Calculated and Empirical Values of Vibronic Transition Dipole Moments of Reactive Chemical Intermediates for Determination of Concentrations.

Absorption spectroscopy has long been known as a technique for making molecular concentration measurements and has received enhanced visibility in recent years with the advent of new techniques, like cavity ring-down spectroscopy, that have increased its sensitivity. To apply the method, it is necessary to have a known molecular absorption cross section for the species of interest, which typically is obtained by measurements of a standard sample of known concentration. However, this method fails if the species is highly reactive, and indirect means for attaining the cross section must be employed.

Controlled deposition of nanoparticles with critical Casimir forces.

Nanocrystal assembly represents the key fabrication step to develop next-generation optoelectronic devices with properties defined from the bottom-up. Despite numerous efforts, our limited understanding of nanoscale interactions has so far delayed the establishment of assembly conditions leading to reproducible superstructure morphologies, therefore hampering integration with large-scale, industrial processes. In this work, we demonstrate the deposition of a layer of semiconductor nanocrystals on a flat and unpatterned silicon substrate as mediated by the interplay of critical Casimir attraction and electrostatic repulsion.

Debye vs. Casimir: controlling the structure of charged nanoparticles deposited on a substrate.

Fine-tuning the interactions between particles can allow one to steer their collective behaviour and structure. A convenient way to achieve this is to use solvent criticality to control attraction, via critical Casimir forces, and to control repulsion via the Debye screening of electrostatic interactions. Herein, we develop a multiscale simulation framework and a method for controlled deposition of quantum dots to investigate how these interactions affect the structure of charged nanoparticles deposited on a substrate, altogether immersed in a binary liquid mixture intermixed with salt.

Strong static and dynamic Jahn-Teller and pseudo-Jahn-Teller effects in niobium tetrafluoride.

We present a first-principles study of the static and dynamic aspects of the strong Jahn-Teller (JT) and pseudo-JT (PJT) effects in niobium tetrafluoride, NbF, in the manifold of its electronic ground state, E, and its first excited state, T. The complex topography of the full-dimensional multi-sheeted adiabatic JT/PJT surfaces is analyzed computationally at the complete-active-space self-consistent-field (CASSCF) and multireference second-order perturbation levels of electronic structure theory, providing a detailed characterization of minima, saddle points, and minimum-energy conical intersection points. The calculations reveal that the tetrahedral (T) configuration of NbF undergoes strong JT distortions along the bending mode of e symmetry, yielding tetragonal molecular structures of D symmetry with T → D stabilization energies of about 2000 cm in the X̃E state and about 6400 cm in the ÃT state.

Bridging transitions and capillary forces for colloids in a slit.

Capillary bridges can form between colloids immersed in a two-phase fluid, e.g., in a binary liquid mixture, if the surface of the colloids prefers the species other than the one favored in the bulk liquid.

Feeling Your Neighbors across the Walls: How Interpore Ionic Interactions Affect Capacitive Energy Storage.

Progress in low-dimensional carbon materials has intensified research on supercapacitors with nanostructured/nanoporous electrodes. The theoretical and simulation work so far has focused on charging single nanopores or nanoporous networks and the effects due to ionic interactions inside the pores, while the effect of interpore ion-ion correlations has received less attention. Herein, we study how the interactions between the ions in the neighboring pores across the pore walls affect capacitive energy storage.

Probing interface localization-delocalization transitions by colloids.

Interface localization-delocalization transitions (ILDT) occur in two-phase fluids confined in a slit with competing preferences of the walls for the two fluid phases. At low temperatures the interface between the two phases is localized at one of the walls. Upon increasing temperature it unbinds.

Nonadditive interactions and phase transitions in strongly confined colloidal systems.

The behaviour of colloids can be controlled effectively by tuning the solvent-mediated interactions among them. An extensively studied example is the temperature-induced aggregation of suspended colloids close to the consolute point of their binary solvent. Here, using mean field theory and Monte Carlo simulations, we study the behaviour of colloids confined to a narrow slit containing a nearly-critical binary liquid mixture.

Cooperative behavior of biased probes in crowded interacting systems.

We study, via extensive numerical simulations, dynamics of a crowded mixture of mutually interacting (with a short-range repulsive potential) colloidal particles immersed in a suspending solvent, acting as a heat bath. The mixture consists of a majority component - neutrally buoyant colloids subject to internal stimuli only, and a minority component - biased probes (BPs) also subject to a constant force. In such a system each of the BPs alters the distribution of the colloidal particles in its vicinity, driving their spatial distribution out of equilibrium.

Chromatic patchy particles: Effects of specific interactions on liquid structure.

We study the structural and thermodynamic properties of patchy particle liquids, with a special focus on the role of "color," i.e., specific interactions between individual patches.

Precursors of order in aggregates of patchy particles.

We study computationally the local structure of aggregated systems of patchy particles. By calculating the probability distribution functions of various rotational invariants we can identify the precursors of orientation order in amorphous phase. Surprisingly, the strongest signature of local order is observed for four-patch particles with tetrahedral symmetry, not for six-patch particles with the cubic one.

Tails of the crossing probability.

The scaling of the tails of the probability of a system to percolate only in the horizontal direction pi(hs) was investigated numerically for the correlated site-bond percolation model (q -state Potts model) for q=1 , 2, 3, 4 (where q is the number of spin states). We have to demonstrate that the crossing probability pi(hs) (p) far from the critical point p(c) has the shape pi(hs) (p) similar to D exp [cL (p- p(c) )(nu) ] where nu is the correlation length index, and p=1-exp (-beta) is the probability of a bond to be closed. For the tail region the correlation length is smaller than the lattice size.

Universality of the crossing probability for the Potts model for q=1, 2, 3, 4.

The universality of the crossing probability pi(hs) of a system to percolate only in the horizontal direction was investigated numerically by a cluster Monte Carlo algorithm for the q-state Potts model for q=2, 3, 4 and for percolation q=1. We check the percolation through Fortuin-Kasteleyn clusters near the critical point on the square lattice by using representation of the Potts model as the correlated site-bond percolation model. It was shown that probability of a system to percolate only in the horizontal direction pi(hs) has the universal form pi(hs)=A(q)Q(z) for q=1,2,3,4 as a function of the scaling variable z=[b(q)L(1/nu(q))[p-p(c)(q,L)]](zeta(q)).

Critical amplitude ratio of the susceptibility in the random-site two-dimensional Ising model.

We present a different way of probing the universality class of the site-diluted two-dimensional Ising model. We analyze Monte Carlo data for the magnetic susceptibility, introducing a fitting procedure in the critical region applicable even for a single sample with quenched disorder. This gives us the possibility to fit simultaneously the critical exponent, the critical amplitude, and the sample-dependent pseudocritical temperature.