Intrinsic Quantum Thermodynamics (IQT) is a theory that combines Thermodynamics and Quantum Mechanics into a single theory and asserts that irreversibility and the increase of entropy has its origin at the fundamental, atomistic level. The merits and details of IQT are discussed and compared with the well-known theory of Quantum Statistical Mechanics (QSM) and the more recent development of Quantum Thermodynamics (QT). IQT is then used to model in 3D the time evolution of the adsorption of hydrogen on a single-walled carbon nanotube. The initial state of the hydrogen molecules is far from stable equilibrium and over time the system relaxes to a state of stable equilibrium with the hydrogen near the walls of the carbon nanotube. The details of the model are presented, which include the construction of the energy eigenlevels for the system, the treatment of the interactions between the hydrogen and the nanotube along with the interactions of the hydrogen molecules with each other, and the solution of the IQT equation of motion as well as approximation methods that are developed to deal with extremely large numbers of energy eigenlevels. In addition, a new extension to the theory of IQT is proposed for modeling systems that undergo heat interactions with a heat reservoir. The formulation of a new heat interaction operator is discussed, implemented, tested, and compared with a previous version extant in the literature. IQT theory is then further extended to encompass simple mass interactions with a mass reservoir. The formulation, implementation, and testing of the mass interaction operator is also discussed in detail. Finally, IQT is used to model the results of two experiments found in the literature. The first experiment deals with the spin relaxation of rubidium atoms and the second tests the relaxation behavior of single trapped ion that is allowed to interact with an external heat reservoir. Good agreement between experiment and the model predictions is found. / Ph. D.

Predicting the kinetics of a chemical reaction is a challenging task, particularly for systems in states far from equilibrium. This work discusses the use of a relatively new theory known as intrinsic quantum thermodynamics (IQT) and its mathematical framework steepest-entropy-ascent quantum thermodynamics (SEA-QT) to predict the reaction kinetics at atomistic levels of chemically reactive systems in the non-equilibrium realm. IQT has emerged over the last three decades as the theory that not only unifies two of the three theories of physical reality, namely, quantum mechanics (QM), and thermodynamics but as well provides a physical basis for both the entropy and entropy production. The SEA-QT framework is able to describe the evolution in state of a system undergoing a dissipative process based on the principle of steepest-entropy ascent or locally-maximal-entropy generation. The work presented in this dissertation demonstrates for the first time the use of the SEA-QT framework to model the evolution in state of a chemically reactive system as its state relaxes to stable equilibrium. This framework brings a number of benefits to the field of reaction kinetics. Among these is the ability to predict the unique non-equilibrium (kinetic) thermodynamic path which the state of the system follows in relaxing to stable equilibrium. As a consequence, the reaction rate kinetics at every instant of time is known as are the chemical affinities, the reaction coordinates, the direction of reaction, the activation energies, the entropy, the entropy production, etc. All is accomplished without any limiting assumption of stable or pseudo-stable equilibrium. The objective of this work is to implement the SEA-QT framework to describe the chemical reaction process as a dissipative one governed by the laws of quantum mechanics and thermodynamics and to extract thermodynamic properties for states that are far from equilibrium. The F+H2-->HF+H and H+F2-->HF+F reaction mechanisms are used as model problems to implement this framework. / Ph. D.

A major challenge in the field of condensed matter physics is to harness the quantum mechanical properties of atomic systems coupled to large environments. Thermal fluctuations destroy quantum information and obstruct the development of quantum technologies such as quantum computers and memory devices. Recent advances in quantum control enable the manipulation of complex quantum states, providing new paths to preserve quantum information and to employ the environment as a resource. In this dissertation, we develop practical quantum control protocols which quickly and efficiently transfer energy to/from an environment. A major contribution of this work is the design of powerful and efficient quantum engines and refrigerators, which use the environment either to generate useful work or to freeze a system to its ground state. In achieving its core objectives, this work has also expanded on several areas of condensed matter quantum physics, including (i) the characterization of special classes of entangled system-environment states, (ii) the discovery of novel quantum chaotic phases of matter, (iii) the design of control schemes which speed-up efficient adiabatic protocols, and (iv) the development of experimentally viable control schemes in trapped ion systems, semiconductors, and nano-diamonds.

Quantum information and quantum computing (QIQC) systems, relying on the phenomena of superposition and entanglement, offer the potential for vast improvements in certain computations. A practical QC realization requires maintaining the stored information for time-scales long enough to implement algorithms. One primary cause of information loss is decoherence, i.e., the loss of coherence between two energy levels in a quantum system. This work attributes decoherence to dissipation occurring as the system evolves and uses steepest-entropy-ascent quantum thermodynamics (SEAQT) to predict the evolution of system state. SEAQT asserts that, at any instant of time, the system state evolves such that the rate of system entropy change is maximized while conserving system energy. With this principle, the SEAQT equation of motion is applicable to systems in any state, near or far from stable equilibrium, making SEAQT particularly well suited for predicting the dissipation occurring as quantum algorithms are implemented. In the present research, the dynamics of qubits (quantum-bits) using the SEAQT framework are first examined during common quantum gates (combinations of which form algorithms). This is then extended to modeling a system of multiple qubits implementing Shor's algorithm on a nuclear-magnetic-resonance (NMR) QC. Additionally, the SEAQT framework is used to predict experimentally observed dissipation occurring in a two-qubit NMR QC undergoing a so called ``quenching'' process. In addition, several methods for perturbing the density or so-called ``state'' operator used by the SEAQT equation of motion subject to an arbitrary set of expectation value constraints are presented. These are then used as the basis for randomly generating states used in analyzing the dynamics of entangled, non-interacting systems within SEAQT. Finally, a reservoir interaction model is developed for general quantum systems where each system locally experiences a heat interaction with an external reservoir. This model is then used as the basis for developing a decoherence control scheme, which effectively transfers entropy out of the QIQC system as it is generated, thus, reducing the decoherence. Reservoir interactions are modeled for single qubits and the control scheme is employed in modeling an NMR QC and shown to eliminate nearly all of the noise caused by decoherence/dissipation. / Doctor of Philosophy / Quantum computers (QCs) have the potential to perform certain tasks much more efficiently than today0 s supercomputers. One primary challenge in realizing a practical QC is maintaining the stored information, the loss of which is known as decoherence. This work attributes decoherence to dissipation (a classical analogue being heat generated due to friction) occurring while an algorithm is run on the QC. Standard quantum modeling approaches assume that for any dissipation to occur, the QC must interact with its environment. However, in this work, steepest-entropy-ascent quantum thermodynamics (SEAQT) is used to model the evolution of the QC as it runs an algorithm. SEAQT, developed by Hatsopolous, Gyftopolous, Beretta, and others over the past 40 years, supplements the laws of quantum mechanics with those of thermodynamics and in contrast to the standard quantum approaches does not require the presence of an environment to account for the dissipation which occurs. This work first applies the SEAQT framework to modeling single qubits (quantum bits) to characterize the effect of dissipation on the information stored on the qubit. This is later extended to a nuclear-magnetic-resonance (NMR) QC of 7 qubits. Additionally, SEAQT is used to predict experimentally observed dissipation in a two-qubit NMR QC. Afterwards, several methods for constrained perturbations of a QC0 s state are presented. These methods are then used with SEAQT to analyze the effect of dissipation on the entanglement of two qubits. Finally, a model is derived within the SEAQT framework accounting for a qubit interacting with its environment, which is at a constant temperature. This model is then used to develop a method for limiting the decoherence and shown to significantly lowering the resulting error due to decoherence.

In this research, a first-principles, non-equilibrium thermodynamic-ensemble approach applicable across all temporal and spatial scales is developed based on steepest-entropy-ascent quantum thermodynamics (SEAQT). The SEAQT framework provides an equation of motion consisting of both reversible mechanical dynamics and irreversible relaxation dynamics, which is able to describe the evolution of any state of any system, equilibrium or non-equilibrium. Its key feature is that the irreversible dynamics is based on a gradient dynamics in system state space instead of the microscopic mechanics of more traditional approaches. System energy eigenstructure and density operator (or ensemble probability distribution) describe the system and system thermodynamic state, respectively. Extensive properties (i.e., energy, entropy, and particle number) play a key role in formulating the equation of motion and in describing non-equilibrium state evolutions. All the concepts involved in this framework (i.e., eigentstructure, density operator, and extensive properties) are well defined at all temporal and spatial scales leading to the extremely broad applicability of SEAQT. The focus of the present research is that of developing non-equilibrium thermodynamic models based specifically on the irreversible part of the equation of motion of SEAQT and applying these to the study of pure relaxation processes of systems in non-equilibrium states undergoing chemical reactions and heat and mass diffusion. As part of the theoretical investigation, the new concept of hypo-equilibrium state is introduced and developed. It is able to describe any non-equilibrium state going through a pure relaxation process and is a generalization of the concept of stable equilibrium of equilibrium thermodynamics to the non-equilibrium realm. Using the concept of hypo-equilibrium state, it is shown that non-equilibrium intensive properties can be fundamentally defined throughout the relaxation process. The definition of non-equilibrium intensive properties also relies on various ensemble descriptions of system state. In this research, three SEAQT ensemble descriptions, i.e., the canonical, grand canonical, and isothermal-isobaric, are derived corresponding, respectively, to the definition of temperature, chemical potential, and pressure. To computationally and not just theoretically permit the application of the SEAQT framework across all scales, a density of states method is developed, which is applicable to solving the SEAQT equation of motion for all types of non-equilibrium relaxation processes. In addition, a heterogeneous multiscale method (HMM) algorithm is also applied to extend the application of the SEAQT framework to multiscale modeling. Applications of this framework are given for systems involving chemical kinetics, the heat and mass diffusion of indistinguishable particles, power cycles, and the complex, coupled reaction-diffusion pathways of a solid oxide fuel cell (SOFC) cathode. / Ph. D.

Landauer's principle states that it costs at least k_BT ln 2 of work to reset one bit in the presence of a heat bath at temperature T. The bound of k_BT ln 2 is achieved in the unphysical infinite-time limit. Here we consider two different finite-time protocols - one with discretised time and the second in the continuous limit. We prove analytically that the discrete time protocol enables one to reset a bit with a work cost close to k_BT ln 2 in a finite time. We construct an explicit protocol that achieves this, which involves thermalising and changing the system's Hamiltonian so as to avoid quantum coherences. Using concepts and techniques pertaining to single-shot statistical mechanics, we furthermore prove that the heat dissipated is exponentially close to the minimal amount possible not just on average, but guaranteed with high confidence in every run. Moreover we exploit the protocol to design a quantum heat engine that works near the Carnot efficiency in finite time. We further contrast this to a continuous time version of the protocol which is substantially less energy sufficient. We also consider the fluctuations in the work cost, and calculate how their magnitude is suppressed by a factor depending on the length of the protocol. We demonstrate with an experiment how molecules are a natural test-bed for probing fundamental quantum thermodynamics. Single-molecule spectroscopy has undergone transformative change in the past decade with the advent of techniques permitting individual molecules to be distinguished and probed. By considering the time-resolved emission spectrum of organic molecules as arising from quantum jumps between states, we demonstrate that the quantum Jarzynski equality is satisfied in this set-up. This relates the heat dissipated into the environment to the free energy difference between the initial and final state. We demonstrate also how utilizing the quantum Jarzynski equality allows for the detection of energy shifts within a molecule, beyond the relative shift.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第24440号 / 理博第4939号 / 新制||理||1706(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 谷村 吉隆, 教授 林 重彦, 教授 鈴木 俊法 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

As ligações entre a termodinâmica e a mecânica quântica mostram-se interessantes tópicos de pesquisa desde os anos 50 e tem atraído cada vez mais atenção nos últimos anos, tanto por suas possíveis aplicações tecnológicas, quanto pelo aspecto teórico - como, por exemplo, as relações de sistemas quânticos com a segunda lei da termodinâmica. Para sistemas quânticos mesoscópicos, restritos apenas a um número relativamente pequeno de estados energéticos, torna-se necessária uma generalização da termodinâmica usual. Neste trabalho mostramos como construir uma máquina de Stirling no contexto de íons aprisionados. Para isso, faz-se necessária a engenharia de frequências dependentes do tempo do modo vibracional do íon, além da engenharia de reservatórios térmicos com temperaturas controladas. Após a construção da máquina de Stirling e do cálculo do trabalho e da eficiência associados apresentamos um protocolo para a medida da função de distribuição do trabalho que recorre às medidas dos níveis de energia eletrônicos do íon para, a partir dessas, extrair-se informação sobre o seu estado vibracional. / The connections between quantum mechanics and thermodynamics have been an interesting research topic since the 1950´s and began attracting more and more attention recently, not only for the technological applications, but also from a theoretical point of view - as, for instance, when dealing with the relations between quantum systems and the second law of thermodynamics. For mesoscopic (or even macroscopic) quantum systems, restricted to relatively few energy states, a generalization of the usual thermodynamics becomes necessary. In the present work we show how to engeneer a Stirling engine in an ionic trap. To achieve this we have to engeneer an ionic vibrational mode with a time dependent frequency, and simutaneously engeneer a thermal reservoir with controled temperatures. After the construction of the Stirling machine and the calculation of the associated work and efficiency, we show a protocol that allows the measurement of the work distribution function which call on the measurement of the electronic energy levels of the ion and, from them, extract information about the vibrational state of the trap.

As ligações entre a termodinâmica e a mecânica quântica mostram-se interessantes tópicos de pesquisa desde os anos 50 e tem atraído cada vez mais atenção nos últimos anos, tanto por suas possíveis aplicações tecnológicas, quanto pelo aspecto teórico - como, por exemplo, as relações de sistemas quânticos com a segunda lei da termodinâmica. Para sistemas quânticos mesoscópicos, restritos apenas a um número relativamente pequeno de estados energéticos, torna-se necessária uma generalização da termodinâmica usual. Neste trabalho mostramos como construir uma máquina de Stirling no contexto de íons aprisionados. Para isso, faz-se necessária a engenharia de frequências dependentes do tempo do modo vibracional do íon, além da engenharia de reservatórios térmicos com temperaturas controladas. Após a construção da máquina de Stirling e do cálculo do trabalho e da eficiência associados apresentamos um protocolo para a medida da função de distribuição do trabalho que recorre às medidas dos níveis de energia eletrônicos do íon para, a partir dessas, extrair-se informação sobre o seu estado vibracional. / The connections between quantum mechanics and thermodynamics have been an interesting research topic since the 1950´s and began attracting more and more attention recently, not only for the technological applications, but also from a theoretical point of view - as, for instance, when dealing with the relations between quantum systems and the second law of thermodynamics. For mesoscopic (or even macroscopic) quantum systems, restricted to relatively few energy states, a generalization of the usual thermodynamics becomes necessary. In the present work we show how to engeneer a Stirling engine in an ionic trap. To achieve this we have to engeneer an ionic vibrational mode with a time dependent frequency, and simutaneously engeneer a thermal reservoir with controled temperatures. After the construction of the Stirling machine and the calculation of the associated work and efficiency, we show a protocol that allows the measurement of the work distribution function which call on the measurement of the electronic energy levels of the ion and, from them, extract information about the vibrational state of the trap.

Work is one of the cornerstones of classical thermodynamics. However, a direct transfer of this concept to quantum systems has proved problematic, especially for non-equilibrium processes. Unlike in the classical case, quantum work cannot be defined unambiguously. Depending on the specific setting and the imposed assumptions, different definitions are well motivated. In particular, in quantum thermodynamics, a clear distinction must be made between the measurement, storage, and use of work, since these three facets of the concept are not necessarily compatible with each other. The present thesis is mainly concerned with the measurement aspect. With the help of illustrative scenarios several approaches to quantum work measurements, their advantages and drawbacks are discussed. The focus will be on the question to what extent quantumness plays a decisive role in such scenarios, both in a qualitative and quantitative sense. Based on the gedankenexperiment of a Szilárd machine a criterion is proposed which can be used to verify genuine quantum correlations between the work medium in a heat engine and its thermal environment. In a Szilárd scenario a Maxwell's demon determines the state of the work medium and uses this information to extract work. We split this model into a bipartite setting. The demon only has access to the environment and, thus, can only indirectly measure the state of the work medium. By sharing the acquired information with another agent, the latter can extract work. The question of the quantumness of the experiment can then be reduced to the question of the maximum attainable work in the context of a suitable quantum steering scenario. For the constructed setting a bound for the work output achievable for classical correlations between the engine and the environment is derived. Work extraction beyond this classical limit thus proves the quantum nature of the machine. The verification of non-classical correlations by means of quantum steering is motivated by the fact that such a scenario reflects the typical asymmetry of a thermodynamic setup. While the machine itself is considered to be controllable and characterized in detail, no requirements are imposed on the correlated environment and the measurements performed on it. Consequently, this verification of a truly quantum heat engine is semi-device-independent. In a second scenario, the compatibility of average work and work fluctuations in a driven system is discussed. Fluctuation theorems play an important role in classical non-equilibrium thermodynamics. The best-known example is the Jarzynski equality. This equation establishes a connection between the free energy difference of two equilibrium states and the fluctuating work measured in a non-equilibrium process. A transfer of the Jarzynski equality to quantum systems succeeds most simply if the work definition is based on a so-called two-point measurement scheme. This approach determines the work as the difference of two projective energy measurements. The disadvantage of this definition is the unavoidable disturbance of the quantum state by the measurement, which makes a determination of the correct average work impossible. By means of a generalized two-point measurement scheme, it is shown how this contradiction between fluctuating and average work can be overcome. The approach is based on the concept of joint measurability. Unsharp measurements with a smaller disturbance of the quantum state can be measured jointly and allow for the determination of the correct average work. Nevertheless, the connection between measured fluctuations and the change of free energy can be preserved by means of a modified Jarzynski equality, as elucidated in this thesis. Even though the two-point measurement scheme - both in its projective form and in the generalized variant presented in this thesis - satisfies a Jarzynski equality, the operationality and the associated experimental significance are to be assessed differently than in the classical case. In classical thermodynamics, the Jarzynski relation can be used practically to determine, for example, the change of free energy in RNA molecules. However, it is crucial for such an experiment that the non-equilibrium work can actually be measured without requiring detailed knowledge of the system under consideration. In contrast, the two-point measurement scheme defines work as the energy difference of the system between the beginning and the end of the process. Crucially, for the measurement of these energies the Hamiltonians have to be known and the free energy difference could therefore be calculated directly from this knowledge without reference to the Jarzynski equality. Thus, the operationality of the quantum Jarzynski relation differs fundamentally from its classical counterpart. In this thesis we develop a measurement scheme which, in principle, allows us to employ a quantum version of the Jarzynski equation without knowledge of the Hamiltonians. The crucial point is to include the apparatus that drives the system out of equilibrium in the quantum picture and to define the work measurement on that very apparatus. Such a work measurement can only be meaningfully defined as a quantum expectation value and work fluctuations cannot directly be measured, in contrast to the classical case. The work along a classical microstate trajectory can be determined in a single run. The trajectory itself does not need to be known for this purpose; its existence is sufficient. Quantum trajectories do not exist unless they are objectified by a measurement. It is shown how measurements on the environment of the system can provide information about the trajectories. A conditioning of the measured work on these trajectories then allows for the determination of work fluctuations in the quantum system. For these fluctuations an inequality is conjectured whose limit is given by the classical Jarzynski equation. Numerical results support the conjecture. A proof is still missing. By means of the presented framework, the free energy difference of a quantum system can, in principle, be determined without knowledge of the underlying Hamiltonian. However, as is shown, this requires an optimization over several external parameters, since the inequality in general provides only an upper bound. Thus, the operationality of the model enforces a quantum disadvantage. The methods presented in this thesis can be applied to various scenarios in quantum thermodynamics. Especially the framework for work measurements on an external apparatus offers an alternative to common approaches when the system under investigation and especially its Hamiltonian is not known in advance. The focus on operationality will help to better understand to what extend the work quantities defined and measured in quantum thermodynamic systems differ from the classical concept of work.