Many charge-transporting molecular systems function as
ordered
or disordered arrays of solid state materials composed of nonpolar
(or weakly polar) molecules. Due to low dielectric constants for nonpolar
systems, it is common to ignore the effects of outer-shell reorganization
energy (λ
out
). However, ignoring
λ
out
has not been properly supported
and it can severely impact predictions and insights derived. Here,
we estimate λ
out
by two means: from
experimental ultraviolet photoelectron spectra, in which vibronic
progression in these spectra can be fitted with the widths of peaks
determining the low-frequency component in reorganization energy,
regarded to be closely associated with λ
out
, and from molecular dynamic (MD) simulation of nonpolar molecules,
in which disorder or fluctuation statistics for energies of charged
molecules are calculated. An upper bound for λ
out
was obtained as 505 and 549 meV for crystalline anthracene
(140 K) and pentacene (50 K), respectively, by fitting of experimental
data, and 212 and 170 meV, respectively, from MD simulations. These
values are comparable to the inner-sphere reorganization energy (λ
in
) arising from intramolecular vibration.
With corresponding spectral density functions calculated, we found
that λ
out
is influenced both by
low- and high-frequency dynamics, in which the former arises from
constrained translational and rotational motions of surrounding molecules.
In an amorphous state, about half of the λ
out
’s obtained are from high-frequency components, which
is quite different from the conventional polar solvation. Moreover,
crystalline systems exhibit super-Ohmic spectral density, whereas
amorphous systems are sub-Ohmic.