Symmetries constrain dynamics. We test this fundamental physical principle, experimentally and by molecular dynamics simulations, for a hot Janus swimmer operating far from thermal equilibrium. Our results establish scalar and vectorial steady-state fluctuation theorems and a thermodynamic uncertainty relation that link the fluctuating particle current to its entropy production at an effective temperature. A Markovian minimal model elucidates the underlying nonequilibrium physics.
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http://dx.doi.org/10.1103/PhysRevE.94.030602 | DOI Listing |
J Chem Theory Comput
January 2025
Yusuf Hamied Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, U.K.
Density functional approximations can reduce the spin symmetry breaking observed for self-consistent field (SCF) solutions compared to Hartree-Fock theory, but the amount of exact Hartree-Fock (HF) exchange appears to be a key determinant in broken symmetry. To elucidate the precise role of exact exchange, we investigate the energy landscape of unrestricted Hartree-Fock and Kohn-Sham density functional theory for benzene and square cyclobutadiene, which provide paradigmatic examples of closed-shell and open-shell electronic structures, respectively. We find that increasing the amount of exact exchange leads to more local SCF minima, which can be characterized as combinatorial arrangements of unpaired electrons in the carbon π system.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States.
Stacking interactions are a recurring motif in supramolecular chemistry and biochemistry, where a persistent theme is a preference for parallel-displaced aromatic rings rather than face-to-face π-stacking. This is typically explained in terms of quadrupole-quadrupole interactions between the arene moieties but that interpretation is inconsistent with accurate calculations, which reveal that the quadrupolar picture is qualitatively wrong. At typical π-stacking distances, quadrupolar electrostatics may differ in sign from an exact calculation based on charge densities of the interacting arenes.
View Article and Find Full Text PDFNat Commun
January 2025
TCM Group, Cavendish Laboratory, Department of Physics, Cambridge, UK.
We report on a class of gapped projected entangled pair states (PEPS) with non-trivial Euler topology motivated by recent progress in band geometry. In the non-interacting limit, these systems have optimal conditions relating to saturation of quantum geometrical bounds, allowing for parent Hamiltonians whose lowest bands are completely flat and which have the PEPS as unique ground states. Protected by crystalline symmetries, these states evade restrictions on capturing tenfold-way topological features with gapped PEPS.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
Department of Chemistry, Indian Institute of Technology Patna, Bihta 801106, India.
This study probes the vibronic interactions in the photoelectron spectra of CAlGe, exploring its six excited electronic states through an approach that combines the electronic structure calculations and the quantum nuclear dynamics. Central to this investigation is utilizing a model diabatic Hamiltonian, which allows for the exact evaluation of Hamiltonian parameters and fitting potential energy cuts (PECs). Notably, the analysis of these PECs uncovers pronounced nonadiabatic effects within the photoelectron spectra, emphasized by the presence of multiple conical intersections.
View Article and Find Full Text PDFPhys Rev Lett
December 2024
Institute for Advanced Study, Tsinghua University, Beijing 100084, China.
The nonintegrable higher spin Kitaev honeycomb model has an exact Z_{2} gauge structure, which exclusively identifies quantum spin liquid in the half-integer spin Kitaev model. But its constraints for the integer-spin Kitaev model are much limited, and even trivially gapped insulators cannot be excluded. The physical implications of exact Z_{2} gauge structure, especially Z_{2} fluxes, in integer-spin models remain largely unexplored.
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