines

Finally. In this formulation of CTCB the off-diagonal orbital communications have been shown to be proportional to the corresponding Wiberg [52] or related quadratic indices of the chemical bond [53–63].and two-electron approaches have been compared. The internal and external indices of molecular fragments (groups of AO) can be efficiently generated using the appropriate reduction of the molecular channel [9. unity-normalized probability distribution of the input signal. which reflects the bonding or antibonding character of the MO in question. This procedure will be applied to determine the π -bond alternation trends in simple hydrocarbons (Section 6) and the localized bonds in octahedral complexes (Section 7). 25. for which predictions from the one. covering both the localized bonds in hydrides and multiple bonds in CO and CO2 . localized chemical bonds in simple hydrides will be qualitatively examined in Section 3. This extension will be shown to be capable of the continuous description of the orbital(s) decoupling limit. Additional. which requires the individual. It will be shown that this new AO-resolved description using the flexible-input (bond) probabilities as weighting factors generates bond descriptors exhibiting excellent agreement with both the chemical intuition and the quantum-mechanical bond orders formulated in the standard SCF-LCAO-MO theory. 46–48]. butadiene. This calls for the variable-input revision of the original and fixed-input formulation of OCT. in these studies the IT bond descriptors have been generated for both the molecule as whole and its constituent fragments. . After a brief summary of the molecular and MO-communication systems and their entropy/information descriptors in OCT (Section 2) the mutually decoupled. It will be argued that each such subsystem defines the separate (externally closed) communication channel.Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 5 the molecular network of chemical bonds. as well as the conjugated π bonds in simple hydrocarbons (allyl. and benzene). closed) character of these localized σ bonds. 46. the weighted-input approach for diatomic fragments in molecules will be formulated (Section 8). occupational aspect of the orbital decoupling in the OCT description of a diatomic molecule will be described in Section 5. which will be presented in Section 4. 48] by combining selected outputs and larger constituent fragment(s). in order to establish the input probability requirements. in accordance with the signs of the associated off-diagonal matrix elements of the CBO matrix. It introduces the separate communication channels for each occupied MO and establishes the relevant weighting factors and the crucial sign convention of their entropic bond increments. Several illustrative model applications of OCT have been presented recently [38. when AO subspace does not mix with (exhibit no communications with) the remaining basis functions. which properly account for the nonbonding status of the lone-pair electrons and the mutually decoupled (noncommunicating. Both the molecule as a whole and its constituent subsystems can be adequately described using the OCT bond indices.

. {γi. (2a) thus. j } ≡ I.6 Roman F. which correspond to the base 2 in the logarithmic (Shannon) measure of information.s } groups the relevant LCAO-expansion coefficients. 2. for example. p = {pi = Ni /N}. ϕ2 . MOLECULAR INFORMATION CHANNELS IN ORBITAL RESOLUTION In the standard MO theory of molecular electronic structure the network of chemical bonds is determined by the system-occupied MO in the electron configuration in question. . ˆ The latter represents the projection operator Pϕ = |ϕ ϕ| = ˆ Ps onto the subspace of all doubly occupied MO. Lowdin’s symmetrically orthogonalized AO. ρ(r) = 2ϕ(r)ϕ †(r) = χ(r)[2CC† ]χ †(r) ≡ χ(r)γχ †(r) = Np(r). doubly occupied MO.i = Ni = Npi }. The entropy/information descriptors are measured in bits. For simplicity. . valence state of AO in the molecule. . χ |χ = {δi. . involving the n lowest (real and orthonormal). ϕn ) = {ϕs } = χ C. . where the rectangular matrix C = {Ci. are determined by the first-order density matrix γ in the AO representation. and Janusz Mrozek Throughout this article. In the LCAO-MO approach. that is. the bold-italic X denotes the row vector. ϕ = (ϕ1 . they are given as linear combinations of the appropriate (orthogonalized) basis functions ¨ χ = (χ1 . . ϕ (3) The CBO matrix reflects the promoted. with the diagonal elements measuring the effective electron occupations of the basis functions. the bold symbol X represents a square or rectangular matrix. . s s (1) |ϕs ϕs | ≡ ˆ ˆ ˆ γ = 2 χ |ϕ ϕ|χ = 2CC† ≡ 2 χ |Pϕ |χ = {γi. and italic X stands for the scalar quantity. Dariusz Szczepanik. . the density per electron or the shape factor of ρ. χ2 . let us first assume the closedshell (cs) ground state of the N = 2n electronic system in the Restricted Hartree–Fock (RHF) description. j = 2 χi |Pϕ |χj ≡ 2 i|Pϕ |j }. χm ) = {χi }. groups the probabilities of the basis functions being occupied in the molecule. satisfying the appropriate idempotency relation ˆ ˆ ˆ ˆ (γ)2 = 4 χ |Pϕ |χ χ |Pϕ |χ = 4 χ |P2 |χ = 4 χ |Pϕ |χ = 2γ. also called the charge and bond order (CBO) matrix. The AO-probability vector in this state. Nalewajski. The system electron density ρ(r) and hence the one-electron probability distribution p(r) = ρ(r)/N.

ˆ ˆ ˆ ˆ (γos )2 = χ Pos χ χ Pos χ = χ (Pos )2 χ = χ Pos χ = γos . (6) (7a) The conditional probabilities of Eqs. Hence. j γj. These (physical) one-electron probabilities explore the dependencies between AOs resulting from their participation in the system-occupied MO.i )−1 γi. The off-diagonal conditional probability of jth AO output given ith AO input is thus proportional to the squared element of the CBO matrix linking the two AOs.j γj. In the one-electron approach [46–48].2j to the Wiberg . In the open-shell (os) case [48] one partitions the CBO matrix into contributions originating from the closed-shell (doubly occupied) MO ϕ cs and the open-shell (singly occupied) MO ϕ os . [3]). respectively. (3). j = γi. these AO-communication connections {P(χj |χi ) ≡ P(j|i)} result from the appropriately generalized superposition principle of quantum mechanics [51]. (4) where the closed-shell normalization constant Ni = (2γi. j .i = γi.Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 7 The information system in the (condensed) orbital resolution involves the AO events χ in its input a = {χi } and output b = {χj }. their involvement in the entire network of chemical bonds in a molecule.i . in order to extract the IT i multiplicities of the ionic and covalent bond components. Such information system constitutes the basis of OCT [46–48]. respectively. ϕ ϕ ϕ ϕ and (γcs )2 = 2γcs (Eq. ϕ os ): ˆ ˆ γ = χ |ϕ os ϕ os |χ + 2 χ |ϕ cs ϕ cs |χ ≡ χ |Pos |χ + 2 χ |Pcs |χ ≡ γos + γcs . it is also proportional to the corresponding AO contribution Mi. ϕ = (ϕ cs .i + 2γi. ˆ P(b|a) = P(j|i) = Ni | i|Pϕ |j |2 = (2γi. This molecular channel can be probed using both the promolecular (p0 = {p0 }) and molecular (p) input probabilities. with the input (row) and output (column) indices. in which the “signals” of the molecular (or promolecular) electron allocations to basis functions are transmitted between the AO inputs and outputs. (4 and 7a) define the probability scattering in the AO-promotion channel of the molecule.i . os cs ˆ P(j|i) = Ni | i|Pϕ |j |2 = (γi. (5) ϕ ϕ They satisfy separate idempotency relations. Therefore.i )−1 follows directly Eq. j P(j|i) = 1.i )−1 γi. It represents the effective promotion of these basis functions in the molecule via the probability/information scattering described by the conditional probabilities of AO outputs given AO inputs. γj. that is.

in the closed-shell system. due to the doubly occupied MO ϕ cs . s ˆ γcs = γi.i (s) . each doubly occupied MO ϕ = {ϕs } generates the corresponding contributions to the CBO matrix of Eq. (7b) were obtained using Eqs. It should be observed at this point that the promolecular input p(a0 ) ≡ p0 in general produces different output probability p0 P(b|a) = p∗ (a0 ) = {p∗ } = p∗ = p. (4a and 7a) with the normalization constants appropriately modified to satisfy the normalization condition for the conditional probabilities: Pcs (j|i) = s j j Pos (j|i) = 1. generated by the singly s s j os occupied MO ϕ . or to generalized quadratic descriptors of molecular bond multiplicities [53–63]. γos = {γi. In the preceding equation we have used the partial normalization of the molecular joint. By separating the CBO contributions due to each occupied MO one similarly defines the information system for each orbital. and Janusz Mrozek index [52] of the chemical bond covalency between two atoms A and B. [3 and 6]): (γcs )2 = 2γcs and (γos )2 = γos . one separately partitions the contrics bution of γcs = s γcs .i (s) j cs 2γi.cs (s)γj. pP(b|a) = i pi P(j|i) ≡ i P(i.os (s) = i|Ps |j }. They satisfy the corresponding idempotency relations (see Eqs. (2): γ=2 s χ |ϕs ϕs |χ ≡ s γcs . j . The molecular input p(a) ≡ p generates the same distribution in the output of the molecular channel.cs (s) = 2 i|Ps |j . j) = pi P(j|i)} to the corresponding one-orbital probabilities. One then determines the s s s s corresponding communication connections for each occupied MO. Nalewajski. the entropy/information indices of the covalent/ionic components of all chemical bonds in a molecule represent the complementary descriptors of the average communication noise and the amount of information flow in the molecular information channel.B) = i∈A j∈B Mi.i (s) and Pcs (b|a) = Pcs (j |i ) = s s cs γi.8 Roman F. and the s os ˆ remaining part γos = s γos . Dariusz Szczepanik. s (7c) In OCT. For example. two-orbital probabilities P(a. Pos (b|a) = Pos (j|i) = s s os γi. M(A. b) = {P(i. j .i (s) j os γi. s j (2b) In the open-shell configuration. j) = pj =p (8) and thus identifying p as the stationary probability vector for the molecular state in question.os (s)γj.

when p0 = p. b)] = − (9b) For the independent input and output events. This quantity reflects the fraction of the initial (promolecular) information content H[p0 ]. H[p] = − i pi log2 pi . In particular. for the molecular input. measured by the conditional entropy S(b|a) ≡ S of the system outputs given inputs: S(b|a) = − i j P(i. 46–48]. 38. before their mixing into MO [9. . which has not been dissipated as noise in the molecular communication system. j)/pi ] pi i j =− P(j|i)log2 P(j|i) ≡ S[p|p] ≡ S[P(b|a)] ≡ S. However. P(i. b)] = 2H[p] and hence Sind. j)log2 P(i. the atomic promolecule—a collection of nonbonded free atoms in their respective positions in a molecule or the AO basis functions with the atomic ground-state occupations. i j H[P(a. with p defining its input signal. j). (a. The AO occupations in this reference state are fractional in general.and two-orbital probabilities. (9a) Thus.Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 9 The purely molecular communication channel [9. for example. b) = {pi pj }. when Pind. (a. is devoid of any reference (history) of the chemical bond formation and generates the average noise index of the molecular IT bond covalency. this average noise descriptor expresses the difference between the Shannon entropies of the molecular one. b)] − H[p]. It gives rise to the average information-flow descriptor of the system IT bond ionicity. = H[p]. b)] i (10) = H[p ] − S = I[p0 : p] ≡ I[P(b|a)] = I. H[Pind. 46–48]. in view of the exploratory character of the present analysis. we shall often refer to the simplest description of the promolecular reference by a single (groundstate) electron configuration. j)log2 [P(i. which exhibits the integral occupations of AO. j)/(pj p0 )] = H[p] + H[p0 ] − H[P(a. The molecular channel with p0 determining its input signal refers to the initial state in the bond formation process. j)log2 [P(i. 38. S = H[P(a. given by the mutual information in the channel inputs and outputs: I(a0 : b) = i 0 j P(i.

p] ≡ N [P(b|a)] ≡ N = H[p0 ]. Thus. It should be emphasized that these entropy/information descriptors and the underlying probabilities depend on the selected basis set. Iind. Nalewajski. when p0 = p. the canonical AO of the isolated atoms or the hybrid orbitals (HOs) of their promoted (valence) states. There are two aspects of the orbital decoupling in chemical bonds. To conclude this section. using simple hydrides as an illustrative example. We shall call these two facets the mixing (shape) and occupation (population) decouplings. for example.10 Roman F. etc. when the bonding and antibonding MO combinations are completely occupied by electrons. we observe that by propagating the AO probabilities through the information channels of the separate MO. calls for the separate unit normalization of its input probabilities since such fragments constitute the mutually nonbonded (closed) building blocks of the molecular electronic structure. In Section 3. Again. On one side. the two AOs are also effectively decoupled. b) = S + I ≡ N [p0 . b) = S(b|a) + I(a : b) = H[p]. The emphasis will be placed on the orbital decoupling in the molecular communication channels and the need for appropriate changes in their input probabilities. In what follows we shall examine these IT descriptors of chemical bonds in illustrative model systems. and Janusz Mrozek I(a : b) = i j P(i. which marks the initial information content of orbital probabilities. for the independent input and output events. Dariusz Szczepanik. (7b). since such MO configuration is physically equivalent to the Slater determinant of the doubly occupied (original) AO. for the molecular input. On the other side. that the fulfillment of this requirement dramatically improves the agreement with the accepted chemical intuition and the alternative bond multiplicity concepts formulated in the MO theory. defined by the conditional probabilities of Eq. It is of vital interest for a wider applicability of CTCB to examine how these two mechanisms can be accommodated in OCT. respectively. when two bonding electrons occupy a single AO. N (a0 . which weigh the contributions to the average information descriptors from each input. in the extreme MO-polarization limit of the electronic lone pair. when they do not mix into MO. the localized MO (LMO). (11) measures the overall IT bond multiplicity of all bonds in the molecular system under consideration. j)/(pj pi )] = H[p] − S = I[p : p]. j)log2 [P(i. the two chemically interacting AOs becomes decoupled. the sum of these two bond components. Finally. It is seen to be conserved at the promolecularentropy level. this quantity preserves the Shannon entropy of the molecular input probabilities: N (a. one could similarly determine the . we shall argue that the mutual decoupling status of several subsets of basis functions. for example. It will be demonstrated. manifesting itself by the absence of any external communications (bond orders) in the whole system. no matter how strong is their mutual mixing. (a : b) = 0.

It reaches the maximum value H(P = 1/2) = 1 for the symmetric bond P = Q = 1/2 and vanishes for the lone-pair configurations. 1/2). b) originating from atoms A and B. Q (13) then generates the information system for such a two-AO model. In this diagram one adopts the molecular input p = (P. 1) : I(P = 0. to calculate the IT ionicity relative to this covalent promolecule. 1) in the assumed promolecular reference. 1). .1a. The associated model CBO matrix.Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 11 IT bond increments for each occupied MO. ϕbond. in which each basis function contributes a single electron to form the chemical bond. ) = P(a|ϕanti. Both components yield the conserved overall bond index N (P) = 1 in the whole range of bond polarizations P ∈ [0. while . to extract the bond IT covalency index measuring the channel average communication noise. We shall implement this idea in Section 5. and the unoccupied antibonding MO ϕanti. γ=2 P PQ PQ . 1]. as a result of an increased occupation of the antibonding MO. gives rise to the doubly occupied. respectively. determining the channel (mutual) information capacity I(P) = H[p0 ] − H(P) = 1 − H(P). The complementary descriptor of the IT ionicity. and the promolecular input p0 = (1/2. 1) = 1. P + Q = 1. relative to the initial AO occupations N 0 = (1. shown in Scheme 1. this model properly accounts for the competition between the bond covalency and ionicity. covering the symmetrical bond combination for P = Q = 1/2 and the limiting lone-pair (nonbonding) configurations for P = (0. when P = (0. marking the alternative ionpair configurations A+ B− and A− B+ . ) = P(b|ϕanti. when tackling the populational decoupling of atomic orbitals. Thus. bonding MO ϕbond. ϕanti. respectively. Therefore. which control the bond polarization. DECOUPLED (LOCALIZED) BONDS IN HYDRIDES REVISITED In the ground-state the chemical interaction between two (singly occupied) orthonormal AOs χ = (a. 3. Q = 1 − P). The bond IT covalency S(P) is then determined by the binary entropy function H(P) = − Plog2 P − Qlog2 Q = H[p]. 1). this ionicity descriptor is seen to identically vanish for the purely covalent. = √ Pa + Qb. = − Qa + √ Pb. symmetric bond. I(P = 1/2) = 0. reaches the highest value for these two limiting electron-transfer configurations P = (0. H(P = 0) = H(P = 1) = 0. ) = Q. (12) Their shapes are determined by the complementary (conditional) probabilities: P(a|ϕbond. ) = P and P(b|ϕbond.

σα = γσα . . one thus predicts H[p 0 ] = 1 and the bond information ionicity I = 1 − H(P). Dariusz Szczepanik. with the antibonding MO ϕanti. Hence. these two bond components give rise to the conserved (P-independent) value of the single overall bond multiplicity N = I + S = 1. j = 0. and Janusz Mrozek P(b|a) a Q P b Q b P a p P Q S = −Plog2 P − Qlog2 Q = H(P) I = H[ p 0 ] − H(P) N = I + S = H[ p 0 ] (b) 1 h0 n 1 h0 n 1 S=I=N =0 Scheme 1. For the n molecular input p = (P. . (15) while for each of 4 − r nonbonded hybrids {hn }. the corresponding CBO matrix γα for a single σ bond X–Hα {γα. Q). r. when both basis functions contribute a single electron each to form the chemical bond.hn = 2 and γhn . 1/2). for r = 4. For the promolecular input p 0 = (1/2. . . NH3 . This localized bond model can be straightforwardly extended to the system of r localized bonds in simple hydrides XHr [49]. or H2 O. γhα . (16) . directed towards the hydrogen ligand Hα .β } then includes the following nonvanishing elements: γhα . γhn . the corresponding nonbonding (deterministic) channel due to the lone-pair hybrid h0 is shown.hα = 2 PQ. (α) = − Qhα + Pσα P + Q = 1. Similar effects transpire from the two-electron CTCB [9] and the quadratic bond indices formulated in the MO theory [53–63]. for example.12 (a) p P Q Roman F. describing the system loneelectronic pairs. preserving the single measure of the overall IT multiplicity of the chemical bond. γσα . (α). Nalewajski. the orbital channel of Panel a gives the bond entropy-covalency represented by the binary entropy function H(P). O and α = 1. (14) In the χ α = (hα . ϕanti.hα = 2P. can then be approximately regarded as resulting from the chemical interaction of a pair of two orthonormal orbitals: the bonding sp3 hybrid hα of the central atom. In Panel b. (α) = Phα + Qσα . 3. CH4 . (α) remaining empty: √ √ ϕbond. a single σ bond X–Hα . 2. N.σα = 2Q. b) and its entropy/information descriptors. respectively. Indeed.1 The molecular information system modeling the chemical bond between two basis functions χ = (a. and the 1sα ≡ σα orbital of the latter. j = hn . The localized bond X–Hα then originates from the double occupation of the corresponding bonding MO ϕbond. σα ) representation. for X = C.

26].1a. Such mutually closed (isolated) subchannels correspond to the separate input/output probability distributions. P(hα |σα ) = Q. (19) We have recognized in these expressions that each lone-pair (doubly occupied) hybrid hn of the central atom. generates the decoupled deterministic subchannel of Scheme 1. consisting of inputs and outputs χ α = (hα .Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 13 The corresponding conditional probabilities (see Eq. b) = {Pα (aα .1b. then read: P(hα |hα ) = P. These separate molecular subsystems give rise to the additive bond contributions Sα (bα |aα ) ≡ Sα . N= α Nα = r. bα ) ≡ Pα [χ α . Therefore. 1/2) or pα = p∗ = (P. χ α ] = P2 QP PQ . P(σα |hα ) = P. it does not contribute to the resultant entropy/information index of all chemical bonds in the molecule. each satisfying the unit norα α malization [9. p0 = (1/2.β } and P(a. P(hn |hn ) = 1. It follows from these expressions that each localized bond X–Hα in this HO representation defines the separate communication system of Scheme 1. [4]). As a result such decoupled subchannels {hn = h0 } representing two lone n pairs of oxygen atom in H2 O or a single nonbonding electron pair of nitrogen in NH3 . Therefore.β }. (17) Therefore. P(σα |σα ) = Q. introduce the exactly vanishing contributions to both bond components and hence to the overall bond index of these molecules in OCT. . determining the mutually decoupled information systems defined by the diagonal blocks Pα (bα |aα ) ≡ Pα [χ α |χ α ] = P P Q . the electron probability is not scattered by the lone-pair hybrids. such orbital pairs constitute the externally closed (nonbonding) subsystems. bα )δα. Q Pα (aα . Q). Q2 (18) of the associated overall probability matrices in the χ = {χ α } basis set: P(b|a) = {Pα (bα |aα )δα. which determine the nonvanishing communication connections. Iα (a0 : bα ) ≡ Iα and Nα (a0 : bα ) = α α Sα + Iα ≡ Nα to the system overall bond descriptors in OCT: S(P) = α Sα = rH(P). σα ). I(P) = α Iα = r[1 − H(P)]. which does not exhibit any external communications with AO involved in the system remaining bonds. which does not form any chemical bonds (communications) with the hydrogen ligands. thus exhibiting the unit input probability.

One observes. Again. with S = 4H(P) and I = 4[1 − H(P)]. each including one sp hybrid of Be and 1s orbital of the corresponding hydrogen. h2 . = 2 and Imax. the IT bond composition reads Smax. (20) √ The associated CBO matrix. and hence for the maximum orbital mixing (P = 1/2). with S = 2H(P) and I = 2[1 − H(P)]. σ2 ) used to generate the localized MO of Eq. 2 W (σ1 − σ2 ). In the localized bond representation. the net result is the four decoupled bonds in the system giving rise to overall IT bond index N = 4. the four delocalized bonds are described by the four (mutually decoupled) orbital-pair interactions between the specified canonical AO of carbon atom and the corresponding symmetry combination of four hydrogen orbitals. the canonical valence-shell MO in CH4 . a change in the bond covalent/ionic composition resulting from this transformation from the localized MO description to the canonical MO perspective [48].  U+T U−T U+T √ √ UV − TW √ √ UV + TW √ TW √ √ UV − TW √ UV + V+W V−W √ TW √ √ UV + TW √ UV − V−W V+W (21) indicates that all these basis orbitals in fact exhibit the nonvanishing communications to all outputs in this delocalized representation of the system electronic structure. Dariusz Szczepanik. 2 Us + Tp + U + V = 1.     U−T γ= √  UV + √TW  √ √ UV − TW . and Janusz Mrozek The same result follows from another. that the three axes of the Cartesian coordinate system pass through the middle of its opposite walls. the two bonding MOs result from the mutually decoupled interactions between two-orbital pairs. As an illustration of this entropic effect. delocalized representation of chemical bonds in these prototype systems. In the delocalized description. read as follows: ψ1 = ψ2 = √ V (σ1 + σ2 ) = 2 W (σ1 − σ2 ) = 2 U (h1 + h2 ) + 2 T (h1 − h2 ) + 2 V (σ1 + σ2 ). T + W = 1. (12). = 0. Consider. In the maximum mixing limit of U = V = T = W = 1/2    . let us briefly examine the bonding pattern in the linear BeH2 . expressed in the basis set χ = (h1 . the two doubly occupied canonical MO.14 Roman F. σ1 . however. as an illustration. Nalewajski. This localized approach thus gives N = 2. with four hydrogen ligands in the alternating corners of the cube placed in such a way. In such an arrangement.

FLEXIBLE-INPUT GENERALIZATION Thus. the lower is the covalency (the higher ionicity) of this localized. = 1 and hence N max. with changing covalent/ionic composition in accordance with the actual MO polarization and the adopted basis set representation. The associated entropy/information indices for this channel read as follows: Smax. in this IT description the total bond multiplicity N = r bits is conserved for changing proportions between the overall covalency and ionicity of all chemical bonds in the system under consideration. the higher the “noise” descriptor of the underlying information system. The more the probability parameter P deviates from the symmetrical bond (maximum covalency) value P = 1/2. this requirement expresses its externally closed status relative to the molecular remainder. . due to the electronegativity difference between the central atom and hydrogen. 4. (22) and so is the associated matrix P(b|a) = 1/2γmax. 1 0 = 1 0  0 1 0 1 1 0 1 0  0 1 . which give rise to the overall unit normalization. this delocalized channel is characterized by the input distributions p = p0 = {1/4}. 0 1 γmax. noncommunicating fragments of the whole molecular system. the more delocalized is this scattering.Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 15 it is only partly decoupled. Therefore. this “rivalry” between bond components reflects a subtle interplay between the electron delocalization (Sα = H(P)) and localization (Iα = 1 − H(P)) aspects of the molecular scattering of electron probabilities in the information channel of a separated single chemical bond. Thus. The more deterministic is this probability propagation. = Imax. decoupled from the molecular remainder. This requirement was hitherto missing in all previous applications of CTCB and OCT to polyatomic systems. Accordingly. = 2. diatomic bond. It modifies the overall norm of the molecular input to the number of such mutually closed. of r bonds in XHr . it follows from the analysis of the preceding section that a general agreement of IT descriptors with the intuitive chemical estimates follows only when each externally decoupled fragment of a molecule exhibits the separate unit normalization of its input probabilities. the higher the ionic component. of molecular communications (see Eq. [4]). The variable-input norm description of the decoupled chemical bonds gives the full agreement with the chemical intuition. In the orbital-communication theory.

Nalewajski. Such bonded fragments of the molecule are mutually open. and Janusz Mrozek In the generalized approach the probabilities p0 = {pα } of the constituent a α inputs in the given externally decoupled (noncommunicating and nonbonded) subchannel α 0 of the system “promolecular” reference M0 = (α 0 |β 0 | . . . the above summation over the internal orbital events then expresses the normalization of all such conditional probabilities in the separate (or isolated) subsystem α 0 : a∈α P(a|α) = 1. conditional in character. we have denoted the externally closed status of each fragment in 0 M by separating it with the vertical solid lines from the rest of the molecule. when this molecular fragment is not considered to be a part of a larger system.16 Roman F. In the previous. . these subsystem probabilities are. that is. which cannot describe this transition in a continuous (“causal”) fashion. only the overall input normalization equal to the number of the decoupled orbital subsystems gives rise to the full agreement with the accepted chemical intuition. pα = P(a|α) = pa /Pα . calculated per unit input probability Pα = 1 of the whole a subsystem α in the collection of the mutually nonbonded subsystems in the reference M0 . fixed-input determination of the IT bond indices this discontinuity in the transition from the decoupled to the coupled descriptions of the molecular fragments prevents an interpretation of the former as the limiting case of the latter. Therefore. the fixedand flexible-input approaches generate the mutually exclusive sets of bond indices. α a∈α pa = 1. Indeed. thus alone exhibiting the unit probability normalization. each decoupled fragment appears as a separate system. flexible-input generalization of the use of the molecular information systems. when the same subsystem exhibits non-vanishing (no matter how small) communications with the remainder of the molecule M = (α β . in fact.) should thus exhibit the internal (intrasubsystem) normalization. In other words. Therefore. We shall demonstrate that in such an extension the above limiting transition in the communication description of the subsystem . Therefore. the input probabilities of the bonded fragment α in M. They are characterized by the fractional condensed probabilities P = {PM < 1}. This situation changes discontinuously in the externally coupled (communicating and bonded) case. As we have demonstrated in the decoupled approach of the preceding section. Dariusz Szczepanik.). when all external communications of the subsystem in question become infinitely small. are then subject to the molecular normalization: a∈α pα = a α a a α PM a∈α pα = PM . the former corresponds to the unit norm of input probabilities for all molecular subsystems. pM = {pM = PM pα }. The need for using the molecular input probabilities then α a α causes a discontinuous change in the system covalent/ionic bond components compared with the corresponding decoupled (promolecular) values. whereas in the latter. α which measure the probabilities of the constituent subsystems in M as a whole. as symbolically denoted by the vertical broken lines separating them. in this section we shall attempt to remove this discontinuity in the unifying. Indeed. .

i0 ) ≡ p(k|i0 ). i0 )} as conditional probabilities of two-orbital events. Consider first the completely coupled molecular channel. have to explicitly depend on the structure of its molecular communications. in which all orbitals interact chemically. it should be emphasized that these probabilities are also conditional on the molecule as a whole. the joint probabilities per unit probability of the specified input: p(k. The reference promolecular probabilities. In order to make this transition continuous. . carried out to extract the IT covalent bond descriptor. The essence of the new proposition lies in a separate determination of the entropy/information contributions due to each AO input in the molecular channel specified by the conditional probabilities P(b|a). However. This goal can be tackled by using the separate probability distributions tailored for each input. these contributions must be weighted with the appropriate ensemble probabilities of each input. i)} and {p(k. the separate input-dependent distributions. i) ≡ p(k|i) and p(k.Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 17 decoupling in the molecule finds the continuous (causal) representation. they have to continuously increase the overall norm of the distribution for the given input orbital with increasing localization of the molecular scattering of this input signal to reach the unit input norm in the limit of this orbital being totally decoupled from the rest of the molecule. . the overall IT bond descriptor of M as a whole will be generated by the summation of all such additive contributions determined in the separate propagations of the input-tailored molecular/promolecular distributions: N = i N (i). also input dependent {p(i0 ) = {p(k. 2. since . these inputdependent contributions generate the corresponding total indices {N (i) = I(i) + S(i) = N [p(i0 ). There are obvious normalization (sum) rules to be satisfied by these inputdependent probabilities. (23) This condition recognizes a general category of these input-dependent probabilities {p(k. will be used to estimate the corresponding ionic contributions due to each input: {I(i) = I[p(i0 )]}. that is. i)} for each molecular input i = 1. Indeed. will now be replaced by the series of m molecular propagations of the separate probability distributions {p(i) = {p(k. which generate the associated covalencies: {S(i) = S[p(i)]}. Together. m. The hitherto single molecular propagation of the overall molecular input probabilities p of the previous approach. . In the average molecular quantities. i)] = k k p(k. p(i)]}. tailored for each ith input event. In this case all molecular inputs have to be effectively probed to the full extent of the unit condensed probability of the molecule as a whole: p(k. which is embodied in the ith row of the system two-orbital conditional probabilities. thus exhibiting nonvanishing direct and/or indirect communications with the system remainder. . i0 )] = 1. for example. i0 )}. the molecular probabilities p = {pi }. Finally.

α → α 0 . In case of the decoupled single-orbital subsystem χi0 . which reflects all communications (bonds) between this orbital input and all orbital outputs {j} (columns in P(b|a)). the AO inputs in α are to be probed with an overall unit condensed probability: a ∈α P(a |a) = 1. and Janusz Mrozek they correspond to the unit input probability in M or M0 . .k . This link must generate the separate subsystem probabilities p0 .1b).β = p(k|a0 α 0 ) = pα (a |a0 )δα. when P(b|aα ) → {P(bα |aα )δα. (27) Since this entropy-covalency corresponds to the overall unit norm of probability distribution associated with ith input. Indeed. (25) In order to make the fragment decoupling continuous in this generalized description. Consider the conditional-entropy contribution from ith channel: S(i) = − k j P(k. they both have to be related explicitly to the ith row in the conditional probability matrix P(b|a) = {P(j|i)}. where P(bα |aα ) = {P(a |a)}. . Therefore. k)/pk ] = − k P(k|i) j P(j|k)log2 P(j|k) .β = P(a |a)δα. only the diagonal probability scattering Pi (i|i) = 1 is observed in the molecule (Scheme 1.k = p(k|i0 ) = p(i|i0 i0 ) = p(i0 |i0 )δi. corresponding to all mutually open basis functions. i (24) p(k|i0 ) = p(k|i0 M0 ) = P(k|i0 ) ≡ P(k|i). j M)/p(i M) = p(j|i M) = P(j|i). i)log2 [P(j. for the decoupled subsystem α 0 = (a. p0 (i)} have to be replaced by the separate distributions reflecting the actual participation of ith AO in the chemical bonds (communications) of the molecule. The input-tailored conditional probabilities then refer to the unit input probability of the input i(i0 ) alone: p(k|i) = p(i|i i) = p(i|i)δi. They also characterize the internal conditional probabilities in α 0 since p(j|i α 0 ) = p(i. (26) Hence. j. Dariusz Szczepanik. In the input-dependent molecular channels. the input probabilities {p(i).18 Roman F. p(k|i) = p(k|i M) = P(k|i).β }. when the fragment α becomes decoupled from the rest of the molecular system. in the average molecular quantity.) only the internal communications of the corresponding block of the molecular conditional probabilities P(bα |aα ) = {P(a |a)} are allowed. {p(k|a α 0 ) = pα (a |a)δα. j α 0 )/p(i α 0 ) = P(i. all these requirements can be shown to be automatically satisfied when one selects the input-tailored probabilities. as the corresponding rows of the molecular conditional probability matrix P(b|a) = {P(j|i)}.β }. it has to be weighted by the actual probability pi of this input in the molecule as a . we seek.k = δi. again. a . . Nalewajski. i pi = i p0 = 1.

As an illustration (see Scheme 1. let us again consider the two-AO channel of Scheme 1. k)/(pj p0 )] = −S(i) − k k j P(j. input AO contributions: N (i) = S(i) + I(i) = − k j P(k0 . 1/2) of the covalent promolecule. k k Ii = −S + H[p0 ]. It can be directly verified that such averaging indeed reproduces the molecular index of Eq. when two AOs contribute a single electron each to form the chemical bond. the promolecular reference distribution is seen to enter the final determination of the ionic (difference) components relative to the initial distribution of electrons before the bond formation. j|i)log2 [P(j. k0 )log2 p0 k = −S(i) − k p0 log2 p0 = −S(i) + H[p0 ]. A similar demonstration can be carried out for the mutual-information (ionic) contributions: I(i) = k j P(k0 . The partial and average IT descriptors are also reported in this diagram.Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 19 whole. = i pi I(i) ≡ (29) Thus. with only the molecular inputs being used in probability propagation. = i pi N (i) ≡ (30) To summarize.2a). i Iav. . k)log2 P(j|k) = S. However. i) P(j|k)log2 P(j|k) = − k j pk P(j|k)log2 P(j|k) (28) =− k j P(j. = i pi S(i) ≡ i Si = − i k j [pi P(k|i)]P(j|k)log2 P(j|k) =− k j i P(k. (9): Sav. [18]). j)log2 p0 . i Nav. in the flexible-input extension of OCT the consistent use of the molecular channel is proposed. k Ni = N = H[p0 ].1a. it follows from these contributions that they also reproduce the overall molecular bond index as the mean value of the partial. We first observe that the input-dependent distributions in this model are identical with the molecular distribution (see Eq. relative to the reference distribution p0 = (1/2.

The corresponding partial and average entropy/information descriptors of the chemical bond are also reported. which was missing in the previous. p(b0) P Q Sa = PH(P) Ia = P[1 − H(P)] Na = Sa + Ia = P Sb = QH(P) Ib = Q[1 − H(P)] Nb = Sb + Ib = Q Sav. Indeed. fixed-input scheme. ϕanti. Therefore. ] since the Slater determinant |ϕbond. 1 1 Such decoupled AO corresponds to the molecular configuration [ϕbond. the resultant input signal corresponds to the unit norm of the condensed probability distribution. Dariusz Szczepanik. this flexible normalization is automatically increased . ϕanti.1a for the promolecular reference distribution p 0 = (1/2. In the former case. 1/2). It is also of interest to examine the dissociation of this model molecule A–B into (one-electron) atoms A and B. In the case of n-mutually separated fragments. using the orthogonal transformations between χ = (a. = Ia + Ib = 1 − H(P) = I Nav.2 that in the limit of the decoupled (lone-pair) orbital ϕbond. ). Nalewajski. 1 1 one can directly verify that γ[ϕbond. so that the decoupled AO inputs become p(a) = p(a0 ) = (1. the flexible-input approach correctly accounts for the MO shape decoupling in the chemical bond. ϕanti. This generalization covers in a common framework both the completely coupled AO in the molecule and the limiting cases of its subsystems being effectively decoupled in the molecular channel. each is separately unity normalized. p(b) Roman F. p(b0) P Q p(a0). It follows from the input probabilities in Scheme 1. while still retaining the essence of the previous approach. b) and ϕ = (ϕbond. ϕanti. The flexible-norm generalization of the previous OCT completely reproduces the overall IT bond order and its components reported in Scheme 1. Therefore.1. so that both orbitals do not contribute to the resultant bond indices. which determine the promolecule. χ =ϕ P − Q √ √Q P ≡ ϕCT and ϕ = χ C. 0) and p(b) = p(b0 ) = (0. as required. | = |ab|. = b(Q = 1) its input probability becomes 1. while that of the other (empty) orbital identically vanishes. CT C = CCT = I.2 The flexible-input generalization of the two-AO channel of Scheme 1. p(b) P(b|a) a b Q P P Q a b p(a0). The unit input probability of the doubly occupied AO in the channel input is then deterministically transmitted to the same AO in the channel output. . = a(P = 1) or ϕbond. = Sa + Sb = H(P) = S Iav. and Janusz Mrozek p(a). 1). ] = CCT = I = P(b|a). with the other (unoccupied) AO not participating in the channel communications. = Na + Nb = 1 = N Scheme 1. the new proposition introduces in OCT of the chemical bond that is the desired input flexibility generating the continuity in the IT description of the fragment decoupling process.20 p(a).

48. reported in Scheme 1. one obtains S = 0. this probability product in fact meaˆ ˆ ˆ ˆ ˆ P sures an ensemble probability of simultaneously finding an electron on orbitals χi and χj .47. one predicts S = 0. (i. we shall use such diatomic (bonding) probability weights. j) represents an effective joint probability of orbitals χi and χj in a molecule. I = 0. in the N = 3. so that the decoupled subsystems appear naturally as those exhibiting infinitely small communications with the molecular remainder. [M] = [ϕbond. ]. [M(1)] = [ϕbond.95. and N = 0. MO the overall bond multiplicity remains almost the same as in the completely bonding 2 configuration of the two-electron system [M(2)] = [ϕbond. This is because the probabilistic models loose the “memory” about the relative phases of AO in MO [43–45]. electron system described 2 1 by the two-AO model. since ˆ χ Pϕ = Pϕ and Pϕ Pϕ = Pϕ . Therefore. ϕanti. In Section 8. which is retained by the elements of the quantum-mechanical CBO matrix and density of the nonadditive Fisher information [34–38].Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 21 to n by the choice of the flexible probabilities for each input represented by the conditional two-orbital probabilities. Indeed. the amplitude interpretation of Eq. [M(4)] = [ϕbond. Therefore. ]. which is not reflected by their condensed electron probabilities in atomic resolution. and N = 2. This diagnosis indicates a need for introducing into the MO-resolved scheme the information about the bonding/antibonding character of specific (occupied) MO. 43–45]. (28). It should be emphasized that in calculating the “ensemble” average bond components of Eq. I = N = 1. the product k pi P(k|i)P(j|k) = k P(i. For example. Similarly. Therefore. . ]. ]. this probabilistic approach cannot distinguish between the two bonding config1 2 urations for N = 1. . despite a half occupation of ϕanti. As we have shown in the previous section. in this approach only the covalent index reflects the nonbonding (noncommunicating) status of AO in this limit. ]. 5. k) P(j|k) ≡ Pens. when χi∈A and χj∈B . ϕanti.1a. for the total popu2 2 lation decoupling in the N = 4 electron system. It also has the conceptual and interpretative advantages by providing a unifying description capable of tacking both the coupled and decoupled molecular fragments in a single theoretical framework and generating the continuous description of the shape-decoupling limit. predicting the same bond indices. such an approach dramatically improves the agreement with the accepted chemical intuition. [M(3)] = [ϕbond. Moreover. in determining the effective IT descriptors of chemical interactions in diatomic fragments of the molecule. The same shortcoming is observed in the fixed-input OCT. (4) gives k pi P(j|k) ˆ ˆ ˆ ˆ P(k|i) ∝ pi k j|ϕ ϕ|k k|ϕ ϕ|i = pi j|Pϕ Pχ Pϕ |i = pi j|Pϕ |i ∝ pi P(j|i). POPULATIONAL DECOUPLING OF ATOMIC ORBITALS The previous formulation of CTCB in atomic resolution was shown to fail to predict a steady decrease in the resultant bond order with increasing occupation of the antibonding MO [9.

the problem of distinguishing between the two bonding cases.b (ϕs ) = H[p0 ]. p0 denotes the input probability in the ϕs infors mation channel. Alternatively. which recognizes that the full bonding/antibonding potential of the given MO is realized only when it is completely occupied.b (ϕs ) > 0. still remains. and nonbonding (zero). a half-bond for N = 1 and the full single bond for N = 2. 1). and by the corresponding MO probability PMO = {Ps = ns /N}. However. Ia. s (31) would then be straightforwardly recognized as bonding (positive). or antibonding (negative). this scheme correctly predicts the nonbonding (nb) character of such a hypothetical electronic structure: Snb = Inb = N nb = 0. b ∈ B). completely localized on a single orbital: p(a) = p(a0 ) = (1.b (ϕs ) = 0. when γa. when γa. Again. which .b (ϕs ) = S[Ps (b |a )]. the input-dependent probabilities separately exhibit the unit probability norm. the same result follows from the flexibleinput contributions to the system average entropy/information descriptors. 0) and p(b) = p(b0 ) = (0. This failure to properly reflect the intuitive MO-population trends by the IT bond indices calls for a thorough revision of the hitherto used overall communication channel in AO resolution. and the descriptors of the N = 3 channel also grossly contradict the chemical intuition.b (ϕs ) = H[p0 ] − S(ϕs ). The bond contributions between this pair of AO in the information system of sth MO. when γa. Obviously.b (ϕs ) < 0. Therefore. when both doubly occupied basis functions remain effectively nonbonding in the molecule. the purely molecular estimate of the mutual information Is [ps : ps ] can be used to index the localized bond ionicity. and Janusz Mrozek Let us now put to the test the performance of the flexible-input channels. In the limiting case of the complete population decoupling in the two-AO model. j) of AO. In combining such MO contributions into the corresponding resultant bond indices for the specified pair (i. [7b]). these increments should be subsequently multiplied by the MO-occupation factor f MO = { fs = ns /2}. Thus. Instead. s Na. one could envisage a use of the separate MO channels introduced in Section 2 (Eq.22 Roman F.b (ϕs ) + Ia. γ = 2I and hence P(b|a) = I. Sa. The resultant A–B descriptors would then be obtained by summation of such occupation/probability-weighted bonding or antibonding contributions from all occupied MOs.b (ϕs ) = Sa. let us assume for simplicity the two-AO model of the chemical bond A–B originating from the quantum-mechanical interaction between two AOs: χ = (a ∈ A. which were shown to properly account for the MO shape decoupling. the two completely occupied AOs remain effectively closed (noncommunicating and decoupled) for any level of their mixing measured by the AO-probability parameter P. Dariusz Szczepanik. which combines the contributions from all occupied MOs in the electron configuration in question. Here. As an illustration. Nalewajski.

3. (2b. in which the input ¯ probabilities are given by the corresponding products {ps = Ps ps }. (32) N(i. are reported in Scheme 1. j (ϕs )]Ps fs Ii. 7a. and 7a) that there are no analytical combination formulas [9] for grouping the partial MO bond indices of Scheme 1. their normalization requires that i p(i|s) = 1. and a variety of their nonvanishing communication connections between AOs generally differ from that for the system as a whole. j) = s sign[γi. j (ϕs )]Ps fs Si. j) = s sign[γi.5.Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 23 determine the system chemical bonds: S(i. where the MO probabilities PMO = {Ps } = (2/3. γ2 =  0 0 2 2 −1 0 1 1 2 1 √   2 2 √0 1 √ γ = γ1 + γ2 =  2 √2 2. with the ¨ consecutive numbering of 2pz = z orbitals in the carbon chain. j) = As shown in Scheme 1. Moreover. s I(i. j (ϕs ). j (ϕs ). √     2 √1 1 0 −1 √1 1 1 0 . j (ϕs )]Ps fs Ni. the MO channels are determined by their own CBO structure. In allyl such molecular inputs ¯ give the following IT descriptors of the two MO channels: S1 = P1 S1 = 1. γ1 =  2 √2 2. generated by the partial CBO matrices {γs }.4. . It follows from Eqs. The latter requirement is only satisfied when the two networks are parallely coupled [42] into the combined information system. Consider now another model system of the π electrons in allyl. Indeed. it is described by two occupied (canonical) MOs: 1 1 (doubly occupied) and ϕ1 = √ √ (z1 + z3 ) + z2 2 2 1 ϕ2 = √ (z1 − z3 ) (singly occupied). 2 which generate the corresponding MO and molecular CBO matrices. 1/3). ps = {p(i|s) = γij (s)/ns }. the input (conditional) probabilities used in Scheme 1.5 do not reflect the two MO channels being a part of the whole molecular channel. 2 0 2 2 (33) (34) and the molecular information system shown in Scheme 1. j (ϕs ).4.5 into their overall analogs of Scheme 1. In the Huckel approximation. using the MO-input probabilities of AO. The corresponding MO information systems. sign[γi. these resultant IT indices from the MO-resolved OCT do indeed represent adequately the population-decoupling trends for N = 1 ÷ 4 electrons in the two-AO model.

Dariusz Szczepanik. 2 S(ϕb ) − N(ϕb ) − I(ϕa ) = 0 1 2 Scheme 1. 3 S(ϕb ) − 1 S(ϕa ) = 2 H(P) I= 2 3 1 1 I(ϕb ) − 6 I(a) = 2 [1 − H(P)] 2 1 1 N = 3 N(ϕb ) − 6 N(ϕa ) = 2 ja jb γ= S= N= 1 2 2 0 0 2 1 2 1 2 P(b|a) = S(ϕa ) = 0 N(ϕa ) = 0 1 0 0 1 I= 1 2 P MO = I(ϕb ) − 1 2 1 1 2. 0) N = N(ϕb ) = 1 S = S(ϕb ) = H(P) √ I = I(ϕb ) = [1 − H(P)] ja jb γ= S= 2P + Q √ PQ 2 3 PQ 2Q + P 1 6 P(b|a) = (P + 1)2 /(3P + 1) PQ/(3P + 1) P MO = QP/(3Q + 1) (Q + 1)2 /(3Q + 1) 2 1 3.3 Decoupling of atomic orbitals in the MO-resolved OCT (2-AO model) with increasing occupation of the antibonding combination of AO. 0) N= 1 2 1 S = 2 S(ϕb ) = 1 2 1 I = 2 I(ϕb ) = N(ϕb ) = 1 2 ϕa ϕb γ=2 √P PQ √ PQ Q P(b|a) = P MO = (1. Nalewajski. . and Janusz Mrozek a Q P b P a P γb = nb Q Q b Q √ PQ √P PQ Q S(ϕb ) = H(P) 1 I(ϕb ) = H 2 − H(P) = 1 − H(P) I(ϕb ) = S(ϕb ) + I(ϕb ) = 1 (b) Q a P Q b Q a Q P P b P √ Q − PQ √ − PQ P S(ϕa ) = H(P) 1 I(ϕa ) = H 2 − H(P) = 1 − H(P) γa = na N(ϕa ) = S(ϕa ) + I(ϕa ) = 1 (c) ϕa ϕb γ= √P PQ √ PQ Q H(P) P(b|a) = P P 1 2 Q Q [1 − H(P)] P P Q Q P MO = (1.24 (a) P Roman F. while Panel c reports the associated probability/occupation-weighted indices. Panels a and b summarize the bonding and antibonding channels.

Such molecular inputs thus generate the nonvanishing IT ionicities.Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 25 p. j 1: p1 1/4 1/2 1/4 S1 = P1(b|a) z1 1/4 1/4 1/4 z2 1/2 1/4 1/4 z3 1/4 1 = 3/2 j 2: p1 z1 1/2 z2 1/2 z3 1/4 1/2 1/2 p2 1/2 P2(b|a) z1 1/2 1/2 p2 z1 1/2 1/4 I1 = 0 1/2 z3 2= 1 1/2 z3 1/2 S2 = I2 = 0 Scheme 1. which sum up to the ¯ ¯ ¯ group entropy I = I1 + I2 = H[PMO ] = − s Ps log2 Ps = 0.96. 1 ¯ ¯ ¯ I1 = −P1 log2 P1 = 0. ϕ1 . One then observes that the overall index of Scheme 1. (36) thus predicting roughly a single π bond in allyl. The latter result reflects the fact that only a single-bonding MO. p0 1/3 1/3 1/3 z1 2/3 1/3 1/4 z2 1/2 1/4 1/3 z3 2/3 z1 z2 z3 p* 11/36 7/18 11/36 S = 1. N = 1.92. gives a diminished bond multiplicity: ¯ ¯ ¯ ¯ ¯ ¯ ¯ N = f1 P1 S1 − f2 P2 S2 + ( f1 I1 − f2 I2 ) = f1 (S1 + I1 ) − f2 (S2 + I2 ) ¯ ¯ ≡ f1 N1 − f2 N2 = 0. whereas the antibonding combination ϕ2 of AO on peripheral carbon atoms remains practically nonbonding.46 N = 1. with f1 = 1 and f2 = 1/2.3. The corresponding MO bond indices (in bits) are also reported.4. can be reconstructed by adding to this additive-ionicity measure.39. S2 = P2 S2 = 3 .58 = H[p0 ]. I2 = −P2 log2 P2 = 0. predicting about 3/2 π -bond multiplicity in allyl.4 The molecular information channel of π electrons in allyl and its overall IT bond indices. the sum of the bonding (posi¯ tive) entropy-covalency S1 of the first MO and the antibonding (negative) ¯ 2 ) due to the second MO: contribution (−S ¯ ¯ ¯ S1 + (−S2 ) + I = N . (35) One also notices that the population-weighting procedure of Scheme 1.58 Scheme 1. is completely occupied. .11 I = 0. [33]).53.5 The molecular π-electron information systems for two occupied MOs in allyl (Eq.

and Janusz Mrozek ¨ In the same Huckel approximation the delocalized π bonds in butadiene 1 are determined by two doubly occupied canonical MOs with PMO = 1 . Dariusz Szczepanik.   2 b a2 ab ab a2  ab ab b2 b2 ab   γ1 = 2  ab b2 b2 ab .64 z4 1/4 =2 Scheme 1.36 z4 2/5 1/2 I = 0. 1).6 and 1. 1/4 z1 1/10 1/2 2/5 z1 1/4 1/4 2/5 z2 1/10 1/2 z2 1/4 1/4 1/10 z3 1/2 2/5 1/10 z3 1/4 1/4 S = 1. a= 1 1 1 − √ = 0. . 2 5 2(a2 + b2 ) = 1. 2 5 ϕ2 = b(z1 − z4 ) + a(z2 − z3 ). b= 1 1 1 + √ = 0.6015.6 The overall π -electron channel in OCT for butadiene derived from the H¨ ckel u MO. γ= √   0 1 5 √2  5 −1 0 2 5  ab −ab a2 −a2 2 −a a2 −ab ab  −b2 −ab . ab  b2 (38) generate the associated AO-information channels as shown in Schemes 1.7.26 Roman F. 2 2 MO and f = (1. γ2 = 2 −ab −b2 a2 ab ab a2 √  5 √ 2 0 −1 1  2 5 √ 1 0 . Nalewajski. ϕ1 = a(z1 + z4 ) + b(z2 + z3 ). (37) The corresponding CBO matrices.3717.

and the chemical coupling between χi and its counterparts on carbon atoms in the relative ortho-. which determine the π bonds in benzene. S ¨ In the Huckel theory the three occupied MO. 6 1 ϕ2 = (z1 + z2 − z4 − z5 ).3818 I1 = 0 S1 = N1 = 1.7 Probability scattering in the H¨ ckel π -MO channels of butadiene for the u representative input orbital zi = 2pz. γi. when one attributes ¯ ¯ ¯ different signs to these AO contributions. The overall data correctly predict the resultant double multiplicity of all π bonds in butadiene. where 1 stands for the unit row matrix.i and the associated MO entropies. meta-.i+3 = −1/3. PMO = 1 1. γi. b2 = 0. and para-positions. The resultant scattering of AO probabilities for the π electrons in benzene is shown in . b2 .i+2 = 0.85. respectively.1382. In the one-electron OCT treatment. γi. as reflected by the negative values of the corresponding elements in the MO CBO matrix. they exhibit rather substantial IT ionicity [48]. a2 ) a2 = 0. thus again predicting roughly two π bonds in the system. a2 . Therefore. 12 (39) They give rise to the overall CBO matrix elements reflecting the π-electron population on orbital χi = zi . I2 = 0 Scheme 1.i = 1. b2 .i = z1 . j 2: p(i|2) zi b2 a2 a2 b2 p2 = {p(i|2)} = (b2 .85. where ¯ s = Ps Ss .Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 27 j 1: p(i|1) zi a2 b2 b2 a2 z1 z2 z3 z4 z1 z2 z3 z4 p1 = {p(i|1)} = (a2 . A reference to the preceding equation indicates that a half of the reported entropy for ϕ2 is associated with the antibonding interactions between AOs.925. which indicates a high degree of determinism (localization) in the orbital probability scattering. a2 . The group ionicity I = I1 + I2 = MO 1¯ 1¯ ¯ ¯ H[P ] = 1 and hence Eq. the bonding and antibonding components in S2 cancel each other. (35) now reads S1 + 2 S2 − 2 S2 + I = 1. b2 ) S2 = N2 = 1. compared with the previous two-electron approach [9]. γi.i+1 = 2/3. read 3 1 ϕ1 = √ (z1 + z2 + z3 + z4 + z5 + z6 ). γi. 2 1 ϕ3 = √ (z1 − z2 − 2z3 − z4 + z5 + 2z6 ).

are positive (bonding). thus representing the antibonding interactions between AOs. which assume the maximum strength in the regular hexagon structure [64–67]. −2  2 4 (41) These CBO matrices of the occupied MO give rise to the following communications and input probabilities in the associated MO channels: 1 1  1 0 P2 (b|a) =  4 1  1 0  1 1 0 1 1 0 0 0 0 0 0 0 1 1 0 1 1 0 1 1 0 1 1 0  0 0  0 . Dariusz Szczepanik. z2 . p1 = 1. z6 ) 3 and all elements in the square matrix 1 are equal to 1. ˆ (40) γ2 = 2 χ |P2 |χ =  −1 −1 1 1 2 −1 −1 1 1 while γ3 explores the whole basis set χ :  1 −1 −2 −1 1 −1 1 2 1 −1   2 4 2 −2 ˆ 3 |χ = 1 −2 γ3 = 2 χ | P −1 1 2 1 −1 6  1 −1 −2 −1 1 2 −2 −4 −2 2  2 −2  −4 .58 Scheme 1. Scheme 1. 0  0 0 P1 (b|a) = 1 1 1. whereas half of them in γ2 and γ3 is negative. ˆ All matrix elements in γ1 = 2 χ |P1 |χ = ( 1 )1. the π -bond alternation is prevented by the stronger σ bonds. z4 .70 I2 = 0.28 Roman F. 6 6 . The overall bond multiplicity is somewhat lower that N = 3 predicted for the three localized π bonds in cyclohexatriene since in benzene. Nalewajski.i and the associated OCT entropy/information descriptors. z5 . where χ = (z1 . z5 ):   1 1 −1 −1 1 1 1 −1 −1 . z3 .89 N = 2.8 The probability scattering in benzene (H¨ ckel theory) for the representative u input orbital zi = 2pz. z4 .8. and Janusz Mrozek 1/6 zi 1/2 2/9 0 1/18 zi zi + 1 zi + 2 zi + 3 S = 1. z2 . The nonvanishing elements in γ2 are limited to the subset χ = (z1 .

0). As discussed elsewhere [9.25. 4. 1. S3 = N3 = 2. Since the OCT analysis of the bonding patterns in molecules provides the supplementary. 1. 12 The corresponding entropy/information descriptors then read as follows: S1 = N1 = 2. 4  4 4 (42) p3 = 1 (1. S2 = N2 = 2. 4). I1 = 0. BOND DIFFERENTIATION IN OCT It has been demonstrated elsewhere that the bond alternation effects are poorly represented in both the CTCB formulated in atomic resolution [9] and in its OCT (fixed-input) extension [48]. the entropy/information indices for the given pair of atomic orbitals can be extracted from the relevant partial channel. The problem can be best illustrated using the simplest allyl case. to generate more realistic “chemical” trends of the π -bond alternation patterns in the three illustrative systems of the preceding section. The OCT indices from the alternative output reduction schemes have been shown to give more realistic but still far from satisfactory description of the bond alternation trends in these molecular systems [48]. (43) ¯ ¯ ¯ ¯ ¯ The group ionicity I = I1 + I2 + I3 = H[PMO ] = 1. 6. a posteriori description to the standard MO scheme in this section we shall attempt to use this extra information.9. I3 = 0.Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 29 p2 = 1 (1. 22].5)-bond multiplicity. defining the localized chemical interaction of interest. 1. which includes all AO inputs (sources of the system chemical bonds) and the twoorbital outputs in question.58 and S1 = S1 /3 then also gives rise to roughly (2. particularly in the separate CBO contributions {γs } from each occupied MO. In Scheme 1. However. 1. 0. 1.58. two examples of such partial information systems are . 4 1 1  1 1  P3 (b|a) = 12 1  1 1  1 1 1 1 1 1 4 4 4 4 4 4 1 1 1 1 1 1 1 1 1 1 1 1  4 4  4 . with the bonding (positive) and ¯ ¯ antibonding (negative) contributions in S2 and S3 approximately canceling each other. This is because in purely probabilistic models. the bonding and antibonding interactions are not distinguished since conditional probabilities (squares of the MO-CBO matrix elements) loose the information about the relative phases of AO in MO. I2 = 0. this distinction is retained in the off-diagonal CBO matrix elements. directly available from the standard SCF MO calculations. 1.

thus failing completely to account for the π -bond alternation.24 N (1.05 1/3 (b) 1/3 z3 z1 z2 z3 1/3 2/3 z1 11/36 1/4 1/3 S(1. with γi. It follows from these illustrative sets of indices that the two partial channels give rise to identical overall index N . Dariusz Szczepanik. In the Huckel theory the corresponding partial information systems in the butadiene π -electron system predict identical indices for all pairs of orbitals. 2) = 1. 2) = 0.68.59 I(1. 2) = 0.45 N (1. including the two specified orbitals in their input and output. one has to bring into play the known signs of interactions between the specified pair (i. j) = 0. j (s) = 0 corresponding to the nonbonding (zero communication) case. It should be observed that in the flexible-input approach of Section 4 the nonbonding AOs. I(i. and using the fragment-renormalized MO probabilities [9. by removing communications involving the third. j (s) < 0. j) of AO in the given MO ϕs . and N (i.9 The molecular partial information channels and their entropy/information descriptors of the chemical interaction between the adjacent (Panel a) and terminal (Panel b) AO in the π-electron system of allyl. They have been obtained from the molecular channel of Scheme 1.93. j) = 0. z2 ) and terminal (z1 . remaining AO of this minimum basis set of π AO. This extraneous information determines the signs of contributions in the weighted contributions of Eqs. which . (31 and 32) from the partial MO channels. j) = 0. with only the IT-covalent/ionic components differentiating the two bonds: the nearest neighbor interaction exhibits a higher “noise” (covalency) component and ¨ hence the lower information-flow (ionicity) content.30 (a) 1/3 Roman F.4. γi. j (s) > 0. or antibonding (involving a “destructive” interference). 3) = 0. displayed for the nearest neighbor (z1 . To remedy this shortcoming of the communication theory. in order to recognize them as bonding (exhibiting a “constructive” interference). γi. 3) = 0. Nalewajski. 3) = 1.05 1/4 1/3 2/3 z3 11/36 Scheme 1.25.82 I(1. z3 ) chemical interactions. and Janusz Mrozek z1 1/3 2/3 z1 z2 11/36 1/3 z2 1/4 1/2 7/18 S(1. 26]. The MO-resolved channels are vital for the success of such an approach since the bonding interaction between the given pair of AOs in one MO can be accompanied by the antibonding interaction between these basis functions in another occupied MO. S(i.

3 (ϕ1 ) = 1 N1. communicate only with themselves. f MO = 1. Let us similarly examine the localized π interactions in butadiene. A 2 reference to Eq. b2 ). which exhibit somewhat diminished bond multiplicity to about 92% . 4 .3 (ϕ1 ) = 1 1/2 1/2 z3 z1 1/4 1/4 ϕ 2 : γ1. for 1 1 2 which PMO = 3 .3 (ϕ2 ) = 1 I1.10 The partial MO-information channels and their entropy/information descriptors of the chemical interactions between the nearest neighbor (Panel a) and terminal (Panel b) AO in the π-electron system of allyl. b2 . and p2 = (b2 . 1 . b2 . while the remaining AO combinations involve the bonding contribution from ϕ1 and the antibonding from ϕ2 . 3) = 2/3 − 1/6 = 1/2 I(1.2 (ϕ1 ) = 0 I(1. p1 = (a2 .11 (see also Scheme 1.2 (ϕ1 ) = 1 N(1. thus not contributing to the resultant bond descriptors. An illustrative application of such scheme to π electrons in allyl.1b. while the effective z1 –z3 interaction combines the bonding contribution due to ϕ1 and the antibonding increment originating from ϕ2 . gives rise to the separate AO channels of Scheme 1. a2 ). This scheme is seen to generate (2/3)-bond multiplicity between the nearest neighbors and a weaker half-bond between the terminal carbon atoms. p1 = 1 . 2) = 2/3 ϕ 1 : γ1. 2) = 0 N1. 2 . a2 . exhibit only the bonding interactions in ϕ1 and ϕ2 . 3) = 0 Scheme 1. f MO = (1. 1 . These diatomic IT indices predict the strongest terminal (1–2) or (3–4) π bonds. 2) = 2/3 S(1. 3 (ϕ2 ) < 0 S1. and p2 = 1 . The reason for a finite value of this bond index in OCT is the dominating delocalization of electrons in ϕ1 throughout the whole π system. These MO increments are summarized in Scheme 1. 0. for 1 which PMO = 2 .7). 2 (ϕ1 ) > 0 S1. a2 .10.3 (ϕ2 ) = 1 N(1. 1).2 (ϕ1 ) = 1 I1. One observes that z1 –z2 interaction has only the bonding contribution from ϕ1 .Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory (a) z1 – z2: 1/3 z1 1/2 2/3 (b) z1 – z3: 1/2 z1 1/4 1/4 1/4 z3 z1 1/2 1/2 1/2 z3 1/2 z3 1/2 1/4 1/2 z1 1/4 1/4 z2 1/2 z2 1/2 1/4 z1 1/4 31 ϕ1: γ1. (38) indicates that the equivalent terminal pairs of AO.3 (ϕ2 ) = 0 N1. z1 –z2 and z3 –z4 . 3 (ϕ1 ) > 0 S1. is reported 3 4 2 2 2 in Scheme 1.3 (ϕ1 ) = 1 I1. This somewhat contradicts the Wiberg’s covalency indices predicting a half z1 –z2 bond and a vanishing z1 –z3 interaction. 1 . 1 . 3) = 1/2 S(1.

3) = 0. 3) = N(1. which are obtained from Eq.3 = 0.12 summarizes the elementary entropy/information increments of the diatomic bond indices generated by the MO channels of Eq. Scheme 1. while the chemical interaction between terminal carbons (1–4) is diagnosed as being antibonding in character. with the bonding and antibonding contributions identified by the signs of the corresponding coupling elements in the MO density matrices {γs }. one finds the following IT bond indices: S(1. 4) = N(1. and para 1 π bonds in benzene. This weighted MO approach makes a separate use of the diatomic parts of the canonical MO channels. respectively.2 = M3.2.52. and para-positions. M1. 1). 4) = −0. in full conformity with the negative value of the corresponding off-diagonal element in the overall CBO matrix (Eq. S(para) = N(para) = − 0. It should be realized that while the canonical (delocalized) MO completely reflect the molecular symmetry. M1. For example. They give rise to the corresponding diatomic descriptors. The middle (2–3) π bond measures about 14% of the ethylene reference value. S(1. However. 48]. j = γi. the bond indices generated in this scheme must exhibit some dispersions so that they have to be appropriately averaged with respect to the admissible choices of the corresponding orbital pairs to ultimately generate the invariant entropy/information descriptors of the ortho-.32 Roman F. which unrealistically equates the partial bonding (2–3) and antibonding (1–4) interactions. Therefore. PMO = 1 . by selecting i = 1 of the diatomic fragment consisting additionally the j = 2. S(meta) = N(meta) = 0.2j of Wiberg.8.25.42. (42). meta-. S(1. Nalewajski. and M1. We further observe that in this π system. Dariusz Szczepanik. 2) = 0. as indeed reflected by the overall CBO matrix elements. these predictions exhibit some dispersions when one explores other pairs of carbon atoms in the ring. 3.and para-positions in benzene [9. These predictions correctly identify the bonding. 2) = N(1. 1 . meta-. As final example let us reexamine from the present perspective a differentiation of the localized π -bonds between the two carbon atoms in the relative ortho-. and the vanishing bond orders of the (1–3) and (2–4) interactions. 3 3 3 MO and f = (1.4 = M2. (32). and the antibonding characters of π bonds between two carbons of the benzene ring in the relative ortho-. [38]).06. a practically nonbonding. .19.01. due to a nonsymmetrical (fragment) use of the symmetrical MO channels. and Janusz Mrozek of the unit value in ethylene. 4 carbon.4 = 0. meta.3 = M2. giving rise to the following average descriptors: S(ortho) = N(ortho) = 0. These predictions should be compared with the associated quadratic indices Mi.4 = 0. its diatomic fragments do not. 1.

γ1.3 (ϕ2 ) < 0 S1. the magnitudes of these IT indices generally agree with the corresponding Wiberg indices: Mortho = 0.2 (ϕ2 ) = 0. S(1.2 (ϕ2 ) > 0.2 (ϕ1 ) = 0.3 (ϕ2 ) = 0 z2 a2 z3 a2 1/2 z3 a2 S(2.3 (ϕ1 ) = 0 b2 b2 a2 ϕ2: γ1. 3) = 0.4 (ϕ1 ) = N1. I(2.925. 4) = N(1.2 (ϕ1 ) > 0. 3) = 0 Scheme 1.789 I2.925 I1.4 (ϕ2 ) = 0 1/2 (c) z2 – z3: 1/2 z4 b2 S(1.3 (ϕ2 ) = N1. Again. 3) = N(1.4 (ϕ2 ) = N1. enforced by the stronger σ bonds [64–67]. 4 (ϕ2 ) < 0 S1.136. The above ortho result shows that the overall IT bond multiplicity between the nearest neighbors N(ortho) ∼ 0. 3 (ϕ2 ) < 0 S2. 3) = 0.3 (ϕ1 ) = 0.3 (ϕ2 ) = 0.925 I1.2 (ϕ2 ) = N1.Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 33 (a) z1 – z2. 3) = N(2.4 (ϕ1 ) = 0 1/2 1/2 a2 b2 b2 z4 z1 a2 b2 ϕ2: γ1. 3) = 0.2 (ϕ1 ) = 0. 3 (ϕ1 ) > 0 S2. . 4) = −0. Mmeta = 0.3 (ϕ1 ) = N1. this distinction is lost. that OCT properly recognizes the para interactions in benzene as antibonding. I(1.4 (ϕ2 ) = 1.3 (ϕ1 ) = 1.2 (ϕ2 ) = 0 S1. I(1. and Mpara = 0. due to the effect of the prohibited bond alternation.3 (ϕ2 ) = 0 S(1.11 The partial MO-information channels and their entropy/information descriptors for the two-orbital interactions in the π -electron system of butadiene.3 (ϕ1 ) = 0 1/2 1/2 b2 a2 a2 z3 z2 b2 a2 ϕ2: γ2.3 (ϕ2 ) = N2.925 I1.44. Note.061 I1. 2) = 0.11. γ1.061 I2.789 I1. compared with N = 1 in ethylene.2 (ϕ1 ) = 0 S1. whereas in the Wiberg scheme. 2) = 0 z2 b2 z3 b2 b2 z2 b2 ϕ1: γ2.925 I1.3 (ϕ1 ) = N2. 2) = 0 z1 a2 ϕ1: 2b2 2b2 2a2 a2 z2(3) z1 a2 z2(3) b2 γ1.2 (ϕ1 ) = N1. however.136.3 (ϕ1 ) > 0 S1. 2) = N(1. z1 – z3: 2a2 z1 a2 b2 b2 b2 a2 z2(3) z1 z2(3) I(1. (b) z1 – z4: 1/2 z1 a2 a2 z4 z1 b2 z4 b2 a2 z1 a2 ϕ1: γ1. 4 (ϕ1 ) > 0 S1.3 (ϕ2 ) = 0.5 is indeed compromised in benzene.

4 (ϕ3 ) > 0 Si. z4. j (ϕ3 ) = Ni. in the coordination compounds of transition metal ions or in SF6 . e = x. j (ϕ1 ) = 0.4 (ϕ2 ) = γ2. the octahedral complex XL6 with the ligands placed along the axes of the Cartesian coordinate system: {L1 (e). z4. j (ϕ2 ) = 0 (zi ≠ zj) ∈(z1.4 (ϕ2 ) = γ1. LOCALIZED σ BONDS IN COORDINATION COMPOUNDS The decoupled description of hydrides (Section 3) can be naturally extended into the localized σ bonds between the central atom/ion X and the coordinated ligands {Lα }. z4. z.5 (ϕ2 ) = γ2.597 Ii. z2.5 (ϕ2 ) < 0 Si. for example. j (ϕ1 ) = 0 zi 1/4 1/4 1/4 zj 1/4 zi zj 1/4 1/4 γ1. z5) 1/5 4/5 zi 1/12 1/3 1/12 zj 1/3 zi zj 1/12 1/3 γ1.5 (ϕ2 ) > 0 γ1. j (ϕ2 ) = Ni. z3.057 I3. z5.6 (ϕ3 ) = 1.12 The elementary entropy/information contributions to chemical interactions between two different AOs in the minimum basis set {zi = 2pz.6 (ϕ3 ) = γ3. z2.827 Ii.3 (ϕ3 ) = γ2. z4. z6) 1/2 1/2 (b) j 2: (zi ≠ zj) ∈(z1. 2 (ϕ2 ) = γ4. z2. j (ϕ3 ) = Ni.2 (ϕ3 ) = γ1.4 (ϕ3 ) = γ2. z6) 1/2 1/2 z3 1/3 1/3 1/3 z6 1/3 z3 z6 1/3 1/3 γ3.j (ϕ3 ) = 0 zi ∈(z3.5 (ϕ3 ) < 0 γ1. j (ϕ1 ) = Ni. y.34 (a) j 1: Roman F. z5) 1/2 1/2 zi 1/12 1/12 1/12 zj 1/12 zi zj 1/12 1/12 γ1. j (ϕ1 ) > 0 Si. Consider.5 (ϕ3 ) = γ4.6 (ϕ3 ) = 0 zi 1/6 1/6 1/6 zj 1/6 zi zj 1/6 1/6 γi.i } of the π-electron system in benzene.4 (ϕ3 ) = γ5. j (ϕ3 ) = 0.3 (ϕ3 ) = γ3. Nalewajski. L2 (e)}. and Janusz Mrozek (zi ≠ zj) ∈(z1. z6). The X–Lα bond then results from the chemical interaction .5 (ϕ3 ) = γ2.6 (ϕ3 ) < 0 γ1.6 (ϕ3 ) = γ2.6 (ϕ3 ) > 0 Si.5 (ϕ3 ) = γ4. z3. Dariusz Szczepanik. z2. zj ∈(z1. j (ϕ3 ) = 0 Scheme 1.6 (ϕ3 ) < 0 S3. z5) 1/2 1/2 (c) j 3: (zi ≠ zj) ∈(z3. j (ϕ2 ) = 1 Ii. for example. 7.6 (ϕ3 ) = N3.862 Ii. j ϕ3 ) = 0.

(45) Indeed. is thus accompanied by the vanishing IT ionicity. nb = Nσ (α) = 2. = 1. Iα (a0 : bα ) = 6[1 − H(P)]. γHα .3). γHα . now include the (doubly occupied) bonding MO ϕb (α). (46) which do not contribute to the entropy/information indices of the localized chemical bond. Imax. which determines the communication channel of the separate bond M–Lα . .Hα = (2 − na ) PQ. determines the maximum value of the magnitude of the coupling CBO element γHα . α α I(P) = N = 6. in general partly occupied with na = NX (α) electrons originating from X. that is. . γHα . Smax.Hα = γσα . It follows from these expressions that in the latter case . For na = 0. α = 1. (44) The associated CBO matrix elements and the corresponding conditional probabilities they generate now depend on the initial number of electrons na on Hα . The corresponding localized MO.Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 35 between six acceptor (partially occupied) d2 sp3 hybrids {Hα } of X and the corresponding donor (doubly occupied) {σα } orbitals of ligands. = 0.σα = γσα . decoupled subchannels for each orbital. ϕa (α) = − QHα + √ Pσα .σα = 2Q + na P. for example. 2. and the antibonding MO ϕa (α). σα = γσα . σα ): ϕb (α) = √ PHα + Qσα . 6. which are contributed by X to the αth σ bond (see also Scheme 1. . which result from the two basis functions χ α = (Hα . (47) The highest IT covalency of the σ bond M–Lα . in SF6 .1a. na = 0. the empty antibonding MO.3c. the IT bond indices correctly predict the overall IT multiplicity reflecting the six decoupled bonds in this molecular system: S(P) = α Sα (bα |aα ) = 6H(P). . when X–Lα channel is given by Scheme 1. The corresponding conditional probabilities Pα (bα |aα ) ≡ Pα [χ α |χ α ] for the single and double occupations of ϕa (α) are reported in the corresponding diagrams of Scheme 1.σα = 2 and γHα . γσα . while the double occupation of ϕa (α) gives rise to the nonbonding state corresponding to the separate. and na = 1 diminishes it by a factor of 2. P + Q = 1. predicted for the strongest mixing of orbitals P = Q = 1/2. Hα = 2 PQ.Hα = 0.σα = γσα . with the two electrons originating from the donor σα orbital.Hα = 2P + na Q.

948 Scheme 1. the off-diagonal elements identically vanish. which recognizes the bonding and antibonding contributions to the resultant bond multiplicity from the signs of the corresponding CBO matrix elements of the system-occupied MO.3c) and the maximum covalency combination P = Q = 1/2.469 (b) p0 1 3 2 3 P(b|a) H 0. Panel b). Therefore.9 H σ p 1 2 1 2 Smax.3c). = 0.1 σ 0.σα = γσα . thus giving rise to the decoupled pair of orbitals and hence to the deterministic channel of Scheme 1. however. 8. one obtains a strongly deterministic information system as shown in Scheme 1. which is lost in the conditional probabilities. Panel a) and ionic (promolecular input. and Janusz Mrozek p 1 2 1 2 P(b|a) H 0.Hα = 0. for P = Q = 1/2. γHα . the contributions due to each AO input should be . RESTRICTED HARTREE–FOCK CALCULATIONS In typical SCF-LCAO-MO calculations the lone pairs of the valence and/or inner shell electrons can strongly affect the IT descriptors of the chemical bond. It follows from these diagrams that the fixed-input approach predicts a practically conserved overall bond order compared with the na = 0 case (the second diagram in Scheme 1. Nalewajski. Therefore. = 0.9 0.1 0.36 (a) Roman F.3. and the singly occupied antibonding MO: covalent (molecular input. Dariusz Szczepanik.13 The orbital-communication channels for the localized M–Lα bond in the fixed-input approach. with the bond weakening being reflected only in the bond composition with now roughly equal (half-bond) covalent and ionic components. It should be emphasized.9 0.1b for each of them (see the fourth diagram in Scheme 1. such separate channels do not contribute to the overall IT bond descriptors. the populational decoupling trends of AO in the coordination bond are properly reflected only in the flexible-input (MO-resolved) description.479 Nmax. As already discussed in Scheme 1. open-shell configuration na = 1 (the third diagram in Scheme 1.13.1 0.1 σ 0. For the partly bonding.3c).9 H σ p∗ 11/30 19/30 Imax. that such treatment ceases to be purely probabilistic in character since it uses the extraneous piece of the CBO information. = 0.

(49) where P(Y|i) measures the conditional probability that an electron on χi will be found on atom Y in the molecule. B)] ≡ {P(j|χAB ). which miss the probability propagations originating from AO of the remaining constituent atoms χ Z ∈ χAB . involving AO contributed by these two bonded atoms. B). to the overall basis set χ = {χX }. B|i)}.B|i) = P(A|i) + P(B|i) = j∈(A. which determines the molecular communication system in OCT [46–48] of the chemical bond: P(χAB |χAB ) ≡ [P(χY |χX ). χB ). P(B|χAB )] = P(X|χAB ) ≡ {P(X|i)}= j∈X P(j χAB ). X = A.1. χj ∈ χAB } ≡ {P(j|i). 8. In this section we describe such an approach to diatomic chemical interactions in molecules and present numerical results from standard RHF calculations for a selection of representative molecular systems. linking the condensed atomic output (A. the square matrix P(χAB |χAB ) contains only the intrafragment communications. two-orbital probabilities that reflect the actual participation of each AO in the system chemical bonds. B) and the given AO input χi in the associated communication system of the diatomic fragment: P(A|χAB ) + P(B|χAB ) = P(A. χi ∈ χAB . B|χAB ) = P(A.Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 37 appropriately weighted (see Eqs.B) P( j i) ≤ 1 . The sum of these conditional probabilities over all AOs contributed by the two atoms then determines the communication connections {P(A. B . χj ) ∈ χAB )}. Orbital and condensed atom probabilities of diatomic fragments in molecules The molecular probability scattering in the specified diatomic fragment (A. Y) ∈ (A. / The atomic output reduction of P(χAB |χAB ) [9] gives the associated condensed conditional probabilities of the associated molecular information system. is completely characterized by the corresponding P(χAB |χAB ) block [22. 26] of the molecular conditional probability matrix of Eq. (χi . (4). [28 and 29] in Section 4) using the joint. (50) . P(XAB |χAB ) = [P(A|χAB ). (48) Thus. (X. χAB = (χA .

i . via relevant partial summations.B) γi. {PAB (X. B reads: NX (AB) = i∈(A. P(A. (54) These vectors of AO probabilities in diatomic fragment AB subsequently define the condensed probabilities {PX (AB)} of both bonded atoms in subsystem AB: PX (AB) = NX (AB) = NAB PAB (X. (51) where NAB stands for the number of electrons in the specified diatomic frag˜ ment of the molecule and pi (AB) denotes the probability that one of them occupies χi∈(A. i) = j∈X ˜ PAB (i. The inequality in the preceding equation reflects the fact that the atomic basis functions participate in chemical bonds with all constituent atoms. i) = i∈(A. B. 2 (56) . with the equality sign corresponding only to a diatomic molecule. (53) For the closed-shell molecular systems one thus finds ˜ PAB (X. and Janusz Mrozek In other words. p NAB = i∈(A. j) = pi (AB)P(j|i) = γi.j γj. Nalewajski. i) = pi (AB) j∈X P( j i) = j∈X γi.i /NAB }. (52) They generate. χAB ) = [PAB (A.i . Dariusz Szczepanik. i∈(A.38 Roman F. 2NAB X = A.B) j∈X γi. B .j γj. B.B) i∈(A. i)}: PAB (XAB . χAB ) = PAB (X. χAB ).j γj. PAB (B. The fragment-normalized AO probabilities ˜ p(AB) = {˜ i (AB) = γi.B) ˜ pi (AB) = 1.j γj.i .i /(2NAB )}. χAB ) = {PAB (i. then determine the simultaneous probabilities of the joint two-orbital events [47]: ˜ PAB (χAB . (55) where the effective number of electrons NX (AB) on atom X = A.i . 2NAB X = A. when χAB = χ .B) j∈X γi. χAB )] = PAB (X. X = A.B|i) measures the probability that the electron occupying χi will be detected in the diatomic fragment AB of the molecule.B) . the joint atom-orbital probabilities in AB. j) ≡ pi (AB)P(X|i).

j∈X X = A. i) = Pb (B. (52 and 53): Pb (A. i ∈ B} and {PAB (B. (59) involves symmetrically the two bonded atoms. i). i ∈ (A. {PAB (A. thus effectively excluding the contributions to the entropy/information bond descriptors due to the lone-pair electrons. i).i γi. when χAB = χ .A) = i∈A j∈B γi. (3). 55) do not reflect the actual AO participation in all chemical bonds in AB. such joint bond probabilities emphasize of AOs have both atoms are simultaneously involved in the occupied MOs. giving rise to comparable values for the bonding and nonbonding (lone-pair) AO in the valence and inner shells. (50). one finds using the idempotency relations of Eq. B|i)/2. B|χAB ) = {P(A. B|i)} of Eq. Thus. B)}.Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 39 Therefore. The relative importance of basis functions of one atom in forming the chemical bonds with the other atom of the specified diatomic fragment is reflected by the (nonnormalized) joint bond probabilities of the two atoms. to be used as weighting factors in the average conditionalentropy (covalency) and mutual-information (ionicity) descriptors of the AB chemical bond(s). indeed assume appreciable magnitudes only when the electron occupying the atomic orbital χi of one atom is simultaneously found with a significant probability on the other atom. B) ≡ i∈B PAB (A. The reference bonding probabilities of AO have to be normalized to the corresponding sums P(A.j = NAB ˜ pj (AB). (52–54) and the associated condensed probabilities of bonded atoms (Eq.i . the last relation does not hold for diatomic fragments in larger molecular systems. we apply the same principle to determine the associated reference bond probabilities of AO to be used to calculate the mutual-information bond index: {pb (i) = P(A. (58) We finally observe that the effective orbital probabilities of Eqs. Clearly. B. i ∈ A}. (57) and hence PA (AB) + PB (AB) = 1. so that in ˜ general PX (AB) = j∈X pj and PA (AB) + PB (AB) = 1.j 2NAB = j∈X γj. 2NAB (59) The underlying joint atom-orbital probabilities. i) = i∈A PAB (B. PX (AB) = j∈X i γj. for which χAB = χ . (60) . in diatomic molecules. defined by the diatomic components of the simultaneous probabilities of Eqs. Since the bond probability concept of Eq.j γj.

i) H(χAB |i).40 Roman F. i) H(χAB |i). Dariusz Szczepanik. Nalewajski. 46–48]. (63) Again. Average entropic descriptors of diatomic chemical interactions As we have already mentioned in Section 2. the probability-weighted contributions to the average mutual-information quantities of bonded atoms are defined in reference to . (61) the conditional entropy SAB (Y|χ X ) quantifies (in bits) the delocalization X→Y per electron so that the total covalency in the diatomic fragment A–B reads as follows: SAB = NAB [HAB (B|χ A ) + HAB (A|χ B )]. respectively. in OCT the complementary quantities characterizing the average noise (conditional entropy of the channel output given input) and the information flow (mutual information in the channel output and input) in the diatomic communication system defined by the conditional AO probabilities of Eq. (48) provide the overall descriptors of the fragment bond covalency and ionicity.and valence-shell lone pairs. since these weighting factors reflect the actual orbital participation in the fragment chemical bonds.B) P(j|i)log2 P(j|i). HAB (A|χ B ) = i∈B PAB (A. 8. Accordingly. Y = X}. (61) as weighting factors of the corresponding contributions due to the specified input AO. it should be emphasized that the simultaneous (diatomic) probabilities {PAB (X. In the A–B fragment development we similarly define the following average contributions of both constituent atoms to the diatomic covalency (delocalization) entropy: HAB (B|χ A ) = i∈A PAB (B. Both molecular and promolecular reference (input) probability distributions have been used in the past to determine the information index characterizing the displacement (ionicity) aspect of the system chemical bonds [9. and Janusz Mrozek where P(A. (61) where the Shannon entropy of the conditional probabilities for the given AO input χi ∈ χAB = (χA . i ∈ Y).2.B|i) denotes the probability that an electron originating from orbital χi will be found on atom A or B in the molecule. effectively eliminate contributions due to the inner. used in Eq. (62) In Eq. χB ) in the diatomic channel: H(χAB |i) = − j∈(A.

Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 41 the unbiased bond probabilities of AO (Eq.j . the single chemical bond between two “hard” atoms in HF appears predominantly covalent. the sum of the above total (diatomic) entropy-covalency and information-ionicity indices determines the overall information-theoretic bond multiplicity in the molecular fragment in question: NAB = SAB + IAB . IAB (χ B : A) = i∈B PAB (A. the trends exhibited by the entropic covalent and ionic components of a roughly conserved overall bond order also agree with intuitive expectations.1 and 1. with the extended basis set predictions being slightly closer to the familiar chemical estimates of the localized bond multiplicities in these typical molecules.2 also reveals generally weak dependence on the adopted AO representation. reporting the numerical RHF data of bond orders in diatomic fragments of representative molecules for their equilibrium geometries in the minimum (STO-3G) and extended (6-31G*) basis sets. (67) which has been previously shown to adequately reflect the chemical intuition in the ground state of typical molecular systems. (65) Finally.B) They generate the total information ionicity of all chemical bonds in the diatomic fragment: IAB = NAB [IAB (χ A : B) + IAB (χ B : A)]. (64) pb (i) I(χ AB : i) = j∈(A. For example. A comparison between corresponding entries in Table 1. i)I(χ AB : i). in hydrides or halides. . i)I(χ AB : i).2. [60]): IAB (χA : B) = i∈A PAB (B.j = i∈A j∈B Mi. for example. respectively. It follows from both these tables that the applied weighting procedure gives rise to an excellent agreement with both the Wiberg bond orders and the chemical intuition. In a series of related compounds. P(j|i)log2 P(j|i) . (66) They can be compared with the diatomic (covalent) bond order of Wiberg [52] formulated in the standard SCF-LCAO-MO theory. MAB = i∈A j∈B 2 γi. Such a comparison is performed in Tables 1.1 and the upper part of Table 1.

511 0. although a substantial ionicity is detected for LiF. both approaches give approximately a single-bond estimate.023 0.071 0. and the triple bond in CO is accurately accounted.000 0.066 0.013 3.071 0.444 0. The significant information-ionicity contribution is also detected for all halides in the lower part of Table 1.42 Roman F.973 2.984 3.091 0.119 SAB 1.976 1. The chemical orders of the single and multiple bonds in ethane.003 0.412 0.144 0. for which both Wiberg and information-theoretic results predict roughly (3/2)-bond in the minimum basis set.980 0. Dariusz Szczepanik.000 0.311 0. . and the increase in the strength of the central bond in propellanes with increase of sizes of the bridges is correctly predicted [9]. and Janusz Mrozek Table 1.592 2.069 1.887 0.939 1.086 1.999 0.619 0.2.093 0.934 0.035 1 For the sequential numbering of carbon atoms in the benzene ring.084 IAB 0.025 1.991 2.003 0.000 0. in the extended basis set.000 0. One also finds that all carbon–carbon interactions in the benzene ring are properly differentiated.947 0.1 Comparison of the diatomic Wiberg and entropy/information bond multiplicity descriptors in selected molecules: the RHF results obtained in the minimum (STO-3G) basis set Molecule H2 F2 HF LiH LiF CO H2 O AlF3 CH4 C 2 H6 C 2 H4 C 2 H2 C 6 H1 6 A–B H–H F–F H–F Li–H Li–F C–O O–H Al–F C–H C–C C–H C–C C–H C–C C–H C1 –C2 C1 –C3 C1 –C4 MAB 1.997 0.094 0. The differentiation of the “equatorial” and “axial” S–F bonds in the irregular tetrahedron of SF4 is reproduced.526 0.605 0.000 0.980 1.980 1. Nalewajski.063 1.991 1.045 0. ethylene.116 NAB 1.009 1.605 1.986 1.947 2. Even more subtle bond differentiation effects are adequately reflected by the present information-theoretic results. and acetylene are also properly reproduced.000 0.079 0.859 0.000 1. consisting of approximately one covalent and 1/2 ionic contributions.151 0. with the information theory predicting the ionic dominance of the overall bond multiplicity.000 1.000 0.000 1.093 1.087 0.781 0.998 0.000 0.018 2.053 0.998 1.592 2.000 1.028 0.021 1.062 0.

095 0.757 0.081 0.066 0.851 0.935 3.926 0.986 IAB 0.598 1.014 0.906 0.323 0.2.603 0.035 0.1] [2.162 0.097 0.943 1.896 1.371 0.732 0.114 1.391 1.976 1.394 0.078 0.979 0.627 0. respectively. .834 1.129 0.1] [2.823 0.119 0.476 0.860 0. Ht and Hb denote the terminal and bridge hydrogen atoms.967 3.1] [2.106 0.055 0.967 0.476 0.797 0.147 0.391 1.1.2] 1 2 For the sequential numbering of carbon atoms in the benzene ring.507 0.254 0.005 1.089 0.009 NAB 1.878 1.490 0.192 0.226 0.234 0.406 0.121 2.878 1.218 0.002 1.005 1.592 0.184 0.829 0.118 0.463 0.878 3.028 0.794 0.065 0.879 2.908 1.462 0.2 The same as in Table 1.106 0.117 1.670 0.533 0.938 0.834 1.473 0.371 0.004 0.921 1.662 0.154 1.429 0.985 2.057 0.085 1.121 2.662 0.063 LiCl LiBr NaF KF SF2 SF4 SF6 B2 H2 6 Propellanes3 [1.787 0.904 0.726 0.2.228 0.494 2.049 SAB 1.061 0.946 1.112 0.404 0.072 0.1 for the extended 6-31G* basis set Molecule F2 HF LiH LiF CO H2 O AlF3 CH4 C 2 H6 C 2 H4 C2 H2 C6 H1 6 A–B F–F H–F Li–H Li–F C–O O–H Al–F C–H C–C C–H C–C C–H C–C C–H C1 –C2 C1 –C3 C1 –C4 Li–Cl Li–Br Na–F K–F S–F S–Fa S–Fb S–F B–B B–Ht B–Hb Cb –Cb Cb –Cb Cb –Cb Cb –Cb MAB 1.024 0.662 0.394 0.681 0.064 0.228 0.063 0. 3 Central bonds between the bridgehead carbon atoms Cb .128 0.035 0.394 0.081 0.816 1.906 0.904 0.748 0.986 1.060 1.874 0.Bond Differentiation and Orbital Decoupling in Orbital-Communication Theory 43 Table 1.273 0.002 0.955 2.729 0.995 0.1.978 0.816 1.108 0.912 0.059 0.827 0.

The off-diagonal conditional probabilities it generates are proportional to the quadratic bond indices of the MO theory. which links the specified AO-input distribution to its involvement in communicating (bonding) with the remaining orbitals. For the fixed alkali metal in halides.2). Such decoupling process can be satisfactorily described only within the flexibleinput approach. 9. It also covers the orbital decoupling limit and properly accounts for the increasing populational decoupling of AO when the antibonding MOs are more occupied. as intuitively expected. LiCl. to a large extent remedies this problem. which blur a diversity of chemical bonds. and ethane. ethylene. the . We have also demonstrated that a dramatic improvement of the overall entropy/information descriptors of chemical bonds and a differentiation of diatomic bond multiplicities is obtained when one recognizes the mutually decoupled groups of orbitals as the separate information systems. Nalewajski. The other improvement of the IT description of the bond diversity in molecules and their weakening with the nonzero occupation of antibonding MO has been gained by applying the MO-resolved channels supplemented with the extra sign convention of their entropy/information bond contributions. which is reflected by the signs of the underlying CBO matrix elements. the correct ≈ (1/2)-bond order of the bridging B–H bond is predicted. and LiBr (Table 1. which is linked to those of the associated MO bond orders. since all quantum-mechanical computations in the orbital approximation already determine the CBO data required by this generalized formulation of OCT. the strong interorbital communications correspond to strong Wiberg bond multiplicities. In B2 H6 . mainly due to a higher entropy-covalency (delocalization) and noise component of the molecular communication channel in AO resolution. the C–H bonds are seen to slightly increase their information ionicity when the number of these terminal bonds increases in a series: acetylene. It should be also emphasized that the extra-computation effort of this IT analysis of the molecular bonding patterns is negligible compared with the standard computations of the molecular electronic structure. the overall bond order is increased for larger (softer) halogen atoms. CONCLUSION Until recently. and approximately single terminal bond multiplicity is detected. for example. We have demonstrated in the present work that the MO-resolved OCT using the flexible-input probabilities and recognizing the bonding/antibonding character of the orbital interactions in a molecule. Indeed. in a series consisting LiF. and Janusz Mrozek Moreover. For the alkali metal fluorides the increase in the bond entropy-covalency (decrease in information ionicity) with increasing size (softness) of the metal is also observed. a wider use of CTCB in probing the molecular electronic structure has been hindered by the originally adopted two-electron conditional probabilities. Dariusz Szczepanik.44 Roman F. hence.

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