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Journal of Chemical Theory and Computation

Differential Shannon Entropies and Mutual Information in a Curve Crossing System: Adiabatic and Diabatic Decompositions

Peter Schürger, Volker Engel

Published Jun 11, 2024• 3 citations
Publisher

Abstract

The differential Shannon entropy provides a measure for the localization of a wave function. We regard the vibrational wave packet motion in a curve crossing system and calculate time-dependent entropies. Using a numerical example, we analyze how localization inside diabatic and adiabatic states can be accessed and discuss the differences between these two representations. In order to do so, we extend the usual entropy definition and introduce novel state-selective entropies. These quantities contain information on the form of the nuclear density components on the one hand and on the state population on the other, and it is shown how the contribution of the population can be removed. Having the state-selective entropies at hand, two additional functions derived from these, namely, the conditional entropy and the mutual information, are determined and compared. We find that these quantities relate closely to correlation effects rooted in different electronic properties of the system.

DOI
10.1021/acs.jctc.4c00245

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The differential Shannon entropy provides a measure for the localization of a wave function. We regard the vibrational wave packet motion in a curve crossing system and calculate time-dependent entropies. Using a numerical example, we analyze how localization inside diabatic and adiabatic states can be accessed and discuss the differences between these two representations. In order to do so, we extend the usual entropy definition and introduce novel state-selective entropies. These quantities contain information on the form of the nuclear density components on the one hand and on the state population on the other, and it is shown how the contribution of the population can be removed. Having the state-selective entropies at hand, two additional functions derived from these, namely, the conditional entropy and the mutual information, are determined and compared. We find that these quantities relate closely to correlation effects rooted in different electronic properties of the system.
We calculate differential Shannon entropies derived from time-dependent coordinate-space and momentum-space probability densities. This is performed for a prototype system of a coupled electron-nuclear motion. Two situations are considered, where one is a Born-Oppenheimer adiabatic dynamics, and the other is a diabatic motion involving strong non-adiabatic transitions. The information about coordinate- and momentum-space dynamics derived from the total and single-particle entropies is discussed and interpreted with the help of analytical models. From the entropies, we derive mutual information, which is a measure for the electron-nuclear correlation. In the adiabatic case, it is found that such correlations are manifested differently in coordinate- and momentum space. For the diabatic dynamics, we show that it is possible to decompose the entropies into state-specific contributions.
We study the Born-Oppenheimer dynamics within a model for a coupled electron-nuclear motion. Differential Shannon entropies are calculated from the time-dependent probability densities of the combined system and, using single particle densities, entropies for the electronic and nuclear degrees of freedom are derived. These functions provide information on details of the wave packet motion. From the entropies, we determine the mutual information which characterizes particle correlations. This quantity is compared to other measures of electron-nuclear entanglement. Numerical results are interpreted within an analytically solvable approach, and it is documented how these functions depend on properties of the Born-Oppenheimer wave function and, in particular, how dynamical effects like wave packet focusing and dispersion influence the correlation between the particles.
Pair density Shannon information measures and their NNN-dependent behaviour in diatomic molecular systems
Pair density Shannon entropies and mutual information in position and in momentum space are calculated for two series of homonuclear and heteronuclear diatomic molecules using Hartree-Fock wave functions. The pair density entropy sum increases with the quality of the basis set. Mutual information, a measure of statistical correlation, is seen to be smaller in momentum space as compared to position space. The interpretation is that the momentum pair density is closer than the position pair density to a Hartree-like reference. The NNN-dependent behaviours of the entropy and mutual information sums are examined by fitting the data to three different model behaviours. Results show that these models are capable of representing the molecular data in differing degrees. The parameters obtained from a particular model are relatively constant across different chemical series. This adds evidence to the argument of a universal NNN-dependent behaviour of the entropy sums.
Applications of information-theoretic measures to a time-dependent coupled electron-nuclear system to analyze the dynamics and correlation between both particles are presented. For this, differential Shannon entropies that are derived from time-dependent coordinate-space and momentum-space probability densities are calculated. Two distinct scenarios are investigated: one exhibiting adiabatic Born-Oppenheimer dynamics and the other involving strong non-adiabatic transitions. The total and single-particle entropies, as well as the mutual information are analyzed and compared to semi-analytical expressions. The results reveal that in the adiabatic regime, correlations manifest differently in coordinate and momentum spaces, which is related to the formation of nodes. In the non-adiabatic case, entropies can be decomposed into state-specific contributions, revealing information about the transition between adiabatic states.
The entropic perspective on the molecular electronic structure is investigated. Information-theoretic description of electron probabilities is extended to cover the complex amplitudes (wave functions) of quantum mechanics. This analysis emphasizes the entropic concepts due to the phase part of electronic states, which generates the probability current density, thus allowing one to distinguish the information content of states generating the same electron density and differing in their current densities. The classical information measures of Fisher and Shannon, due to the probability/density distributions themselves, are supplemented by the nonclassical terms generated by the wave-function phase or the associated probability current. A complementary character of the Fisher and Shannon information measures is explored and the relationship between these classical information densities is derived. It is postulated to characterize also their nonclassical (phase/current-dependent) contributions. The continuity equations of the generalized information densities are examined and the associated nonclassical information sources are identified. The variational rules involving the quantum-generalized Shannon entropy, which generate the stationary and time-dependent Schrödinger equations from the relevant maximum entropy principles, are discussed and their implications for the system “thermodynamic” equilibrium states are examined. It is demonstrated that the lowest, stationary “thermodynamic” state differs from the true ground state of the system, by exhibiting the space-dependent phase, linked to the modulus part of the wave function, and hence also a nonvanishing probability current.
The article intertwines the study of wave packet dynamics with information-theoretic measurements in one dimensional (D =1) system. A localized wave packet at time t=0 has been considered here and its change at later instant of time t is calculated for the position space wave function. The momentum space wave function is obtained by taking the Fourier transform of the position space wave function at time t= 0 . These wave functions are then employed to construct the wave packet's respective probability densities in position and momentum space, and later have been used to compute the corresponding position and momentum space Shannon (S) and Fisher information (I) entropies. It has been observed that although the Shannon and Fisher information entropies explicitly depend on the standard deviation, neither the Shannon entropy sum nor the product of Fisher information entropies is. Moreover, for D dimensional systems, the computed values of the Shannon and Fisher entropies are found to satisfy the lower bounds of the Bialynicki-Birula and Myceilski (BBM) inequality relation and the Stam-Cramer-Rao inequalities better known as the Fisher based uncertainty relation. Thus, our theoretical study explores the validation of information-theoretic measurements for wave packet dynamics using the basic formulations of information theory.