6 research outputs found
Bond-order and entropic probes of the chemical bonds
An overview of the recent bond-order and
entropy/information measures of the chemical bond mul-
tiplicity and of its covalent/ionic composition is given. The
former include the Wiberg index of the molecular orbital
(MO) theory and its atomic/diatomic components, while
the latter explore the communication-noise (covalency) and
information-flow (ionic) descriptors of molecular infor-
mation channels in the atomic-orbital (AO) resolution. The
illustrative application to the
two
-orbital model is presented
and the atomic resolution of bond contributions is pre-
sented. Alternative information distributions, including
densities of the displacement in the system Shannon
entropy and its entropy deficiency relative to the ‘‘pro-
molecule,’’ are advocated as effective probes of chemical
bonds. They complement the familiar density difference
diagrams of electron redistributions accompanying the
bond formation process. These quantities are applied to
investigate the central bond in small propellanes and the
contragradience
criterion, based upon the
non
-additive
Fisher information in electron distribution, is shown to
efficiently locate the bonding regions in butadiene and
benzene. The novel,
indirect
bonding mechanism through
the orbital intermediaries, inferred from the orbital com-
munication theory in the AO resolution, is probed in these
two illustrative
p
-electron systems using the generalized
Wiberg bond-orders. It is shown to give rise to a more realistic representation of the
second
-neighbor interactions,
which have previously been diagnosed as the
direct
(through-
space
)
non
-bonding. In MO theory, these
through-
bridge
bond components are due to the implicit
dependencies between the (
non
-orthogonal) AO projec-
tions onto the molecular bonding subspace of the occupied
MO. They do not require the bond-charge accumulation
between the nuclei of bonded atoms and can be realized at
longer distances. The effective range of such indirect
interactions is probed in representative polymers. Finally,
the entropy/information concepts for three dependent
probability distributions are used to qualitatively examine
the promotion of reactants in catalysis. The chemisorbed
species are predicted to undergo an ionic promotion,
compared to the gas-phase reference, thus exhibiting more
deterministic communications on the catalytic surfac