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We present an ab initio molecular dynamics (MD) investigation of the tautomeric equilibrium for aqueous solutions of glycine and acetone at realistic experimental conditions. Metadynamics is used to accelerate proton migration among tautomeric centers. Due to the formation of complex water-ion structures involved the proton dynamics in the aqueous environment, standard enhanced sampling approaches may face severe limitations in providing a general description of the phenomenon. Recently, we developed a set of Collective Variables (CVs) designed to study protons transfer reactions in complex condensed systems [Grifoni et al. PNAS, 2019, 116(10), 4054-4057]. In this work we applied this approach to study proton dissociation dynamics leading to tautomeric interconversion of biologically and chemically relevant prototypical systems, namely glycine and acetone in water. Although relatively simple from a chemical point of view, the results show that even for these small systems complex reaction pathways and non-trivial conversion dynamics are observed. The generality of our method allows obtaining these results without providing any prior information on the dissociation dynamics but only the atomic species that can exchange protons in the process. Our results agree with literature estimates and demonstrate the general applicability of this method in the study of tautomeric reactions.
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The quantum many-body problem in condensed phases is often simplified using a quasiparticle description, such as effective mass theory for electron motion in a periodic solid. These approaches are often the basis for understanding many fundamental condensed phase processes, including the molecular mechanisms underlying solar energy harvesting and photocatalysis. Despite the importance of these effective particles, there is still a need for computational methods that can explore their behavior on chemically relevant length and time scales. This is especially true when the interactions between the particles and their environment are important. We introduce an approach for studying quasiparticles in condensed phases by combining effective mass theory with the path integral treatment of quantum particles. This framework incorporates the generally anisotropic electronic band structure of materials into path integral simulation schemes to enable modeling of quasiparticles in quantum confinement, for example. We demonstrate the utility of effective mass path integral simulations by modeling an exciton in solid potassium chloride and electron trapping by a sulfur vacancy in monolayer molybdenum disulfide.
We demonstrate that the critical temperature for valence tautomeric interconversion in Cobalt dioxolene complexes can be significantly changed when a static electric field is applied to the molecule. This is achieved by effectively manipulating the redox potential of the metallic acceptor forming the molecule. Importantly our accurate density functional theory calculations demonstrate that already a field of 0.1 V/nm, achievable in Stark spectroscopy experiments, can produce a change in the critical temperature for the interconversion of 20 K. Our results indicate a new way for switching on and off the magnetism in a magnetic molecule. This offers the unique chance of controlling magnetism at the atomic scale by electrical means.
We characterize several equilibrium vortex effects in a rotating Bose-Einstein condensate. Specifically we attempt precision measurements of vortex lattice spacing and the vortex core size over a range of condensate densities and rotation rates. These measurements are supplemented by numerical simulations, and both experimental and numerical data are compared to theory predictions of Sheehy and Radzihovsky [17] (cond-mat/0402637) and Baym and Pethick [25] (cond-mat/0308325). Finally, we study the effect of the centrifugal weakening of the trapping spring constants on the critical temperature for quantum degeneracy and the effects of finite temperature on vortex contrast.
The recent advances in creating nearly degenerate quantum dipolar gases in optical lattices are opening the doors for the exploration of equilibrium physics of quantum systems with anisotropic and long-range dipolar interactions. In this paper we study the zero- and finite-temperature phase diagrams of a system of hard-core dipolar bosons at half-filling, trapped in a two-dimensional optical lattice. The dipoles are aligned parallel to one another and tilted out of the optical lattice plane by means of an external electric field. At zero-temperature, the system is a superfluid at all tilt angles $theta$ provided that the strength of dipolar interaction is below a critical value $V_c(theta)$. Upon increasing the interaction strength while keeping $theta$ fixed, the superfluid phase is destabilized in favor of a checkerboard or a stripe solid depending on the tilt angle. We explore the nature of the phase transition between the two solid phases and find evidence of a micro-emulsion phase, following the Spivak-Kivelson scenario, separating these two solid phases. Additionally, we study the stability of these quantum phases against thermal fluctuations and find that the stripe solid is the most robust, making it the best candidate for experimental observation.
We present a comprehensive review of the physical behavior of yield stress materials in soft condensed matter, which encompass a broad range of materials from colloidal assemblies and gels to emulsions and non-Brownian suspensions. All these disordered materials display a nonlinear flow behavior in response to external mechanical forces, due to the existence of a finite force threshold for flow to occur: the yield stress. We discuss both the physical origin and rheological consequences associated with this nonlinear behavior, and give an overview of experimental techniques available to measure the yield stress. We discuss recent progress concerning a microscopic theoretical description of the flow dynamics of yield stress materials, emphasizing in particular the role played by relaxation time scales, the interplay between shear flow and aging behavior, the existence of inhomogeneous shear flows and shear bands, wall slip, and non-local effects in confined geometries.
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