Quantum coherence profoundly alters classical thermodynamic expectations by modifying the structure and accessibility of probability distributions. Classically, transitions to lower-entropy states (local second-law violations) are exponentially suppressed, as lower-entropy configurations have fewer available microstates and are statistically improbable. However, introducing quantum coherence and structured quantum interference among semiclassical trajectories significantly changes this scenario. Quantum coherence reduces local entropy by establishing correlations among states that are classically independent, effectively restructuring probability amplitudes to channel transitions toward otherwise improbable low-entropy states. We analyze this phenomenon explicitly within the framework of semiclassical approximations, employing the Van Vleck-Gutzwiller propagator to quantify how interference terms arising from coherent superpositions modify classical fluctuation theorems. We demonstrate that quantum coherence, especially when combined with chaos-assisted dynamical tunneling, greatly enhances the probability of transitions to low-entropy configurations, creating pronounced counter-ergodic effects. Furthermore, by considering purification of mixed quantum states, we propose methodologies for deliberately engineering quantum phases among interfering pathways. This phase engineering can explicitly enhance coherence-driven transitions into lower-entropy states, providing a novel thermodynamic resource. Finally, we explore the feasibility of molecular-scale quantum machines exploiting these principles, highlighting their potential applications in quantum thermodynamics and quantum biology for performing useful work through coherence-mediated entropy reduction.
Quantum coherence profoundly alters classical thermodynamic expectations by modifying the structure and accessibility of probability distributions. Classically, transitions to lower-entropy states (local second-law violations) are exponentially suppressed, as lower-entropy configurations have fewer available microstates and are statistically improbable. However, introducing quantum coherence and structured quantum interference among semiclassical trajectories significantly changes this scenario. Quantum coherence reduces local entropy by establishing correlations among states that are classically independent, effectively restructuring probability amplitudes to channel transitions toward otherwise improbable low-entropy states. We analyze this phenomenon explicitly within the framework of semiclassical approximations, employing the Van Vleck-Gutzwiller propagator to quantify how interference terms arising from coherent superpositions modify classical fluctuation theorems. We demonstrate that quantum coherence, especially when combined with chaos-assisted dynamical tunneling, greatly enhances the probability of transitions to low-entropy configurations, creating pronounced counter-ergodic effects. Furthermore, by considering purification of mixed quantum states, we propose methodologies for deliberately engineering quantum phases among interfering pathways. This phase engineering can explicitly enhance coherence-driven transitions into lower-entropy states, providing a novel thermodynamic resource. Finally, we explore the feasibility of molecular-scale quantum machines exploiting these principles, highlighting their potential applications in quantum thermodynamics and quantum biology for performing useful work through coherence-mediated entropy reduction.
In quantum systems with a classical limit, advanced semiclassical methods provide the crucial link between phase-space structures, reflecting the distinction between chaotic, mixed or integrable classical dynamics, and the corresponding quantum properties. Well established techniques dealing with ergodic wave interference in the usual semiclassical limit ℏ→0, where the classical limit is given by Hamiltonian mechanics of particles, constitute a now standard part of the toolkit of theoretical physics. During the last years, these ideas have been extended into the field theoretical domain of systems composed of N indistinguishable particles, aka quantum fields, displaying a different type of semiclassical limit ℏeff=1/N→0 and accounting for genuine many-body quantum interference. The foundational concept behind this idea of many-body interference, the many-body version of the van Vleck-Gutzwillers semiclassical propagator, is explained in detail. Based on this the corresponding semiclassical many-body theory is reviewed. It provides a unified framework for understanding a variety of quantum chaotic phenomena addressed, including random-matrix spectral correlations in many-body systems, the universal morphology of many-body eigenstates, interference effects kin to mesoscopic weak localization, and the key to the scrambling of many-body correlations characterized by out-of-time-order correlators.
The famous Nils Bohr's quantum-classical correspondence principle states that the classical mechanics is a limiting case of the more general quantum mechanics. This implies that ``under certain conditions" quantum laws of motion become equivalent to classical laws. One of the conditions is fairly obvious: the corresponding classical action should be very large as compared with the Planck's constant. But this condition is not sufficient. Suppression of effects of quantum interference ("decoherence") is the phenomenon of primary importance for understanding of the Bohr's principle. Being, in essence, of quite general nature, this problem takes on special significance in the case of non-linear classically chaotic quantum systems. Whereas the rapid decay of phase correlations is an underlying feature of the classical dynamical chaos, the "quantum chaos" by itself is not capable of destroying the quantum phase coherence. Strictly speaking, any initially pure quantum state remains pure during an arbitrary long unitary evolution. Basically, formation of incoherent mixed states (decoherence) results only from the process of preparation of a mixed initial state or interaction with a noisy environment. Just the decoherence brigdes the quantum and classical worlds. Peculiarities of the time behavior of Peres fidelity, state purity, Shanon and von Neumann entropies are analyzed in detail. We demonstrate the ways the decoherence shows up in periodically driven systems that can be associated with Ramsey-type interferomentry experiments with ion traps. Finally, decoherence in ballistic electron quantum transport caused by interaction with a disordered environment is considered.
I compare the quantum and classical dynamics of a particle moving in a cosine potential while subject to a time-dependent force. I concentrate here on the behavior of an initially well-localized wave packet at times before the classically chaotic motion is fully developed. I find that the quantum and classical dynamics are indistinguishable well beyond the Ehrenfest time where the wave packet delocalizes. The quantum and classical descriptions first differ precisely when the classical probability density is folded in the vicinity of a hyperbolic fixed point. At this point, the wave function acquires a nodal structure which I show to be the result of a simple beating phenomenon between paths in the semiclassical propagator. When the interaction of the classical manifold with the hyperbolic fixed point leads to escape from the remnant separatrix, representing the onset of classical chaos, the interference associated with the tendril leads to a long-lived accumulation of quantum amplitude on top of the cosine barrier. This effect also has a semiclassical interpretation, meaning that it arises from the interference between classical paths, but one must expand to second order in Planck's constant to describe the behavior correctly. Both the nodal structure and this pinning of amplitude on the barrier are dynamic mechanisms for the quantum inhibition of mixing. I then couple the system to a bath of harmonic oscillators in order to study the effect of the environment on these mechanisms. Although an oscillator bath environment brings dissipation as well as noise to the problem, the noise effect dominates for the high temperature, weak coupling regime I study. When there is sufficient noise to render the interfering classical paths indistinguishable, I find that the quantum interference gets erased. This dephasing occurs at very early times, long before there is appreciable dissipation of energy to the environment. Consequently, one can argue that the presence of an environment, even if its effect would be negligible in a nonchaotic setting, allows for the possibility of quantum mixing.
At the heart of physics lies the human fascination with natural phenomena and the wish to understand the underlying principles. A well-known example is the butterfly effect. It describes how small changes in the initial state can cause significantly different measurement outcomes at later times. Such sensitivity to initial conditions is a key signature of chaotic systems and reflects their instability under small perturbations. The principle underlying this phenomenon is information spreading: with time, information about the perturbation propagates through the system, changing measurement results even at distant locations. In quantum systems, information not only spreads but can also scramble, meaning that the precise details about the perturbation are hidden in highly nonlocal correlations. Information scrambling has emerged as a universal feature of quantum chaos and, together with other universal features, serves as an organizing principle for quantum systems. This motivates imposing structure like locality on quantum systems in order to probe the capabilities and limits of such organizing principles. There have been significant advances in both theoretical and experimental directions in recent years. The newly gained flexibility in designing experiments and simulations also inspires the analytical study of quantum systems from the bottom up, where tractable models offer insights into the generic features of quantum mechanics. In this thesis we build upon these advances to explore the implications of adding structure to chaotic quantum systems for the behavior of such features. In particular, we consider the measures entanglement entropy and Krylov complexity as probes of structure. These quantities are closely connected to information spreading. This motivates us to study the influence of structure on information spreading in the second part. In the first part, we begin with a detailed discussion of the behavior of entanglement in chaotic systems. We impose a minimal amount of local structure by separating the system into two parts, each modeled as a single spin. We validate the predicted entanglement for typical states in such systems and show that it saturates the Page limit as the Hilbert space dimension increases. We then study how different initially unentangled product states approach the Page limit under time evolution. We consider three types of product states, each representing a distinct case. Random product states represent generic states only restricted by the absence of entanglement. Random dipole and quadrupolar states represent two distinct types of semi-classical structure. The results on the entanglement generation in the three different types of states refine our earlier conclusion, demonstrating that the semi-classical limit can suppress the generation of extensive entanglement. This suppression does not occur for random product or quadrupolar states; where the imposed structure is insufficient. We conclude the second chapter by presenting two protocols that can stabilize the dynamics at finite spin sizes, similar to the semi-classical limit. In the following chapter, we move from measuring the complexity of time-evolved states using entanglement entropy to investigating time-evolved operators through the lens of Krylov complexity. After a short introduction to Krylov complexity for Hamiltonian dynamics, we generalize the framework for discrete time evolution. We identify the linear growth of Krylov complexity as a universal feature of generic systems and analyze its behavior as we transition from chaotic to increasingly structured systems. Dual-unitary circuits converge toward this universal behavior at rates that can be as fast as exponential, consistent with their classification as maximally chaotic. We then approximately restore energy conservation by considering trotterized systems, ranging from unstructured and chaotic to highly structured and integrable ones. We find these systems to thermalize on a scale set by the trotterization step, slowly approaching the universal linear Krylov complexity growth regime. Approaching the linear growth regime is a fundamental property of trotterized systems with an unbounded spectrum, while systems with a bounded energy spectrum can evade thermalization as probed by Krylov complexity. Instead, they have a nonanalytic transition as the Trotter step size increases. Our study of Krylov complexity establishes its universal properties for discrete time evolution. The presented results deepen our understanding of the thermalizing behavior of different classes of systems in relation to their spectral properties by introducing an intuitive notion of a bath with chaotic characteristics. We link this thermalization behavior to information spreading, which we explore in the second part of this thesis. Information scrambling, along with the associated spreading, is a key phenomenon in chaotic systems with local structure. In the fourth chapter, we investigate information spreading in proximity to an integrable system exhibiting spontaneous symmetry breaking, the transverse field Ising model (TFIM). As expected, integrability prevents the scrambling of information. At the same time, information spreading probed by quenched out-of-time ordered correlators (OTOCs) exhibits features reminiscent of the quantum phase transition present in the TFIM. We unravel the intricate behavior of these OTOCs and identify the underlying mechanism that stabilizes the long-time values of OTOCs: dynamical relocalization. We provide two variations of the TFIM in which the relocalization phenomenon is not directly related to the presence of a quantum phase transition. This shows that no direct, universal relation exists between the two. Finally, we discuss the effects of breaking the integrable structure of the TFIM. Our results show that for short times, chaotic systems in proximity of integrability can retain signatures of integrability. In contrast, we observe significant changes at large times. This suggests that information scrambling, as a universal feature of chaotic systems, is restored at large times—even in systems near integrability that exhibit order. Following the analysis of information spreading close to integrable regimes, we study the stability of information spreading in more generic systems. First, we consider charge-conserving random circuits. In these systems, charge-charge correlators exhibit large fluctuations across different circuit instances with a slow polynomial decay in time. At the same time, they remain stable against fine-tuned perturbations, which can be interpreted as dephasing noise in the eigenbasis of the charge density operators. Equivalently, charge-charge correlators are mostly insensitive to decoherence, with interference effects contributing only subleading corrections. In this sense, the charge information spreading probed by charge-charge correlators is effectively classical. We perform a detailed analysis and quantify the dephasing insensitivity of these correlators. This suggests that circuit-to-circuit fluctuations can be captured by considering small regions where “quantum” effects are included, embedded within otherwise “classical” dynamics. This observation motivates the development of an algorithm to compute charge-charge correlators for individual circuits on classical computers with high accuracy. We quantitatively relate the algorithm’s performance to the dephasing analysis. We demonstrate the algorithm’s accuracy numerically for charge-charge correlators. Then, we argue that in generic circuits without conservation laws, the information spreading, as probed by OTOCs, follows similar principles. We conclude by comparing OTOC values measured on quantum devices with up to 95 superconducting qubits and 1000 gates to predictions from the approximate algorithm. This cross-validates experimental measurements and theoretical predictions. In this thesis, we explore the implications of adding structure to chaotic quantum systems, contributing to a deeper understanding of the organizing principles governing quantum chaos. We establish that entanglement can be suppressed in the semiclassical limit and that Krylov complexity behaves differently in thermalizing or integrable time-dependent systems. We show that the phenomenon information scrambling is also present in chaotic quantum systems even in the vicinity of a quantum phase transition. Conversely, when charge conservation is added, information spreading is stabilized and becomes reminiscent of that in classical systems. This work opens up further research directions towards a better understanding of the quantum nature of chaotic quantum systems and the development of probes of chaos in time dependent systems with different types of structure.
The interplay between classical chaos and quantum tunneling is examined in driven nonlinear systems, with emphasis on how semi classical phase space structures influence purely quantum transport phenomena. We show that, in the presence of external driving and stochastic perturbations, tunneling rates acquire an activated form determined by effective classical barriers, providing a transparent link between chaotic dynamics and quantum tunneling. Within this framework, chaos assisted tunneling and coherent destruction of tunneling emerge as closely related manifestations of the same underlying phase space restructuring and interference effects induced by driving. The results offer a unified perspective on tunneling control in non integrable systems and remain relevant for modern studies of driven quantum dynamics and decoherence resistant transport.
The subtle and fundamental issue of indistinguishability and interference between independent pathways to the same target state is examined in the context of coherent control of atomic and molecular processes, with emphasis placed on possible "which-way" information due to quantum entanglement established in the quantum dynamics. Because quantum interference between independent pathways to the same target state occurs only when the independent pathways are indistinguishable, it is first shown that creating useful coherence between nondegenerate states of a molecule for subsequent quantum interference manipulation cannot be achieved by collisions between atoms or molecules that are prepared in momentum and energy eigenstates. Coherence can, however, be transferred from light fields to atoms or molecules. Using a particular coherent control scenario, it is shown that this coherence transfer and the subsequent coherent phase control can be readily realized by the most classical states of light, i.e., coherent states of light. It is further demonstrated that quantum states of light may suppress the extent of phase-sensitive coherent control by leaking out some which-way information while "incoherent interference control" scenarios proposed in the literature have automatically ensured the indistinguishability of multiple excitation pathways. The possibility of quantum coherence in photodissociation product states is also understood in terms of the disentanglement between photodissociation fragments. Results offer deeper insights into quantum coherence generation in atomic and molecular processes.