Active particles, like motile microorganisms and active colloids, are often found in confined environments where they can be arrested in a persistent orbital motion. Here, we investigate noise-induced switching between different coexisting orbits of a confined active particle as a stochastic escape problem. We show that, in the low-noise regime, this problem can be formulated as a least-action principle, which amounts to finding the most probable escape path from an orbit to the basin of attraction of another coexisting orbit. The corresponding action integral coincides with the activation energy, a quantity readily accessible in experiments and simulations via escape rate data. To illustrate how this approach can be used to tackle specific problems, we calculate optimum escape paths and activation energies for noise-induced transitions between clockwise and counterclockwise circular orbits of an active particle in radially symmetric confinement. We also investigated transitions between orbits of different topologies (ovals and lemniscates) coexisting in elliptic confinement. In all worked examples, the calculated optimum paths and minimum actions are in excellent agreement with mean-escape-time data obtained from direct numerical integration of the Langevin equations.
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http://dx.doi.org/10.1103/PhysRevE.108.044605 | DOI Listing |
Acc Chem Res
January 2025
The Wolfson Catalysis Centre, Department of Chemistry, University of Oxford, Oxford OX1 3QR, U.K.
ConspectusThe discovery of reversible hydrogenation using metal-free phosphoborate species in 2006 marked the official advent of frustrated Lewis pair (FLP) chemistry. This breakthrough revolutionized homogeneous catalysis approaches and paved the way for innovative catalytic strategies. The unique reactivity of FLPs is attributed to the Lewis base (LB) and Lewis acid (LA) sites either in spatial separation or in equilibrium, which actively react with molecules.
View Article and Find Full Text PDFJ Chem Theory Comput
January 2025
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany.
X-ray absorption spectroscopy (XAS) is a powerful method for exploring molecular electronic structure by exciting core electrons into higher unoccupied molecular orbitals. In this study, we present the first integration of the spin-unrestricted similarity-transformed equation-of-motion coupled cluster method (CVS-USTEOM-CCSD) for core-excited and core-ionized states into the ORCA quantum chemistry package. Using the core-valence separation (CVS) approach, we evaluate the accuracy of CVS-USTEOM-CCSD across 13 open-shell organic systems, covering over 20 core excitations with diverse spin multiplicities (doublet, triplet, and quartet).
View Article and Find Full Text PDFJ Chem Theory Comput
January 2025
Department of Chemistry, Graduate School of Advanced Science and Engineering, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima City, Hiroshima 739-8526, Japan.
Exploring electronic states in actinide compounds is a critical aspect of nuclear science. However, considering relativistic effects and electron correlation in theoretical calculations poses a complex challenge. To tackle this, we developed the CASPT2/RASPT2 program along with the DIRAC program, enabling calculations of electron correlation methods using multiconfigurational perturbation theory with various relativistic Hamiltonians.
View Article and Find Full Text PDFJ Chem Phys
January 2025
Department of Chemistry and Pharmaceutical Sciences, Amsterdam Institute of Molecular and Life Sciences (AIMMS), Vrije Universiteit Amsterdam, De Boelelaan 1108, 1081 HZ Amsterdam, The Netherlands, https://www.theochem.nl.
We have quantum chemically analyzed the trends in bond dissociation enthalpy (BDE) of H3C-XHn single bonds (XHn = CH3, NH2, OH, F, Cl, Br, I) along three different dissociation pathways at ZORA-BLYP-D3(BJ)/TZ2P: (i) homolytic dissociation into H3C∙ + ∙XHn, (ii) heterolytic dissociation into H3C+ + -XHn, and (iii) heterolytic dissociation into H3C- + +XHn. The associated BDEs for the three pathways differ not only quantitatively but, in some cases, also in terms of opposite trends along the C-X series. Based on activation strain analyses and quantitative molecular orbital theory, we explain how these differences are caused by the profoundly different electronic structures of, and thus bonding mechanisms between, the resulting fragments in the three different dissociation pathways.
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