Treatment of the predictive aspect of statistical mechanics as a form of statistical inference is extended to the density-matrix formalism and applied to a discussion of the relation between irreversibility and information loss. A principle of "statistical complementarity" is pointed out, according to which the empirically verifiable probabilities of statistical mechanics necessarily correspond to incomplete predictions. A preliminary discussion is given of the second law of thermodynamics and of a certain class of irreversible processes, in an approximation equivalent to that of the semiclassical theory of radiation.It is shown that a density matrix does not in general contain all the information about a system that is relevant for predicting its behavior. In the case of a system perturbed by random fluctuating fields, the density matrix cannot satisfy any differential equation because $\stackrel{\ifmmode \dot{}\else \.{}\fi{}}{\ensuremath{\rho}}(t)$ does not depend only on $\ensuremath{\rho}(t)$, but also on past conditions The rigorous theory involves stochastic equations in the type $\ensuremath{\rho}(t)=\mathcal{G}(t, 0)\ensuremath{\rho}(0)$, where the operator $\mathcal{G}$ is a functional of conditions during the entire interval ($0\ensuremath{\rightarrow}t$). Therefore a general theory of irreversible processes cannot be based on differential rate equations corresponding to time-proportional transition probabilities. However, such equations often represent useful approximations.Treatment of the predictive aspect of statistical mechanics as a form of statistical inference is extended to the density-matrix formalism and applied to a discussion of the relation between irreversibility and information loss. A principle of "statistical complementarity" is pointed out, according to which the empirically verifiable probabilities of statistical mechanics necessarily correspond to incomplete predictions. A preliminary discussion is given of the second law of thermodynamics and of a certain class of irreversible processes, in an approximation equivalent to that of the semiclassical theory of radiation.It is shown that a density matrix does not in general contain all the information about a system that is relevant for predicting its behavior. In the case of a system perturbed by random fluctuating fields, the density matrix cannot satisfy any differential equation because $\stackrel{\ifmmode \dot{}\else \.{}\fi{}}{\ensuremath{\rho}}(t)$ does not depend only on $\ensuremath{\rho}(t)$, but also on past conditions The rigorous theory involves stochastic equations in the type $\ensuremath{\rho}(t)=\mathcal{G}(t, 0)\ensuremath{\rho}(0)$, where the operator $\mathcal{G}$ is a functional of conditions during the entire interval ($0\ensuremath{\rightarrow}t$). Therefore a general theory of irreversible processes cannot be based on differential rate equations corresponding to time-proportional transition probabilities. However, such equations often represent useful approximations.

Physical ReviewOct 15, 19573,251 citations

Irreversibility, time, and fluctuations in quantum statistical theory of dissipative molecular systems. II. Application to fluorescence spectroscopy

C. A. Chatzidimitriou‐Dreismann

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.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.

International Journal of Quantum ChemistryApr 1, 198317 citations

Irreversibility in Quantum Statistical Mechanics

Henry B. Hollinger, Michael John Zenzen

Springer eBooksJan 1, 19850 citations

\mathcal{G}

is a functional of conditions during the entire interval ($0\ensuremath{\rightarrow}t$). Therefore a general theory of irreversible processes cannot be based on differential rate equations corresponding to time-proportional transition probabilities. However, such equations often represent useful approximations.