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International Journal of Quantum Chemistry

On time superoperator and dynamical fluctuations in photoemission

C. A. Chatzidimitriou‐Dreismann

Published Jun 19, 2009• 0 citations
Publisher

Abstract

Some basic concepts of the Prigogine microscopic theory of irreversibility are discussed in the physical context of molecular dynamical processes in condensed systems. The removal of the “dual role” that the Hamiltonian plays within conventional quantum theory corresponds to the introduction of a star-Hermitian superoperator called “intrinsic time.” The existence of dynamically induced fluctuations around steady states is predicted. With the aid of a new photon-counting experiment these fluctuations have been detected. The experiment allows us to resolve broad luminescence bands through the detection of the underlying vibrational structure.

DOI
10.1002/qua.560280835

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Abstract Prigogine has emphasized that there is a “degeneracy” in quantum theory, where the Hamiltonian plays a dual role as (a) the generator of time evolution and (b) the energy observable. This prevents the exact treatment of irreversible phenomena on the microscopic quantum mechanical level. The removal of the aforementioned degeneracy can be achieved with the aid of a star‐unitary similarity transformation depending explicitly on the star‐Hermitian operator of the “intrinsic time”. Its physical significance is shown in the context of luminescence spectroscopy, where a novel kind of (dynamically induced or D‐) fluctuations around steady photoemission states is predicted. A photon counting/spectroscopic experiment has been performed which permits to detect D‐fluctuations and, at the same time, allows us to resolve broad spectroscopic bands by detection of the underlying finer “pure” vibronic transitions. The experimental findings clearly show the physical significance of Prigogine's Microscopic Theory.

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It is difficult to incorporate the concept of interacting physical particles in the frame of conventional quantum mechanics. It comes from the fact that in this formalism the Hamiltonian plays a dual role as the generator of motion and as the observable associated with the energy. As a result it is easy to define either a representation in which particles interact but are not well defined (a representation in which the Hamiltonian is not diagonal) or a representation in which the units are well defined but do not interact. We expect that in the search for a representation in which we may speak of both well defined and still interacting particles, the distinction between reversible and irreversible processes should play a basic role. Certainly we do not want to eliminate irreversible processes such as scattering, production or decay which are basically related to the mechanisms through which we observe particles. To distinguish between reversible and irreversible processes we have to work in a representation such that a Liapounov function (the entropy) may be ascribed to the time evolution of the system. The introduction of such a representation through a specific class of non-unitary transforms is described. We then propose newmore » quantum rules directly applicable to dissipative systems with a Liapounov function. For systems with a discrete spectrum these new quantum rules reduce trivially to the usual quantum rules as formulated by Born, Jordan and Heisenberg. The theory is applied to a simple field theoretical model - the so-called Friedrichs model-for which all calculations can be performed exactly.« less

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I. Prigogine has proposed, and the writings of N. S. Krylov to some extent suggest, a novel and unorthodox solution to foundational problems in statistical mechanics. In particular, the view claims to offer new insight into two interconnected problems: underst and ing the role of probability in physics, and that of reconciling the irreversibility of physical processes with the temporal symmetry (time reversal invariance) of dynamical theories. The approach in question advocates a conception of the state of a system which incorporates features of the quantum mechanical state concept in a context, classical statistical mechanics, where quantum considerations are generally considered to be irrelevant. I examine the plausibility of this new approach by offering an analysis of the various notions of state employed in modern physics. In the first chapter, I analyze the conceptual connections between dynamical laws and the nature of a system's state. I argue that laws and states are correlative. In constructing dynamical theories one does not start with a fixed or pre-determined state concept. Neither is one given the laws of the theory from which the conception of state is derived. Rather, we get the law/state structure as a "package." In light of this general analysis, I next examine the notion of state employed in the quantum theory. Here I consider a variety of conceptions of quantum states and assess their ability to answer the "paradoxes" of quantum theory. I pay particular attention to the role of probability and related restrictions on the realization of certain states. The new approach to statistical mechanics proposes to exploit similar restrictions on states in order to resolve the irreversibility problem. But is this unorthodox approach viable? In the final four chapters, I offer a detailed critique of this approach, examining the plausibility of the radical reworking of the state concept. I argue that while some important progress can be made, certain old puzzles remain, and new and difficult ones arise--ones which raise serious doubts about the ultimate success of this particular approach. I conclude, however, by arguing that such radical proposals are not unmotivated; and that novel and unorthodox proposals concerning the foundations of statistical mechanics must be taken seriously.

•Jan 1, 1987•0 citations
Some basic concepts of the Prigogine microscopic theory of irreversibility are discussed in the physical context of molecular dynamical processes in condensed systems. The removal of the “dual role” that the Hamiltonian plays within conventional quantum theory corresponds to the introduction of a star-Hermitian superoperator called “intrinsic time.” The existence of dynamically induced fluctuations around steady states is predicted. With the aid of a new photon-counting experiment these fluctuations have been detected. The experiment allows us to resolve broad luminescence bands through the detection of the underlying vibrational structure.
Abstract Prigogine has emphasized that there is a “degeneracy” in quantum theory, where the Hamiltonian plays a dual role as (a) the generator of time evolution and (b) the energy observable. This prevents the exact treatment of irreversible phenomena on the microscopic quantum mechanical level. The removal of the aforementioned degeneracy can be achieved with the aid of a star‐unitary similarity transformation depending explicitly on the star‐Hermitian operator of the “intrinsic time”. Its physical significance is shown in the context of luminescence spectroscopy, where a novel kind of (dynamically induced or D‐) fluctuations around steady photoemission states is predicted. A photon counting/spectroscopic experiment has been performed which permits to detect D‐fluctuations and, at the same time, allows us to resolve broad spectroscopic bands by detection of the underlying finer “pure” vibronic transitions. The experimental findings clearly show the physical significance of Prigogine's Microscopic Theory.
Abstract Some basic concepts of the Prigogine quantum statistical theory of irreversible processes are discussed in connection with a previous paper by Chatzidimitriou‐Dreismann and Lippert. The removal of the “dual role” that the Hamiltonian plays within conventional quantum theory corresponds to the introduction of a star‐unitary operator 𝒯 called “intrinsic time.” The formalism of the previous paper is extended to systems that interact with external fields. A formal specification of 𝒯, furthermore, follows from the Lt invariance of the basic equations of motion and its connection with the intrinsic time. As an application to fluorescence spectroscopy, a photon counting experiment is presented. It allows us to detect certain predicted “dynamical” fluctuations in emission spectra. Some current experimental results are reported concerning the resolution of the broad fluorescence band of fluoranthene (dissolved in ethanol) through detection of the underlying finer vibrational structure.
In many problems of molecular physics of condensed matter the coupling V of the system of interest with its environment is strong. During a time interval of the order of the characteristic relaxation time ΓTy due to V, both the energy spectrum and the time evolution of the system cannot be determined exactly. A new representation is introduced in which the coupling V does not affect the energy spectrum, but it determines the time evolution. This causes the appearance of a new quantity ΓT, called “intrinsic time.” Some results of this procedure are (a) invariance of the basic physical equations under the new trnsformation, (b) noncommutation of ΓT with the Liouvillian, and (c) existence of a nonvanishing “entropy production” with respect to the intrinsic time.
Time development of electromagnetic fields in closed cavities under continuous detection of photons continues to be a subject of confusing controversy. Recently Dodonov et al. [Phys. Rev. A, 75, 013806, 2007] argued that their model of quantum superoperators (E model) invalidates some of the predictions of the previously introduced photon counting model of Srinivas and Davies [J. Mod. Optic. 28, 981, 1981] (SD model). Both the SD and the E models are based on two postulated quantum jump superoperators: (1) the one-count operator corresponding to the absorption of a single photon and (2) the no-count operator. In this work we develop a stochastic difference equation that describes the dissipative coupling of the cavity field and the detector. The difference equation is based on non-perturbative treatment of the cavity-detector coupling. In spite of being non-integrable due to the coupling of the detector with an external reservoir it can be used to derive the exact forms of the quantum jump superoperators. When applied to a particular photon counting measurement our theory gives predictions identical with those of the SD model which should be considered a non-perturbative and ab-initio result. It is pointed out that available experimental results coincide with the results given by the ab-initio SD model. We summarize some of the key characteristics of cavity fields and photon counting processes to demonstrate that the results given by the SD model are consistent with the principles of quantum mechanics while those given by the E model are not.
It is difficult to incorporate the concept of interacting physical particles in the frame of conventional quantum mechanics. It comes from the fact that in this formalism the Hamiltonian plays a dual role as the generator of motion and as the observable associated with the energy. As a result it is easy to define either a representation in which particles interact but are not well defined (a representation in which the Hamiltonian is not diagonal) or a representation in which the units are well defined but do not interact. We expect that in the search for a representation in which we may speak of both well defined and still interacting particles, the distinction between reversible and irreversible processes should play a basic role. Certainly we do not want to eliminate irreversible processes such as scattering, production or decay which are basically related to the mechanisms through which we observe particles. To distinguish between reversible and irreversible processes we have to work in a representation such that a Liapounov function (the entropy) may be ascribed to the time evolution of the system. The introduction of such a representation through a specific class of non-unitary transforms is described. We then propose newmore » quantum rules directly applicable to dissipative systems with a Liapounov function. For systems with a discrete spectrum these new quantum rules reduce trivially to the usual quantum rules as formulated by Born, Jordan and Heisenberg. The theory is applied to a simple field theoretical model - the so-called Friedrichs model-for which all calculations can be performed exactly.« less
I. Prigogine has proposed, and the writings of N. S. Krylov to some extent suggest, a novel and unorthodox solution to foundational problems in statistical mechanics. In particular, the view claims to offer new insight into two interconnected problems: underst and ing the role of probability in physics, and that of reconciling the irreversibility of physical processes with the temporal symmetry (time reversal invariance) of dynamical theories. The approach in question advocates a conception of the state of a system which incorporates features of the quantum mechanical state concept in a context, classical statistical mechanics, where quantum considerations are generally considered to be irrelevant. I examine the plausibility of this new approach by offering an analysis of the various notions of state employed in modern physics. In the first chapter, I analyze the conceptual connections between dynamical laws and the nature of a system's state. I argue that laws and states are correlative. In constructing dynamical theories one does not start with a fixed or pre-determined state concept. Neither is one given the laws of the theory from which the conception of state is derived. Rather, we get the law/state structure as a "package." In light of this general analysis, I next examine the notion of state employed in the quantum theory. Here I consider a variety of conceptions of quantum states and assess their ability to answer the "paradoxes" of quantum theory. I pay particular attention to the role of probability and related restrictions on the realization of certain states. The new approach to statistical mechanics proposes to exploit similar restrictions on states in order to resolve the irreversibility problem. But is this unorthodox approach viable? In the final four chapters, I offer a detailed critique of this approach, examining the plausibility of the radical reworking of the state concept. I argue that while some important progress can be made, certain old puzzles remain, and new and difficult ones arise--ones which raise serious doubts about the ultimate success of this particular approach. I conclude, however, by arguing that such radical proposals are not unmotivated; and that novel and unorthodox proposals concerning the foundations of statistical mechanics must be taken seriously.