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Register a new userEntangled system-and-environment dynamics: Phase-space dissipaton theory
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Dissipaton-equation-of-motion (DEOM) theory [Y. J. Yan, J. Chem. Phys. 140, 054105 (2014)] is an exact and nonperturbative many-particle method for open quantum systems. The existing dissipaton algebra treats also the dynamics of hybrid bath solvation coordinates. The dynamics of conjugate momentums remain to be addressed within the DEOM framework. In this work, we establish this missing ingredient, the dissipaton algebra on solvation momentums, with rigorous validations against necessary and sufficient criteria. The resulted phase-space DEOM theory will serve as a solid ground for further developments of various practical methods toward a broad range of applications. We illustrate this novel dissipaton algebra with the phase-space DEOM-evaluation on heat current fluctuation.
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Forty-five years after the point de depart [1] of density functional theory, its applications in chemistry and the study of electronic structures keep steadily growing. However, the precise form of the energy functional in terms of the electron density still eludes us -- and possibly will do so forever [2]. In what follows we examine a formulation in the same spirit with phase space variables. The validity of Hohenberg-Kohn-Levy-type theorems on phase space is recalled. We study the representability problem for reduced Wigner functions, and proceed to analyze properties of the new functional. Along the way, new results on states in the phase-space formalism of quantum mechanics are established. Natural Wigner orbital theory is developed in depth, with the final aim of constructing accurate correlation-exchange functionals on phase space. A new proof of the overbinding property of the Mueller functional is given. This exact theory supplies its home at long last to that illustrious ancestor, the Thomas-Fermi model.
We analyze the role of coherent, non-perturbative system-bath interactions in a photosynthetic heat engine. Using the reaction-coordinate formalism to describe the vibrational phonon-environment in the engine, we analyze the efficiency around an optimal parameter regime predicted in earlier works. We show that, in the limit of high-temperature photon irradiation, the phonon-assisted population transfer between bright and dark states is suppressed due to dephasing from the photon environment, even in the Markov limit where we expect the influence of each bath to have an independent and additive affect on the dynamics. Manipulating the phonon bath properties via its spectral density enables us to identify both optimal low- and high-frequency regimes where the suppression can be removed. This suppression of transfer and its removal suggests that it is important to consider carefully the non-perturbative and cooperative effects of system-bath environments in designing artificial photosynthetic systems, and also that manipulating inter-environmental interactions could provide a new multidimensional lever by which to optimize photocells and other types of quantum device.
The possibility of suddenly ionized molecules undergoing extremely fast electron hole dynamics prior to significant structural change was first recognized more than 20 years ago and termed charge migration. The accurate probing of ultrafast electron hole dynamics requires measurements that have both sufficient temporal resolution and can detect the localization of a specific hole within the molecule. We report an investigation of the dynamics of inner valence hole states in isopropanol where we use an x-ray pump/x-ray probe experiment, with site and state-specific probing of a transient hole state localized near the oxygen atom in the molecule, together with an ab initio theoretical treatment. We record the signature of transient hole dynamics and make the first observation of dynamics driven by frustrated Auger-Meitner transitions. We verify that the hole lifetime is consistent with our theoretical prediction. This state-specific measurement paves the way to widespread application for observations of transient hole dynamics localized in space and time in molecules and thus to charge transfer phenomena that are fundamental in chemical and material physics.
In a previous article [J. Chem. Phys. 138, 084108 (2013)], we showed that the $tto 0_+$ limit of ring-polymer molecular dynamics (RPMD) rate-theory is also the $tto 0_+$ limit of a new type of quantum flux-side time-correlation function, in which the dividing surfaces are invariant to imaginary-time translation; in other words, that RPMD transition-state theory (RPMD-TST) is a $tto 0_+$ quantum transition-state theory (QTST). Recently, Jang and Voth [J. Chem. Phys. 144, 084110 (2016)] rederived this quantum $tto 0_+$ limit, and claimed that it gives instead the centroid-density approximation. Here we show that the $tto 0_+$ limit derived by Jang and Voth is in fact RPMD-TST.
A model Hamiltonian for the reaction CH$_4^+ rightarrow$ CH$_3^+$ + H, parametrized to exhibit either early or late inner transition states, is employed to investigate the dynamical characteristics of the roaming mechanism. Tight/loose transition states and conventional/roaming reaction pathways are identified in terms of time-invariant objects in phase space. These are dividing surfaces associated with normally hyperbolic invariant manifolds (NHIMs). For systems with two degrees of freedom NHIMS are unstable periodic orbits which, in conjunction with their stable and unstable manifolds, unambiguously define the (locally) non-recrossing dividing surfaces assumed in statistical theories of reaction rates. By constructing periodic orbit continuation/bifurcation diagrams for two values of the potential function parameter corresponding to late and early transition states, respectively, and using the total energy as another parameter, we dynamically assign different regions of phase space to reactants and products as well as to conventional and roaming reaction pathways. The classical dynamics of the system are investigated by uniformly sampling trajectory initial conditions on the dividing surfaces. Trajectories are classified into four different categories: direct reactive and non reactive trajectories,which lead to the formation of molecular and radical products respectively, and roaming reactive and non reactive orbiting trajectories, which represent alternative pathways to form molecular and radical products. By analysing gap time distributions at several energies we demonstrate that the phase space structure of the roaming region, which is strongly influenced by non-linear resonances between the two degrees of freedom, results in nonexponential (nonstatistical) decay.
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