RESUMO

Zebrafish have become an important model animal for studying the emergence of collective behavior in nature. Here, we show how to properly analyze the polarization statistics to distinguish shoal regimes. In analogy with the statistical properties of optical speckles, we show that exponential and Rayleigh distributions emerge in shoals with many fish with uncorrelated velocity directions. In the opposite limit of just two fish, the polarization distribution peaks at high polarity, with the average value being a decreasing function of the shoal's size, even in the absence of correlations. We also perform a set of experiments unveiling two shoaling regimes. Large shoals behave as small domains with strong intra-domain and weak inter-domain correlations. A strongly correlated regime develops for small shoals. The reported polarization statistical features shall guide future automated neuroscience, pharmacological, toxicological, and embryogenesis-motivated experiments aiming to explore the collective behavior of fish shoals.

Assuntos

RESUMO

The ground-state ordering of a quantum mixed-spin Heisenberg tetramer chain composed of an alternate sequence ofs = 1 andS=3/2dimers is studied in detail as a function of two considered exchange interactions ascribed to similar and dissimilar spin pairs. At zero magnetic field, the ferrimagnetic mixed spin-(1, 1, 3/2, 3/2) Heisenberg tetramer chain displays, depending on a mutual interplay between two considered exchange interactions, three distinct gapped valence-bond-solid phases separated by gap-closing quantum critical points. Using density-matrix renormalization group calculations we construct the full ground-state phase diagram as a function of the interaction ratio and magnetic field, which exhibits besides three gapped valence-bond-solid phases special Kosterlitz-Thouless and topological quantum critical points. A tangential finite-size scaling analysis is employed to obtain precise estimates of the zero-field valence-bond-solid transitions and unveil their common logarithmic correction to a power-law scaling of the correlation length.

RESUMO

Ground-state and magnetocaloric properties of a site-diluted sawtooth magnetic chain in the presence of an external magnetic field are exactly investigated by using the transfer-matrix method. The model captures the main magnetic interactions along CuO chains present in some hole-doped cuprates. The ground-state diagram is exhibited and analytical expressions for the residual entropy within each ground state and along the transition lines are derived. We explicitly discuss the role of the underlying pairing correlations and the entropy maximization principle. The isothermal entropy change is determined as a function of interaction parameters, doping concentration, and magnetic-field amplitude. Normal and inverse magnetocaloric effects are reported. Adiabatic demagnetization curves are discussed in connection with configurational and spin contributions to the residual entropy.

RESUMO

The nonlinear optical response, more specifically the Hyper-Rayleigh Scattering (HRS) response of the Brooker's merocyanine, has been calculated at the time-dependent density functional theory level and rationalized in terms of the structural changes and polarization effects induced by applied external electric fields. The structural change leads to large changes in the HRS response, while only slight variations were observed due to the polarization effects on the fixed quinoid form. Considering both structural and polarization contributions concurrently, the HRS response is dominated by cooperative behavior of those effects for weak and intermediate electric field strengths. At the same time, the competition between both effects was a crucial factor in the region of strong electric fields. The obtained results can lead to an easier understanding for upcoming studies considering more realistic models of solvents where it is not simple to disentangle these contributions.

RESUMO

The short-time relaxation critical behavior of the XY model on a simple-cubic lattice is investigated within the scope of deterministic Hamiltonian dynamics. The Hamiltonian includes a first-neighbor interaction between planar vectors and a rotational kinetic term from which the motion equations are derived. The dynamical evolution from a fully ordered initial state is followed by employing a symplectic algorithm based on a high-order Trotter-Suzuki decomposition of the time-evolution operator. A finite-time scaling analysis is performed to provide accurate estimates of the critical energy density, the order-parameter relaxation exponent, and the dynamical critical exponent. The estimated critical exponents are consistent with prior theoretical and experimental values reported for the superfluid ^{4}He, extreme type-II superconducting, and Bose-Einstein condensation transitions.

RESUMO

In this work, we demonstrate that the inclusion of long-range interactions has a significant impact on the estimation of ligand-protein binding energies. Within the scope of the electrostatically embedded adaptation of the molecular fragmentation with conjugated caps (EE-AMFCC) scheme, we unveil the role played by long-range contributions in distinct levels of quantum mechanical calculations. As a prototypical system, we consider ibuprofen coupled to the human serum albumin. In particular, we show that some relevant ligand-residue interaction energies can only be accurately captured in density functional theory (DFT) approaches when the electrostatic background is properly represented by an explicit point charge distribution. Graphical Abstract (left) The binding site FA3/FA4 of HSA containing the attached IBU. (right) Absolute value of difference between the biding energies calculated including the electrostatic embedding and the energies calculated without the electrostatic embedding using the HF, B3LYP, CAM-B3LYP, and MP2 methodologies.

RESUMO

Within the harmonic approximation, we analytically determine the elastic-mediated interaction between colloidal nanoparticles adsorbed on the surface of smectic films under the influence of an external field. Both cases of free-standing films and films deposited over a solid substrate are considered. We show that the asymptotic decay (1/R in free-standing and exponential in deposited films) is not altered by the external field. However, the external field plays distinct roles according to the film configuration, the interparticle distance, the film thickness, and the surface tension at the film-gas interface. We provide a detailed discussion under the light of the distinct mechanisms controlling the undulations of the surface layer.

Assuntos

RESUMO

Special localized wave modes show up in several physical scenarios including BEC in optical lattices, nonlinear photonic crystals, and systems with strong electron-phonon interaction. These result from an underlying nonlinear contribution to the wave equation that is usually assumed to be instantaneous. Here we demonstrate that the relaxation process of the nonlinearity has a profound impact in the wave-packet dynamics and in the formation of localized modes. We illustrate this phenomenology by considering the one-electron wave packet spreading in a C60 buckball structure whose dynamics is governed by a discrete nonlinear Schrödinger equation with a Debye relaxation of the nonlinearity. We report the full phase diagram related to the spacial extension of the asymptotic wave packet and unveil a complex wave-packet dynamical behavior.

RESUMO

A combination of the polarizable continuum model (PCM) and the hybrid quantum mechanics/molecular mechanics (QM/MM) methodology, PCM-MM/QM, is used to include the solute electronic polarization and then study the solvent effects on the low-lying n→π(∗) excitation energy and the (15)N nuclear magnetic shielding of pyrazine and pyridazine in aqueous environment. The results obtained with PCM-MM/QM are compared with two other procedures, i.e., the conventional PCM and the iterative and sequential QM/MM (I-QM/MM). The QM calculations are made using density functional theory in the three procedures. For the excitation energies, the time-dependent B3LYP/6-311+G(d) model is used. For the magnetic shielding, the B3LYP/aug-pcS2(N)/pcS2(C,O,H) is used with the gauge-including atomic orbitals. In both cases, i.e., PCM-MM/QM and I-QM/MM, that use a discrete model of the solvent, the solute is surrounded by a first shell of explicit water molecules embedded by an electrostatic field of point charges for the outer shells. The best results are obtained including 28 explicit water molecules for the spectral calculations and 9 explicit water molecules for the magnetic shielding. Using the PCM-MM/QM methodology the results for the n→π(∗) excitation energies of pyridazine and pyrazine are 32,070 ± 80 cm(-1) and 32,675 ± 60 cm(-1), respectively, in good agreement with the corresponding I-MM/QM results of 32,540 ± 80 cm(-1) and 32,710 ± 60 cm(-1) and the experimental results of 33,450-33,580 cm(-1) and 32,700-33,300 cm(-1). For the (15)N magnetic shielding, the corresponding numbers for the gas-water shifts obtained with PCM-MM/QM are 47.4 ± 1.3 ppm for pyridazine and 19.7 ± 1.1 ppm for pyrazine, compared with the I-QM/MM values of 53.4 ± 1.3 ppm and 19.5 ± 1.2 ppm and the experimental results of 42-54 ppm and 17-22 ppm, respectively. The agreement between the two procedures is found to be very good and both are in agreement with the experimental values. PCM-MM/QM approach gives a good solute polarization and could be considered in obtaining reliable results within the expected QM/MM accuracy. With this electronic polarization, the solvent effects on the electronic absorption spectra and the (15)N magnetic shielding of the diazines in water are well described by using only an electrostatic approximation. Finally, it is remarked that the experimental and theoretical results suggest that the (15)N nuclear magnetic shielding of any diazine has a clear dependence with the solvent polarity but not directly with the solute-solvent hydrogen bonds.

Assuntos

RESUMO

We study the smectic to nematic (SmA-N) phase transition taking place at the center of a free-standing film that exhibits enhanced surface order due to the anchoring promoted by a surrounding gas. The usual McMillan mean-field approach predicts that the SmA-N transition in bulk samples can be continuous or discontinuous (first or second order) depending on the molecular geometry, with a tricritical point separating these two regimes. Here we show that the additional orientational order imposed by the surface anchoring stabilizes the surface-induced smectic and nematic phases, leading to the breakdown of the tricritical point and to the emergence of a critical end point. We report the full phase diagram, which depicts four distinct structures as the film thickness is reduced.

RESUMO

The solvent effects on the low-lying absorption spectrum and on the (15)N chemical shielding of pyrimidine in water are calculated using the combined and sequential Monte Carlo simulation and quantum mechanical calculations. Special attention is devoted to the solute polarization. This is included by an iterative procedure previously developed where the solute is electrostatically equilibrated with the solvent. In addition, we verify the simple yet unexplored alternative of combining the polarizable continuum model (PCM) and the hybrid QM/MM method. We use PCM to obtain the average solute polarization and include this in the MM part of the sequential QM/MM methodology, PCM-MM/QM. These procedures are compared and further used in the discrete and the explicit solvent models. The use of the PCM polarization implemented in the MM part seems to generate a very good description of the average solute polarization leading to very good results for the n-π* excitation energy and the (15)N nuclear chemical shield of pyrimidine in aqueous environment. The best results obtained here using the solute pyrimidine surrounded by 28 explicit water molecules embedded in the electrostatic field of the remaining 472 molecules give the statistically converged values for the low lying n-π* absorption transition in water of 36 900 ± 100 (PCM polarization) and 36 950 ± 100 cm(-1) (iterative polarization), in excellent agreement among one another and with the experimental value observed with a band maximum at 36 900 cm(-1). For the nuclear shielding (15)N the corresponding gas-water chemical shift obtained using the solute pyrimidine surrounded by 9 explicit water molecules embedded in the electrostatic field of the remaining 491 molecules give the statistically converged values of 24.4 ± 0.8 and 28.5 ± 0.8 ppm, compared with the inferred experimental value of 19 ± 2 ppm. Considering the simplicity of the PCM over the iterative polarization this is an important aspect and the computational savings point to the possibility of dealing with larger solute molecules. This PCM-MM/QM approach reconciles the simplicity of the PCM model with the reliability of the combined QM/MM approaches.

RESUMO

Strongly anchored free-standing smectic films usually present a stepwise reduction of the number of layers when the temperature is raised above the smectic-isotropic bulk transition temperature. Here, we demonstrate that a field-induced layer thinning transition can take place in smectic films with a negative dielectric anisotropy even below the bulk transition temperature. Using an extended McMillan's model, we provide the phase diagram of this layering transition and show that, when the field is raised above the bulk transition field, the film thickness reduction is well described by a power law with an exponent that depends on the temperature and the aspect ratio of the liquid-crystal molecule.