A new method for enhancing the charge separation and photo‐electrochemical stability of CuBi₂O₄ photoelectrodes by sequentially depositing Bi₂O₃ and CuO layers on fluorine‐doped tin oxide substrates with pulsed laser deposition (PLD), followed by rapid thermal processing (RTP), resulting in phase‐pure, highly crystalline films after 10 min at 650 °C, is reported. Conventional furnace annealing of similar films for 72 h at 500 °C do not result in phase‐pure CuBi₂O₄. The combined PLD and RTP approach allow excellent control of the Bi:Cu stoichiometry and results in photoelectrodes with superior electronic properties compared to photoelectrodes fabricated through spray pyrolysis. The low photocurrents of the CuBi₂O₄ photocathodes fabricated through PLD/RTP in this study are primarily attributed to their low specific surface area, lack of CuO impurities, and limited, slow charge transport in the undoped films. Bare (without protection layers) CuBi₂O₄ photoelectrodes made with PLD/RTP shows a photocurrent decrease of only 26% after 5 h, which represents the highest stability reported to date for this material. The PLD/RTP fabrication approach offers new possibilities of fabricating complex metal oxides photoelectrodes with a high degree of crystallinity and good electronic properties at higher temperatures than the thermal stability of glass‐based transparent conductive substrates would allow.

We present a comprehensive study of semiclassical phase-space propagation in the Wigner representation, emphasizing numerical applications, in particular as an initial-value representation. Two semiclassical approximation schemes are discussed. The propagator of the Wigner function based on van Vleck’s approximation replaces the Liouville propagator by a quantum spot with an oscillatory pattern reflecting the interference between pairs of classical trajectories. Employing phase-space path integration instead, caustics in the quantum spot are resolved in terms of Airy functions. We apply both to two benchmark models of nonlinear molecular potentials, the Morse oscillator and the quartic double well, to test them in standard tasks such as computing autocorrelation functions and propagating coherent states. The performance of semiclassical Wigner propagation is very good even in the presence of marked quantum effects, e.g., in coherent tunneling and in propagating Schrödinger cat states, and of classical chaos in four-dimensional phase space. We suggest options for an effective numerical implementation of our method and for integrating it in Monte-Carlo–Metropolis algorithms suitable for high-dimensional systems.

Quantum chaos is presented as a paradigm of information processing by dynamical systems at the bottom of the range of phase-space scales. Starting with a brief review of classical chaos as entropy flow from micro- to macro-scales, I argue that quantum chaos came as an indispensable rectification, removing inconsistencies related to entropy in classical chaos: bottom-up information currents require an inexhaustible entropy production and a diverging information density in phase-space, reminiscent of Gibbs’ paradox in statistical mechanics. It is shown how a mere discretization of the state space of classical models already entails phenomena similar to hallmarks of quantum chaos and how the unitary time evolution in a closed system directly implies the “quantum death” of classical chaos. As complementary evidence, I discuss quantum chaos under continuous measurement. Here, the two-way exchange of information with a macroscopic apparatus opens an inexhaustible source of entropy and lifts the limitations implied by unitary quantum dynamics in closed systems. The infiltration of fresh entropy restores permanent chaotic dynamics in observed quantum systems. Could other instances of stochasticity in quantum mechanics be interpreted in a similar guise? Where observed quantum systems generate randomness, could it result from an exchange of entropy with the macroscopic meter? This possibility is explored, presenting a model for spin measurement in a unitary setting and some preliminary analytical results based on it.

We construct a microscopic model to study discrete randomness in bistable systems coupled to an environment comprising many degrees of freedom. A quartic double well is bilinearly coupled to a finite number N of harmonic oscillators. Solving the time-reversal invariant Hamiltonian equations of motion numerically, we show that for $N=1$, the system exhibits a transition with increasing coupling strength from integrable to chaotic motion, following the Kolmogorov-Arnol’d-Moser (KAM) scenario. Raising N to values of the order of 10 and higher, the dynamics crosses over to a quasi-relaxation, approaching either one of the stable equilibria at the two minima of the potential. We corroborate the irreversibility of this relaxation on other characteristic timescales of the system by recording the time dependences of autocorrelation, partial entropy, and the frequency of jumps between the wells as functions of N and other parameters. Preparing the central system in the unstable equilibrium at the top of the barrier and the bath in a random initial state drawn from a Gaussian distribution, symmetric under spatial reflection, we demonstrate that the decision whether to relax into the left or the right well is determined reproducibly by residual asymmetries in the initial positions and momenta of the bath oscillators. This result reconciles the randomness and spontaneous symmetry breaking of the asymptotic state with the conservation of entropy under canonical transformations and the manifest symmetry of potential and initial condition of the bistable system.

We study directed transport of charge and intrinsic angular momentum by periodically driven scattering in the regime of fast and strong driving. A spin-orbit coupling through a kicked magnetic field confined to a compact region in space leads to irregular scattering and triggers spin flips in a spatially asymmetric manner which allows us to generate polarized currents. The dynamical mechanisms responsible for the spin separation carry over to the quantum level and give rise to spin pumping. Our theory based on the Floquet formalism is confirmed by numerical solutions of the time-dependent inhomogeneous Schrödinger equation with a continuous source term.

Spin measurement is studied as a unitary time evolution of the spin coupled to an environment representing the meter and the apparatus. Modeling the environment as a heat bath comprising only a finite number of boson modes and represented in a basis of coherent states, following the Davydov ansatz, it can be fully included in the quantum time evolution of the total system. We perform numerical simulations of projective measurements of the polarization, with the spins prepared initially in a neutral pure state. The likewise pure initial state of the environment is constructed as a product of coherent states of the boson modes with a random distribution of their centroids around the origin of phase space. Switching the self-energy of the spin and the coupling to the heat bath on and off by a time-dependent modulation, we observe the outcome of the measurement in terms of the long-time behavior of the spin. Interacting with the heat bath, the spins get entangled with it and lose coherence, thus reproducing the collapse of the wave function. The expected quantum randomness in the final state is manifest in our simulations as a tendency of the spin to approach either one of the two eigenstates of the measured spin operator, recovering an almost pure state. The unitary time evolution allows us to reproducibly relate these random final states to the respective initial states of the environment and to monitor the exchange of information between the two subsystems in terms of their purity and mutual entropy.