Herein, we investigated
the molecular dynamics as well as intramolecular
interactions in two primary monohydroxy alcohols (MA), 2-ethyl-1-hexanol
(2EHOH) and
n
-butanol (
n
BOH), by
means of broad-band dielectric (BDS) and Fourier transform infrared
(FTIR) spectroscopy. The modeling data obtained from dielectric studies
within the Rubinstein approach [
Macromolecules
2013
46
7525
7541
] originally
developed to describe the dynamical properties of self-assembling
macromolecules allowed us to calculate the energy barrier (
E
a
) of dissociation from the temperature dependences
of relaxation times of Debye and structural processes. We found
E
a
∼ 19.4 ± 0.8 and 5.3 ± 0.4
kJ/mol for the former and latter systems, respectively. On the other
hand, FTIR data analyzed within the van’t Hoff relationship
yielded the energy barriers for dissociation
E
a
∼ 20.3 ± 2.1 and 12.4 ± 1.6 kJ/mol for 2EHOH
and
n
BOH, respectively. Hence, there was almost a
perfect agreement between the values of
E
a
estimated from dielectric and FTIR studies for the 2EHOH, while
some notable discrepancy was noted for the second alcohol. A quite
significant difference in the activation barrier of dissociation indicates
that there are probably supramolecular clusters of varying geometry
or a ring-chain-like equilibrium is strongly affected in both alcohols.
Nevertheless, our analysis showed that the association/dissociation
processes undergoing within nanoassociates are one of the main factors
underlying the molecular origin of the Debye process, supporting the
transient chain model.