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You are on page 1of 48

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

Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 2 #2

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

Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 3 #3

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

Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 4 #4

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

Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 5 #5

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.

Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 6 #6

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

†

]χ

†

(r) ≡ χ(r)γχ

†

(r) = Np(r). (1)

The latter represents the projection operator

ˆ

P

ϕ

=[ϕ)¸ϕ[ =

s

[ϕ

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

[χ

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.

Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 7 #7

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

[χ

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,

(γ

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

=γ

i, j

. Therefore, it is also

proportional to the corresponding AO contribution M

i, j

=γ

2

i, j

to the Wiberg

Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 8 #8

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

=γ

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)

2γ

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.

Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 9 #9

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

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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

÷

_

Qσ

α

, ϕ

anti.

(α) = −

_

Qh

α

÷

√

Pσ

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

{γ

α,β

] then includes the following nonvanishing elements:

γ

h

α

,h

α

=2P, γ

σ

α

,σ

α

=2Q, γ

h

α

,σ

α

=γ

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

[σ

α

) = Q, P(h

α

[σ

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

[χ

α

[χ

α

] =

_

P Q

P Q

_

, P

α

(a

α

, b

α

) ≡P

α

[χ

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

)δ

α,β

] and P(a, b) ={P

α

(a

α

, b

α

)δ

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.

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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

(σ

1

÷σ

2

) =

_

U

2

(h

1

÷h

2

) ÷

_

V

2

(σ

1

÷σ

2

), U ÷V = 1,

ψ

2

=

√

Tp ÷

_

W

2

(σ

1

−σ

2

) =

_

T

2

(h

1

−h

2

) ÷

_

W

2

(σ

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

=

(α

0

[β

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

)δ

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

)δ

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

|α

0

) =p

α

(a

/

[a

0

)δ

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

Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 19 #19

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.

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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.

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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

(ϕ

s

) = S[P

s

(b [a)],

I

a,b

(ϕ

s

) = H[p

0

s

] −S(ϕ

s

),

N

a,b

(ϕ

s

) = S

a,b

(ϕ

s

) ÷I

a,b

(ϕ

s

) = H[p

0

s

], (31)

would then be straightforwardly recognized as bonding (positive), when

γ

a,b

(ϕ

s

) > 0, or antibonding (negative), when γ

a,b

(ϕ

s

) < 0, and nonbonding

(zero), when γ

a,b

(ϕ

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

(ϕ

s

)]P

s

f

s

S

i, j

(ϕ

s

), I(i, j) =

s

sign[γ

i, j

(ϕ

s

)]P

s

f

s

I

i, j

(ϕ

s

),

N(i, j) =

s

sign[γ

i, j

(ϕ

s

)]P

s

f

s

N

i, j

(ϕ

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,

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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.

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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.

Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 26 #26

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.

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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

[χ

/

) =

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

_

¸

¸

¸

¸

¸

¸

_

,

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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

(ϕ

1

) > 0

S

1,2

(ϕ

1

) = 1 I

1,2

(ϕ

1

) = 0 N

1,2

(ϕ

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

(ϕ

1

) > 0

S

1,3

(ϕ

1

) = 1 I

1,3

(ϕ

1

) = 1 N

1,3

(ϕ

1

) = 1

ϕ

2

: γ

1, 3

(ϕ

2

) < 0

S

1,3

(ϕ

2

) = 1 I

1,3

(ϕ

2

) = 0 N

1,3

(ϕ

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

=γ

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

(ϕ

1

) > 0, γ

1,3

(ϕ

1

) > 0

S

1,2

(ϕ

1

) = N

1,2

(ϕ

1

) = 0.925 I

1,2

(ϕ

1

) = 0

S

1,3

(ϕ

1

) = N

1,3

(ϕ

1

) = 0.925 I

1,3

(ϕ

1

) = 0

ϕ

2

: γ

1,2

(ϕ

2

) > 0, γ

1,3

(ϕ

2

) < 0

S

1,2

(ϕ

2

) = N

1,2

(ϕ

2

) = 0.925 I

1,2

(ϕ

2

) = 0

S

1,3

(ϕ

2

) = N

1,3

(ϕ

2

) = 0.925 I

1,3

(ϕ

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

(ϕ

1

) > 0

S

1,4

(ϕ

1

) = N

1,2

(ϕ

1

) = 0.789 I

1,4

(ϕ

1

) = 0

ϕ

2

: γ

1, 4

(ϕ

2

) < 0

S

1,4

(ϕ

2

) = N

1,4

(ϕ

2

) = 1.061 I

1,4

(ϕ

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

(ϕ

1

) > 0

S

2,3

(ϕ

1

) = N

2,3

(ϕ

1

) = 1.061 I

2,3

(ϕ

1

) = 0

ϕ

2

: γ

2, 3

(ϕ

2

) < 0

S

2,3

(ϕ

2

) = N

2,3

(ϕ

2

) = 0.789 I

2,3

(ϕ

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.

Sabin 05-ch01-001-048-9780123860132 2011/6/29 9:11 Page 34 #34

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

(ϕ

1

) > 0

S

i, j

(ϕ

1

) = N

i, j

(ϕ

1

) = 0.862 I

i, j

(ϕ

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

(ϕ

2

) = γ

4,5

(ϕ

2

) > 0

γ

1,4

(ϕ

2

) = γ

1,5

(ϕ

2

) = γ

2,4

(ϕ

2

) = γ

2,5

(ϕ

2

) < 0

S

i, j

(ϕ

2

) = N

i, j

(ϕ

2

) = 1 I

i, j

(ϕ

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

(ϕ

3

) < 0

S

3,6

(ϕ

3

) = N

3,6

(ϕ

3

) = 1.057 I

3,6

(ϕ

3

) = 0

γ

1,2

(ϕ

3

) = γ

1,4

(ϕ

3

) = γ

2,5

(ϕ

3

) = γ

4,5

(ϕ

3

) < 0

γ

1,5

(ϕ

3

) = γ

2,4

(ϕ

3

) > 0

S

i, j

(ϕ

3

) = N

i, j

(ϕ

3

) = 0.597 I

i,j

(ϕ

3

) = 0

γ

1,3

(ϕ

3

) = γ

2,6

(ϕ

3

) = γ

3,5

(ϕ

3

) = γ

4,6

(ϕ

3

) < 0

γ

1,6

(ϕ

3

) = γ

2,3

(ϕ

3

) = γ

3,4

(ϕ

3

) = γ

5,6

(ϕ

3

) > 0

S

i, j

(ϕ

3

) = N

i, j

ϕ

3

) = 0.827 I

i, j

(ϕ

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

÷

_

Qσ

α

, ϕ

a

(α) = −

_

QH

α

÷

√

Pσ

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

,σ

α

=2Q÷n

a

P, γ

H

α

,σ

α

=γ

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

=γ

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

=γ

σ

α

,σ

α

=2 and γ

H

α

,σ

α

=γ

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

[χ

α

[χ

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

,σ

α

=γ

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

[χ

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

[χ

AB

) ≡ [P(χ

Y

[χ

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

[χ

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

[χ

AB

) [9] gives the associated con-

densed conditional probabilities of the associated molecular information

system,

P(X

AB

[χ

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

(χ

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

(χ

A

: B) =

i∈A

P

AB

(B, i)I(χ

AB

: i), I

AB

(χ

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

(χ

A

: B) ÷I

AB

(χ

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

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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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