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. The HO2 and alkyl peroxy radicals are examples of reactive species for which absorption cross sections have been reported. This work explores and describes for these peroxy radicals the details of an alternative approach for obtaining these cross sections using quantum chemistry methods for the calculation of the transition dipole moment upon whose square the cross section depends. Likewise, details are given for obtaining the transition moment from the experimentally measured cross sections of individual rovibronic lines in the near-IR Ã-X̃ electronic spectrum of HO2 and the peaks of the rotational contours in the corresponding electronic transitions for the alkyl (methyl, ethyl, and acetyl) peroxy radicals. In the case of the alkyl peroxy radicals, good agreement for the transition moments, ≈20%, is found between the two methods. However, rather surprisingly, the agreement is significantly poorer, ≈40%, for the HO2 radical. Possible reasons for this disagreement are discussed.

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, NbF4, in the manifold of its electronic ground state, 2E, and its first excited state, 2T2. 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 (Td) configuration of NbF4 undergoes strong JT distortions along the bending mode of e symmetry, yielding tetragonal molecular structures of D2d symmetry with Td → D2d stabilization energies of about 2000 cm-1 in the X̃2E state and about 6400 cm-1 in the Ã2T2 state. In addition, there exists strong X̃2E-Ã2T2 PJT coupling via the bending mode of t2 symmetry, which becomes important near the crossing seam of the X̃2E and Ã2T2 potential energy surfaces. A five-state five-mode JT/PJT vibronic-coupling Hamiltonian is constructed in terms of symmetry-invariant polynomial expansions of the X̃2E and Ã2T2 diabatic potential energy surfaces in the e and t2 bending coordinates. The parameters of the Hamiltonian are determined by a least-squares fit of its eigenvalues to the CASSCF ab initio data. The vibronic spectra and the time evolution of adiabatic electronic population probabilities are computed with the multi-configuration time-dependent Hartree method. The complexity of the spectra reflects the effects of the exceptionally strong E × e and T2 × e JT couplings and (E + T2) × (e + t2) PJT coupling. The time evolution of the populations of the adiabatic electronic states after the initial preparation of the Ã2T2 state reveals the femtosecond nonadiabatic dynamics through a multidimensional seam of conical intersection. These results represent the first study of the static and dynamical JT/PJT effects in the X̃2E and Ã2T2 electronic states of NbF4.

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. Here, we study the formation of liquid bridges induced by confining colloids to a slit, with the slit walls having a preference opposite to the one of the colloid surface. Using mean field theory, we show that there is a line of first-order phase transitions between the bridge and the no-bridge states, which ends at a critical point. By decreasing the slit width, this critical point is shifted toward smaller separations between the colloids. However, at very small separations and far from criticality, we observe only a minor influence of the slit width on the location of the transition. Monte Carlo simulations of the Ising model, which mimics incompressible binary liquid mixtures, confirm the occurrence of the bridging transitions, as manifested by the appearance of "spinodal" regions where both bridge and no-bridge configurations are stable or metastable. Interestingly, we find that there is no such spinodal region in the case of small colloids, but we observe a sharpening of the transition when the colloid size increases. In addition, we demonstrate that the capillary force acting between the colloids can depend sensitively on the slit width and varies drastically with temperature, thus achieving strengths orders of magnitude higher than at criticality of the fluid.

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. We found that the effective interactions in this system are highly non-additive. In particular, the effective interactions among the colloids can be a few times stronger than the corresponding sum of the effective pair potentials. Inter alia, this non-additivity manifests itself in the phase behaviour of confined colloids, which depends sensitively on the slit width and temperature. In addition, we demonstrate the possibility of a first-order bridging transition between colloids confined to a slit and suspended in a phase-separated fluid well below the critical point of the solvent and at its critical composition in the bulk. This transition is accompanied by a remarkably large hysteresis loop, in which the force between the colloids varies by two orders of magnitude.

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. This induces effective long-range interactions and multi-tag correlations between the BPs, mediated by an out-of-equilibrium majority component, and prompts the BPs to move collectively assembling in clusters. We analyse the size-distribution of the self-assembling clusters in the steady-state, their specific force-velocity relations and also properties of the effective interactions emerging between the BPs.

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. We consider nanoparticles and substrates favouring the same component of the mixture and find that the critical Casimir interactions between the nanoparticles become drastically reduced at the substrate. In particular, the interactions can become a few kBT weaker and their decay length a few orders of magnitude smaller than in the bulk. At off-critical compositions, the decay length increases upon approaching criticality, as expected, but the interaction strength decreases. With molecular dynamics simulations and experiments, we reveal that the nanoparticles can self-assemble into crystalline clusters which form superstructures resembling cluster fluids and spinodal morphology. The simulations additionally predict the formation of fractal-like nanoparticle gels and bicontinuous phases. Our results demonstrate that charged nanoparticles in a salty binary liquid mixture provide exciting opportunities to study the formation of complex structures experimentally and theoretically, which may lead to applications in optoelectronics and photonics.

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. We show experimentally and rationalize with Monte Carlo and molecular dynamics simulations how this assembly process can be biased towards the formation of 2D layers or 3D islands and how the morphology of the deposited superstructure can be tuned from crystalline to amorphous. Our findings demonstrate the potential of the critical Casimir interaction to direct the growth of future artificial solids based on nanocrystals as the ultimate building blocks.

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. We develop a simple lattice model for the ions in a stack of parallel-aligned nanotubes, solve it by using the perturbation and "semi-mean-field" theories, and test the results by Monte Carlo simulations. We demonstrate that the interpore ionic interactions can have a profound effect on charge storage; in particular, such interactions can enhance or diminish the stored energy density, depending on the sign of like-charge interactions. We also find that charging can proceed either continuously or via a phase transition. Our results call for more detailed investigations of the properties of carbon pore walls and suggest that tuning their electrostatic response may be promising for the rational design of an optimal supercapacitor.

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. Although intensively studied theoretically and computationally, such transitions have not yet been observed experimentally due to severe challenges in resolving fine details of the fluid structure. Here, using mean field theory and Monte Carlo simulations of the Ising model, we propose to detect these ILDT by using colloids. We show that the finite-size and fluctuation induced force acting on a colloid confined in such a system experiences a vivid change if, upon lowering the temperature, the interface localizes at one of the walls. This change can serve as a more easily accessible experimental indicator of the transition.

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. At criticality the correlation length reaches the sample size and we observe crossover to another scaling pi(hs) (p) similar to A exp {-b [L (p- p(c) )(nu)](x)}. Here x is a scaling index describing the central part of the crossing probability.

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. A possible experimental realization of such "chromatic" interactions is by decorating the particle patches with single-stranded DNA linkers. The complementarity of the linkers can promote selective bond formation between predetermined pairs of patches. By using MD simulations, we compare the local connectivity, the bond orientation order, and other structural properties of the aggregates formed by the "colored" and "colorless" systems. The analysis is done for spherical particles with two different patch arrangements (tetrahedral and cubic). It is found that the aggregated (liquid) phase of the "colorless" patchy particles is better connected, denser and typically has stronger local order than the corresponding "colored" one. This, in turn, makes the colored liquid less stable thermodynamically. Specifically, we predict that in a typical case the chromatic interactions should increase the relative stability of the crystalline phase with respect to the disordered liquid, thus expanding its region in the phase diagram.

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)). Here, p=1-exp(-beta) is the probability of a bond to be closed, A(q) is the nonuniversal crossing amplitude, b(q) is the nonuniversal metric factor, nu(q) is the correlation length index, and zeta(q) is the additional scaling index. The universal function Q(x) approximately equal exp(-/z/). The nonuniversal scaling factors were found numerically.

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. The critical amplitude ratio of the magnetic susceptibility is seen to be independent of the concentration q of the empty sites for all investigated values of q < or =0.25. At the same time the average effective exponent gamma(eff) is found to vary with the concentration q, which may be argued to be due to logarithmic corrections to the power law of the pure system. These corrections are canceled in the susceptibility amplitude ratio as predicted by theory. The central charge of the corresponding field theory was computed and compared well with the theoretical predictions.

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. This trend is exactly opposite to their known ability to crystallize. We relate this anomaly to the observation that a generic aggregate of patchy systems has a coordination number close to 4. Our results also suggest a significant correlation between rotational order in the studied liquids with the corresponding crystalline phases, making this approach potentially useful for a broader range of patchy systems.