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Dense or glassy active matter, as a result of its remarkable resemblance to passive glass-forming materials, is enjoying increasing scientific interest. To better grasp the subtle effect of active motion on the process of vitrification, a number of active mode-coupling theories (MCTs) have recently been developed. These have proven capable of qualitatively predicting important parts of the active glassy phenomenology. However, most efforts so far have only considered single-component materials, and their derivations are arguably more complex than the standard MCT case, which might hinder broader usage. Here we present a detailed derivation of a distinct active MCT for mixtures of athermal self-propelled particles that is more transparent than previously introduced versions. The key insight is that we can follow a similar strategy for our overdamped active system as is typically used for passive underdamped MCT. Interestingly, when only considering one particle species, our theory gives the exact same result as the one obtained in previous work, which employed a highly different mode-coupling strategy. Moreover, we assess the quality of the theory and its novel extension to multi-component materials by using it to predict the dynamics of a Kob–Andersen mixture of athermal active Brownian quasi-hard spheres. We demonstrate that our theory is able to capture all qualitative features, most notably the location of the optimum of the dynamics when the persistence length and cage length coincide, for each combination of particle types. [ABSTRACT FROM AUTHOR]

Memory effects are ubiquitous in a wide variety of complex physical phenomena, ranging from glassy dynamics and metamaterials to climate models. The Generalized Langevin Equation (GLE) provides a rigorous way to describe memory effects via the so-called memory kernel in an integro-differential equation. However, the memory kernel is often unknown, and accurately predicting or measuring it via, e.g., a numerical inverse Laplace transform remains a herculean task. Here, we describe a novel method using deep neural networks (DNNs) to measure memory kernels from dynamical data. As a proof-of-principle, we focus on the notoriously long-lived memory effects of glass-forming systems, which have proved a major challenge to existing methods. In particular, we learn the operator mapping dynamics to memory kernels from a training set generated with the Mode-Coupling Theory (MCT) of hard spheres. Our DNNs are remarkably robust against noise, in contrast to conventional techniques. Furthermore, we demonstrate that a network trained on data generated from analytic theory (hard-sphere MCT) generalizes well to data from simulations of a different system (Brownian Weeks–Chandler–Andersen particles). Finally, we train a network on a set of phenomenological kernels and demonstrate its effectiveness in generalizing to both unseen phenomenological examples and supercooled hard-sphere MCT data. We provide a general pipeline, KernelLearner, for training networks to extract memory kernels from any non-Markovian system described by a GLE. The success of our DNN method applied to noisy glassy systems suggests that deep learning can play an important role in the study of dynamical systems with memory. [ABSTRACT FROM AUTHOR]

Recent years have seen a rapid increase of interest in dense active materials, which, in the disordered state, share striking similarities with the conventional passive glass-forming matter. For such passive glassy materials, it is well established (at least in three dimensions) that the details of the microscopic dynamics, e.g., Newtonian or Brownian, do not influence the long-time glassy behavior. Here, we investigate whether this still holds true in the non-equilibrium active case by considering two simple and widely used active particle models, i.e., active Ornstein-Uhlenbeck particles (AOUPs) and active Brownian particles (ABPs). In particular, we seek to gain more insight into the role of the self-propulsion mechanism on the glassy dynamics by deriving a mode-coupling theory (MCT) for thermal AOUPs, which can be directly compared to a recently developed MCT for ABPs. Both theories explicitly take into account the active degrees of freedom. We solve the AOUP- and ABP-MCT equations in two dimensions and demonstrate that both models give almost identical results for the intermediate scattering function over a large variety of control parameters (packing fractions, active speeds, and persistence times). We also confirm this theoretical equivalence between the different self-propulsion mechanisms numerically via simulations of a polydisperse mixture of active quasi-hard spheres, thereby establishing that, at least for these model systems, the microscopic details of self-propulsion do not alter the active glassy behavior. [ABSTRACT FROM AUTHOR]

We develop a first-principles-based generalized mode-coupling theory (GMCT) for the tagged-particle motion of glassy systems. This theory establishes a hierarchy of coupled integro-differential equations for self-multi-point density correlation functions, which can formally be extended up to infinite order. We use our GMCT framework to calculate the self-nonergodicity parameters and the self-intermediate scattering function for the Percus–Yevick hard-sphere system based on the first few levels of the GMCT hierarchy. We also test the scaling laws in the α- and β-relaxation regimes near the glass-transition singularity. Furthermore, we study the mean-square displacement and the Stokes–Einstein relation in the supercooled regime. We find that qualitatively our GMCT results share many similarities with the well-established predictions from standard mode-coupling theory, but the quantitative results change, and typically improve, by increasing the GMCT closure level. However, we also demonstrate on general theoretical grounds that the current GMCT framework is unable to account for violation of the Stokes–Einstein relation, underlining the need for further improvements in the first-principles description of glassy dynamics. [ABSTRACT FROM AUTHOR]

Mode-coupling theory (MCT) constitutes one of the few first-principles-based approaches to describe the physics of the glass transition, but the theory's inherent approximations compromise its accuracy in the activated glassy regime. Here, we show that microscopic generalized mode-coupling theory (GMCT), a recently proposed hierarchical framework to systematically improve upon MCT, provides a promising pathway toward a more accurate first-principles description of glassy dynamics. We present a comprehensive numerical analysis for Percus–Yevick hard spheres by performing explicitly wavenumber- and time-dependent GMCT calculations up to sixth order. Specifically, we calculate the location of the critical point, the associated non-ergodicity parameters, and the time-dependent dynamics of the density correlators at both absolute and reduced packing fractions, and we test several universal scaling relations in the α- and β-relaxation regimes. It is found that higher-order GMCT can successfully remedy some of MCT's pathologies, including an underestimation of the critical glass transition density and an overestimation of the hard-sphere fragility. Furthermore, we numerically demonstrate that the celebrated scaling laws of MCT are preserved in GMCT and that the predicted critical exponents manifestly improve as more levels are incorporated in the GMCT hierarchy. Although formally the GMCT equations should be solved up to infinite order to reach full convergence, our finite-order GMCT calculations unambiguously reveal a uniform convergence pattern for the dynamics. We thus argue that GMCT can provide a feasible and controlled means to bypass MCT's main uncontrolled approximation, offering hope for the future development of a quantitative first-principles theory of the glass transition. [ABSTRACT FROM AUTHOR]

Generalized mode-coupling theory (GMCT) constitutes a systematically correctable, first-principles theory to study the dynamics of supercooled liquids and the glass transition. It is a hierarchical framework that, through the incorporation of increasingly many particle density correlations, can remedy some of the inherent limitations of the ideal mode-coupling theory (MCT). However, despite MCT's limitations, the ideal theory also enjoys several remarkable successes, notably including the analytical scaling laws for the α- and β-relaxation dynamics. Here, we mathematically derive similar scaling laws for arbitrary-order multi-point density correlation functions obtained from GMCT under arbitrary mean-field closure levels. More specifically, we analytically derive the asymptotic and preasymptotic solutions for the long-time limits of multi-point density correlators, the critical dynamics with two power-law decays, the factorization scaling laws in the β-relaxation regime, and the time-density superposition principle in the α-relaxation regime. The two characteristic power-law-divergent relaxation times for the two-step decay and the non-trivial relation between their exponents are also obtained. The validity ranges of the leading-order scaling laws are also provided by considering the leading preasymptotic corrections. Furthermore, we test these solutions for the Percus–Yevick hard-sphere system. We demonstrate that GMCT preserves all the celebrated scaling laws of MCT while quantitatively improving the exponents, rendering the theory a promising candidate for an ultimately quantitative first-principles theory of glassy dynamics. [ABSTRACT FROM AUTHOR]

We derive a general renormalized potential-following propagation method that efficiently solves the coupled-channels equations. The step size is variable, the method is compatible with reactive boundary conditions, and the algorithm may be combined with other renormalized algorithms, such as renormalized Numerov. We diagonalize the coupling matrix and consider piece-wise constant and linear reference potentials. The constant reference potential algorithm is very simple to implement, yet for multichannel problems almost as accurate as the linear reference potential method. The applicability of the proposed algorithms to realistic problems is demonstrated for cold collisions of NH radicals. The renormalized approach has the advantage of producing wave functions in a straightforward way, which is illustrated for a shape resonance in NH-NH collisions. These scattering wave functions can be used to study ultracold photoassociation and near-threshold photodissociation. [ABSTRACT FROM AUTHOR]

The rotationally resolved magnetic dipole absorption spectrum of the oxygen A-band b1Σ + g (v=0) ←X3Σ- g (v=0) perturbed by collisions with helium was studied theoretically using the impact approximation. To calculate the relaxation matrix, scattering calculations were performed on a newly computed helium-oxygen (b1Σ + g ) interaction potential as well as on a helium-oxygen (X3Σ- g ) interaction potential from the literature. The calculated integrated line cross sections and broadening coefficients are in good agreement with experimental results from the literature. Additionally, cavity ring-down experiments were performed in the wings of the spectral lines for a quantitative study of line-mixing, i.e., the redistribution of rotational line intensities by helium-oxygen collisions. It is shown that inclusion of line-mixing in the theory is required to reproduce the experimentally determined absolute absorption strengths as a function of the density of the helium gas. [ABSTRACT FROM AUTHOR]

We present elastic and inelastic spin-changing cross sections for cold and ultracold NH(X 3Σ-) + NH(X 3Σ-) collisions, obtained from full quantum scattering calculations on an accurate ab initio quintet potential-energy surface. Although we consider only collisions in zero field, we focus on the cross sections relevant for magnetic trapping experiments. It is shown that evaporative cooling of both fermionic 14NH and bosonic 15NH is likely to be successful for hyperfine states that allow s-wave collisions. The calculated cross sections are very sensitive to the details of the interaction potential, due to the presence of (quasi)bound state resonances. The remaining inaccuracy of the ab initio potential-energy surface therefore gives rise to an uncertainty in the numerical cross-section values. However, based on a sampling of the uncertainty range of the ab initio calculations, we conclude that the exact potential is likely to be such that the elastic-to-inelastic cross-section ratio is sufficiently large to achieve efficient evaporative cooling. This likelihood is only weakly dependent on the size of the channel basis set used in the scattering calculations. [ABSTRACT FROM AUTHOR]

We present four-dimensional ab initio potential energy surfaces for the three different spin states of the NH(3Σ-)–NH(3Σ-) complex. The potentials are partially based on the work of Dhont et al. [J. Chem. Phys. 123, 184302 (2005)]. The surface for the quintet state is obtained at the RCCSD(T)/augmented correlation-consistent polarized valence triple-zeta (aug-cc-pVTZ) level of theory and the energy differences with the singlet and triplet states are calculated at the complete active space with nth-order perturbation theory/aug-cc-pVTZ (n=2,3) level of theory. The ab initio potentials are fitted to coupled spherical harmonics in the angular coordinates, and the long range is further expanded as a power series in 1/R. The RCCSD(T) potential is corrected for a size-consistency error of about 0.5×10-6 Eh prior to fitting. The long-range coefficients obtained from the fit are found to be in good agreement with first and second-order perturbation theory calculations. [ABSTRACT FROM AUTHOR]

Time-resolved dynamics of the photodissociation of molecular oxygen, O2, via the 3Σu- ion-pair state have been studied with femtosecond time resolution using a pump-probe scheme in combination with velocity map imaging of the resulting O+ and O- ions. The fourth harmonic of a femtosecond titanium-sapphire (Ti:sapphire) laser (λ≈205 nm) was found to cause three-photon pumping of O2 to a level at 18.1 eV. The parallel character of the observed O+ and O- images allowed us to conclude that dissociation takes place on the 3Σu- ion-pair state. The 815 nm fundamental of the Ti:sapphire laser used as probe was found to cause two-photon electron photodetachment starting from the O2 ion-pair state, giving rise to (O(3P)+O+(4S)) products. This was revealed by the observed depletion of the yield of the O- anion and the appearance of a new O+ cation signal with a kinetic energy Etransl(O+) dependent on the time delay between the pump and probe lasers. This time-delay dependence of the dissociation dynamics on the ion-pair state has also been simulated, and the experimental and simulated results coincide very well over the experimental delay-time interval from about 130 fs to 20 ps where two- or one-photon photodetachment takes place, corresponding to a change in the R(O+,O-) interatomic distance from 12 to about 900 Å. This is one of the first implementations of a depletion scheme in femtosecond pump-probe experiments which could prove to be quite versatile and applicable to many femtosecond time-scale experiments. [ABSTRACT FROM AUTHOR]

Ultraviolet photodissociation of SH (X 2Π, υ″=2–7) and SD (X 2Π, υ″=3–7) has been studied at 288 and 291 nm, using the velocity map imaging technique to probe the angular and speed distributions of the S(1D2) products. Photodissociation cross sections for the A 2Σ+←X 2Π(υ″) and 2Δ←X 2Π(υ″) transitions have been obtained by ab initio calculations at the CASSCF-MRSDCI/aug-cc-pV5Z level of theory. Both the experimental and theoretical results show that SH/SD photodissociation from X 2Π (υ″<=7) proceeds via the repulsive wall of the A 2Σ+ state. The angular distributions of S(1D2) indicate that the dissociation approaches the sudden recoil limit of the A 2Σ+ state, yielding strongly polarized fragments. The S(1D2) atoms are predominantly produced with total electronic angular momentum perpendicular to the recoil axis. [ABSTRACT FROM AUTHOR]

The transition from a liquid to a glass remains one of the most poorly understood phenomena in condensed matter physics, and still no fully microscopic theory exists that can describe the dynamics of supercooled liquids in a quantitative manner over all relevant time scales. Here, we present a theoretical framework that yields near-quantitative accuracy for the time-dependent correlation functions of a glass-forming system over a broad density range. Our approach requires only simple static structural information as input and is based entirely on first principles. Owing to its ab initio nature, the framework offers a unique platform to study the relation between structure and dynamics in glass-forming matter, and paves the way towards a systematically correctable and ultimately fully quantitative theory of microscopic glassy dynamics. [ABSTRACT FROM AUTHOR]

The mode-coupling theory of the glass transition treats the dynamics of supercooled liquids in terms of two-point density correlation functions. Here we consider a generalized, hierarchical formulation of schematic mode-coupling equations in which the full basis of multipoint density correlations is taken into account. By varying the parameters that control the effective contributions of higher-order correlations, we show that infinite hierarchies can give rise to both sharp and avoided glass transitions. Moreover, small changes in the form of the coefficients result in different scaling behaviors of the structural relaxation time, providing a means to tune the fragility in glass-forming materials. This demonstrates that the infinite-order construct of generalized mode-coupling theory constitutes a powerful and unifying framework for kinetic theories of the glass transition. [ABSTRACT FROM AUTHOR]

We investigate the ultracold reaction dynamics of magnetically trapped NH(X3Σ-) radicals using rigorous quantum scattering calculations involving three coupled potential energy surfaces. We find that the reactive NH + NH cross section is driven by a short-ranged collisional mechanism, and its magnitude is only weakly dependent on magnetic field strength. Unlike most ultracold reactions observed so far, the NH + NH scattering dynamics is nonuniversal. Our results indicate that chemical reactions can cause more trap loss than spin-inelastic NH + NH collisions, making molecular evaporative cooling more difficult than previously anticipated. [ABSTRACT FROM AUTHOR]

This paper describes a joint experimental and theoretical study of the photodissociation of vibrationally excited hydroxyl radicals. OH and OD radicals produced in a pulsed electric discharge supersonic beam are state-selected and focused by a hexapole and then photo-dissociated by a single laser tuned to various H/D or O atom (2 + 1) resonance enhanced multiphoton ionization (REMPI) wavelengths between 243 nm and 200 nm. The angle velocity distributions of the resulting O+ and D+ photofragment ions were recorded using velocity map imaging. Photodissociation to the O(3PJ) + H(2S) limit is shown to take place by one-photon excitation to the repulsive 1 2Σ- state. The experimental data shows that vibrationally excited OH/OD which are formed in the discharge are dissociated, and a vibrational temperature of ≈2000 K was estimated for the beam source. An analysis in the high-energy recoil sudden limit is used to predict the O(3PJ) fine structure branching ratios and alignment information in the molecular and laboratory velocity frame of the imaging experiment. The measured and predicted fine structure branching ratios and alignment parameters agree well at all dissociation wavelengths, supporting the model for photodissociation in the sudden limit regime. Several aspects of the experiment such as OH pre-alignment and orientation, ion-recoil, and Doppler-free imaging are discussed. [ABSTRACT FROM AUTHOR]

A correction to the article "Ab Initio Potential Energy Surfaces for NH3 - NH3 with Analytical Long Range" in the December 10, 2009 issue is presented.

Dense active matter is gaining widespread interest due to its remarkable similarity with conventional glass-forming materials. However, active matter is inherently out of equilibrium and even simple models such as active Brownian particles (ABPs) and active Ornstein-Uhlenbeck particles (AOUPs) behave markedly differently from their passive counterparts. Controversially, this difference has been shown to manifest itself via either a speedup, slowdown, or nonmonotonic change of the glassy relaxation dynamics. Here we rationalize these seemingly contrasting views on the departure from equilibrium by identifying the ratio of the short-time length scale to the cage length, i.e., the length scale of local particle caging, as a vital and unifying control parameter for active glassy matter. In particular, we explore the glassy dynamics of both thermal and athermal ABPs and AOUPs upon increasing the persistence time. We find that for all studied systems there is an optimum of the dynamics; this optimum occurs when the cage length coincides with the corresponding short-time length scale of the system, which is either the persistence length for athermal systems or a combination of the persistence length and a diffusive length scale for thermal systems. This new insight, for which we also provide a simple physical argument, allows us to reconcile and explain the manifestly disparate departures from equilibrium reported in many previous studies of dense active materials. [ABSTRACT FROM AUTHOR]

We study the collective dynamics of self-propelled rods in an inhomogeneous motility field. At the interface between two regions of constant but different motility, a smectic rod layer is spontaneously created through aligning interactions between the active rods, reminiscent of an artificial, semipermeable membrane. This "active membrane" engulfes rods which are locally trapped in low-motility regions and thereby further enhances the trapping efficiency by self-organization, an effect which we call "self-encapsulation." Our results are gained by computer simulations of self-propelled rod models confined on a two-dimensional planar or spherical surface with a stepwise constant motility field, but the phenomenon should be observable in any geometry with sufficiently large spatial inhomogeneity. We also discuss possibilities to verify our predictions of active-membrane formation in experiments of self-propelled colloidal rods and vibrated granular matter. [ABSTRACT FROM AUTHOR]

One of the key hallmarks of dense active matter in the liquid, supercooled, and solid phases is the so-called equal-time velocity correlations. Crucially, these correlations can emerge spontaneously, i.e., they require no explicit alignment interactions, and therefore represent a generic feature of dense active matter. This indicates that for a meaningful comparison or possible mapping between active and passive liquids one not only needs to understand their structural properties, but also the impact of these velocity correlations. This has already prompted several simulation and theoretical studies, though they are mostly focused on athermal systems and thus overlook the effect of translational diffusion. Here, we present a fully microscopic method to calculate nonequilibrium correlations in two-dimensional systems of thermal active Brownian particles (ABPs). We use the integration through transients formalism together with (active) mode-coupling theory and analytically calculate qualitatively consistent static structure factors and active velocity correlations. We complement our theoretical results with simulations of both thermal and athermal ABPs which exemplify the disruptive role that thermal noise has on velocity correlations.

The complete quantitative description of the structure of dense and supercooled liquids remains a notoriously difficult problem in statistical physics. Most studies to date focus solely on two-body structural correlations, and only a handful of papers have sought to consider additional three-body correlations. Here, we go beyond the state of the art by extracting many-body static structure factors from molecular dynamics simulations and by deriving accurate approximations up to the six-body structure factor via density functional theory. We find that supercooling manifestly increases four-body correlations, akin to the two- and three-body case. However, at small wave numbers, we observe that the four-point structure of a liquid drastically changes upon supercooling, both qualitatively and quantitatively, which is not the case in two-point structural correlations. This indicates that theories of the structure or dynamics of dense liquids should incorporate many-body correlations beyond the two-particle level to fully capture their intricate behavior., (© The Author(s) 2023. Published by Oxford University Press on behalf of National Academy of Sciences.)

Chiral active matter is enjoying a rapid increase of interest, spurred by the rich variety of asymmetries that can be attained in, e.g., the shape or self-propulsion mechanism of active particles. Though this has already led to the observance of so-called chiral crystals, active chiral glasses remain largely unexplored. A possible reason for this could be the naive expectation that interactions dominate the glassy dynamics and the details of the active motion become increasingly less relevant. Here, we show that quite the opposite is true by studying the glassy dynamics of interacting chiral active Brownian particles. We demonstrate that when our chiral fluid is pushed to glassy conditions, it exhibits highly nontrivial dynamics, especially compared to a standard linear active fluid such as common active Brownian particles. Despite the added complexity, we are still able to present a full rationalization for all identified dynamical regimes. Most notably, we introduce a new "hammering" mechanism, unique to rapidly spinning particles in high-density conditions, that can fluidize a chiral active solid.

Building on the recently derived inhomogeneous mode-coupling theory, we extend the generalized mode-coupling theory of supercooled liquids to inhomogeneous environments. This provides a first-principles-based, systematic, and rigorous way of deriving high-point dynamical susceptibilities from variations of the many-body dynamic structure factors with respect to their conjugate field. This framework allows for a fully microscopic possibility to probe for collective relaxation mechanisms in supercooled liquids near the mode-coupling glass transition. The behavior of these dynamical susceptibilities is then studied in the context of simplified self-consistent relaxation models.

It is widely believed that the emergence of slow glassy dynamics is encoded in a material's microstructure. First-principles theory [mode-coupling theory (MCT)] is able to predict the dramatic slowdown of the dynamics from only static two-point correlations as input, yet it cannot capture all of the observed dynamical behavior. Here we go beyond two-point spatial correlation functions by extending MCT systematically to include higher-order static and dynamic correlations. We demonstrate that only adding the static triplet direct correlations already qualitatively changes the predicted glass-transition diagram of binary hard spheres and silica. Moreover, we find a nontrivial competition between static triplet correlations that work to stabilize the glass state and dynamic higher-order correlations that destabilize it for both materials. We conclude that the conventionally neglected static triplet direct correlations as well as higher-order dynamic correlations are, in fact, non-negligible in both fragile and strong glassformers.

Generalized mode-coupling theory (GMCT) has recently emerged as a promising first-principles theory to study the poorly understood dynamics of glass-forming materials. Formulated as a hierarchical extension of standard mode-coupling theory (MCT), it is able to systematically improve its predictions by including the exact dynamics of higher-order correlation functions into its hierarchy. However, in contrast to Newtonian dynamics, a fully generalized version of the theory based on Brownian dynamics is still lacking. To close this gap, we provide a detailed derivation of GMCT for colloidal mixtures obeying a many-body Smoluchowski equation. We demonstrate that a hierarchy of coupled equations can again be established and show that these, consistent with standard MCT, are identical to the ones obtained from Newtonian GMCT when taking the overdamped limit. Consequently, the nontrivial similarity between Brownian and Newtonian MCT is maintained for our multicomponent GMCT. As a proof of principle, we also solve the generalized mode-coupling equations for the binary Kob-Andersen Lennard-Jones mixture undergoing Brownian dynamics and confirm the improved predictive power of the theory upon using more levels of the GMCT hierarchy of equations.

Sticky hard spheres, i.e., hard particles decorated with a short-ranged attractive interaction potential, constitute a relatively simple model with highly non-trivial glassy dynamics. The mode-coupling theory of the glass transition (MCT) offers a qualitative account of the complex reentrant dynamics of sticky hard spheres, but the predicted glass transition point is notoriously underestimated. Here we apply an improved first-principles-based theory, referred to as generalized mode-coupling theory (GMCT), to sticky hard spheres. This theoretical framework seeks to go beyond MCT by hierarchically expanding the dynamics in higher-order density correlation functions. We predict the phase diagrams from the first few levels of the GMCT hierarchy and the dynamics-related critical exponents, all of which are much closer to the empirical observations than MCT. Notably, the prominent reentrant glassy dynamics, the glass-glass transition, and the higher-order bifurcation singularity classes (A 3 and A 4 ) of sticky hard spheres are found to be preserved within GMCT at arbitrary order. Moreover, we demonstrate that when the hierarchical order of GMCT increases, the effect of the short-ranged attractive interactions becomes more evident in the dynamics. This implies that GMCT is more sensitive to subtle microstructural differences than MCT, and that the framework provides a promising first-principles approach to systematically go beyond the MCT regime.

Soft particles such as microgels can undergo significant and anisotropic deformations when adsorbed to a liquid interface. This, in turn, leads to a complex phase behavior upon compression. To date, experimental efforts have predominantly provided phenomenological links between microgel structure and resulting interfacial behavior, while simulations have not been entirely successful in reproducing experiments or predicting the minimal requirements for the desired phase behavior. Here, we develop a multiscale framework to link the molecular particle architecture to the resulting interfacial morphology and, ultimately, to the collective interfacial phase behavior. To this end, we investigate interfacial morphologies of different poly( N -isopropylacrylamide) particle systems using phase-contrast atomic force microscopy and correlate the distinct interfacial morphology with their bulk molecular architecture. We subsequently introduce a new coarse-grained simulation method that uses augmented potentials to translate this interfacial morphology into the resulting phase behavior upon compression. The main novelty of this method is the possibility to efficiently encode multibody interactions, the effects of which are key to distinguishing between heterostructural (anisotropic collapse) and isostructural (isotropic collapse) phase transitions. Our approach allows us to qualitatively resolve existing discrepancies between experiments and simulations. Notably, we demonstrate the first in silico account of the two-dimensional isostructural transition, which is frequently found in experiments but elusive in simulations. In addition, we provide the first experimental demonstration of a heterostructural transition to a chain phase in a single-component system, which has been theoretically predicted decades ago. Overall, our multiscale framework provides a phenomenological bridge between physicochemical soft-particle characteristics at the molecular scale and nanoscale and the collective self-assembly phenomenology at the macroscale, serving as a stepping stone toward an ultimately more quantitative and predictive design approach.

Most cells possess the capacity to locomote. Alone or collectively, this allows them to adapt, to rearrange, and to explore their surroundings. The biophysical characterization of such motile processes, in health and in disease, has so far focused mostly on two limiting cases: single-cell motility on the one hand and the dynamics of confluent tissues such as the epithelium on the other. The in-between regime of clusters, composed of relatively few cells moving as a coherent unit, has received less attention. Such small clusters are, however, deeply relevant in development but also in cancer metastasis. In this work, we use cellular Potts models and analytical active matter theory to understand how the motility of small cell clusters changes with N, the number of cells in the cluster. Modeling and theory reveal our two main findings: cluster persistence time increases with N, whereas the intrinsic diffusivity decreases with N. We discuss a number of settings in which the motile properties of more complex clusters can be analytically understood, revealing that the focusing effects of small-scale cooperation and cell-cell alignment can overcome the increased bulkiness and internal disorder of multicellular clusters to enhance overall migrational efficacy. We demonstrate this enhancement for small-cluster collective durotaxis, which is shown to proceed more effectively than for single cells. Our results may provide some novel, to our knowledge, insights into the connection between single-cell and large-scale collective motion and may point the way to the biophysical origins of the enhanced metastatic potential of small tumor cell clusters., (Copyright © 2021 Biophysical Society. Published by Elsevier Inc. All rights reserved.)

The volume phase transition of microgels is one of the most paradigmatic examples of stimuli-responsiveness, enabling a collapse from a highly swollen microgel state into a densely coiled state by an external stimulus. Although well characterized in bulk, it remains unclear how the phase transition is affected by the presence of a confining interface. Here, we demonstrate that the temperature-induced volume phase transition of poly( N -isopropylacrylamide) microgels, conventionally considered an intrinsic molecular property of the polymer, is in fact largely suppressed when the microgel is adsorbed to an air/liquid interface. We further observe a hysteresis in the core morphology and interfacial pressure between heating and cooling cycles. Our results, supported by molecular dynamics simulations, reveal that the dangling polymer chains of microgel particles, spread at the interface under the influence of surface tension, do not undergo any volume phase transition. The balance in free energy responsible for the volume phase transition is fundamentally altered by interfacial confinement. These results imply that important technological properties of such systems, including the temperature-induced destabilization of emulsions, do not occur via a decrease in the interfacial coverage of the microgels.

The coupling of active, self-motile particles to topological constraints can give rise to novel non-equilibrium dynamical patterns that lack any passive counterpart. Here we study the behavior of self-propelled rods confined to a compact spherical manifold by means of Brownian dynamics simulations. We establish the state diagram and find that short active rods at sufficiently high density exhibit a glass transition toward a disordered state characterized by persistent self-spinning motion. By periodically melting and revitrifying the spherical spinning glass, we observe clear signatures of time-dependent aging and rejuvenation physics. We quantify the crucial role of activity in these non-equilibrium processes, and rationalize the aging dynamics in terms of an absorbing-state transition toward a more stable active glassy state. Our results demonstrate both how concepts of passive glass phenomenology can carry over into the realm of active matter, and how topology can enrich the collective spatiotemporal dynamics in inherently non-equilibrium systems.

We investigate the ultracold reaction dynamics of magnetically trapped NH(X (3)Σ(-)) radicals using rigorous quantum scattering calculations involving three coupled potential energy surfaces. We find that the reactive NH+NH cross section is driven by a short-ranged collisional mechanism, and its magnitude is only weakly dependent on magnetic field strength. Unlike most ultracold reactions observed so far, the NH+NH scattering dynamics is nonuniversal. Our results indicate that chemical reactions can cause more trap loss than spin-inelastic NH+NH collisions, making molecular evaporative cooling more difficult than previously anticipated.

We present four-dimensional ab initio potential energy surfaces for the three different spin states of the NH((3)Sigma(-))-NH((3)Sigma(-)) complex. The potentials are partially based on the work of Dhont et al. [J. Chem. Phys. 123, 184302 (2005)]. The surface for the quintet state is obtained at the RCCSD(T)/augmented correlation-consistent polarized valence triple-zeta (aug-cc-pVTZ) level of theory and the energy differences with the singlet and triplet states are calculated at the complete active space with nth-order perturbation theory/aug-cc-pVTZ (n=2,3) level of theory. The ab initio potentials are fitted to coupled spherical harmonics in the angular coordinates, and the long range is further expanded as a power series in 1/R. The RCCSD(T) potential is corrected for a size-consistency error of about 0.5x10(-6) E(h) prior to fitting. The long-range coefficients obtained from the fit are found to be in good agreement with first and second-order perturbation theory calculations.

Ultraviolet photodissociation of SH (X 2Pi, upsilon"=2-7) and SD (X 2Pi, upsilon"=3-7) has been studied at 288 and 291 nm, using the velocity map imaging technique to probe the angular and speed distributions of the S(1D2) products. Photodissociation cross sections for the A 2Sigma+<--X 2Pi(upsilon") and 2Delta<--X 2Pi(upsilon") transitions have been obtained by ab initio calculations at the CASSCF-MRSDCI/aug-cc-pV5Z level of theory. Both the experimental and theoretical results show that SH/SD photodissociation from X 2Pi (upsilon"