Conspectus
The review improves our understanding
of how electrostatic interactions
in the electrolyte, gas phase, and on surfaces can drive the fragmentation
and assembly of particles. This is achieved through the overview of
our advanced theoretical and computational modeling toolbox suitable
for interpretation of experimental observations and discovery of novel,
tunable assemblies and architectures. In the past decade, we have
produced a significant, fundamental body of work on the development
of comprehensive theories based on a rigorous mathematical foundation.
These solutions are capable of accurate predictions of electrostatic
interactions between dielectric particles of arbitrary size, anisotropy,
composition, and charge, interacting in solvents, ionized medium,
and on surfaces. We have applied the developed electrostatic approaches
to describe physical and chemical phenomena in dusty plasma and planetary
environments, in Coulomb fission and electrospray ionization processes,
and in soft matter, including a counterintuitive but widespread attraction
between like-charged particles.
Despite its long history, the
search for accurate methods to provide
a deeper understanding of electrostatic interactions remains a subject
of significant interest, as manifested by a constant stream of theoretical
and experimental publications. While major international effort in
this area has focused predominantly on the computational modeling
of biocatalytic and biochemical performance, we have expanded the
boundaries of accuracy, generality, and applicability of underlying
theories. Simple solvation models, often used in calculating the electrostatic
component of molecular solvation energy and polarization effects of
solvent, rarely go beyond the induced dipole approximation because
of computational costs. These approximations are generally adequate
at larger separation distances; however, as particles approach the
touching point, more advanced charged-induced multipolar descriptions
of the electrostatic interactions are required to describe accurately
a collective behavior of polarizable neutral and charged particles.
At short separations, the electrostatic forces involving polarizable
dielectric and conducting particles become nonadditive which necessitates
further developments of quantitatively accurate many-body approaches.
In applications, the electrostatic response of materials is commonly
controlled by externally applied electric fields, an additional complex
many-body problem that we have addressed most recently, both theoretically
and numerically.
This review reports on the most significant
results and conclusions
underpinning these recent advances in electrostatic theory and its
applications. We first discuss the limitations of classical approaches
to interpreting electrostatic phenomena in electrolytes and complex
plasmas, leading to an extended analytical theory suitable for accurate
estimation of the electrostatic forces in a dilute solution of a strong
electrolyte. We then introduce the concept and numerical rea...