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Effective potential analytic continuation approach for real time quantum correlation functions involving nonlinear operators

Horikoshi, A, Kinugawa, K

Published May 6, 2005• 33 citations
OpenAlex

Abstract

We apply the effective potential analytic continuation (EPAC) method to the calculation of real time quantum correlation functions involving operators nonlinear in the position operator $\\hat{q}$. For a harmonic system the EPAC method provides the exact correlation function at all temperature ranges, while the other quantum dynamics methods, the centroid molecular dynamics and the ring polymer molecular dynamics, become worse at lower temperature. For an asymmetric anharmonic system, the EPAC correlation function is in very good agreement with the exact one at $t=0$. When the time increases from zero, the EPAC method gives good coincidence with the exact result at lower temperature. Finally, we propose a simplified version of the EPAC method to reduce the computational cost required for the calculation of the standard effective potential.

Related papers

Effective potential analytic continuation approach for real time quantum correlation functions involving nonlinear operators

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We apply the effective potential analytic continuation (EPAC) method to the calculation of real time quantum correlation functions involving operators nonlinear in the position operator q. For a harmonic system the EPAC method provides the exact correlation function at all temperature ranges, while the other quantum dynamics methods, the centroid molecular dynamics and the ring polymer molecular dynamics, become worse at lower temperature. For an asymmetric anharmonic system, the EPAC correlation function is in very good agreement with the exact one at t = 0. When the time increases from zero, the EPAC method gives good coincidence with the exact result at lower temperature. Finally, we propose a simplified version of the EPAC method to reduce the computational cost required for the calculation of the standard effective potential.

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We apply the effective potential analytic continuation (EPAC) method to one-dimensional asymmetric potential systems to obtain the real time quantum correlation functions at various temperatures. Comparing the EPAC results with the exact results, we find that for an asymmetric anharmonic oscillator the EPAC results are in very good agreement with the exact ones at low temperature, while this agreement becomes worse as the temperature increases. We also show that the EPAC calculation for a certain type of asymmetric potentials can be reduced to that for the corresponding symmetric potentials.

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Effective potential analytic continuation calculations of real time quantum correlation functions: Asymmetric systems

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Quantum dynamical correlations: Effective potential analytic continuation approach

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We propose a new quantum dynamics method called the effective potential analytic continuation (EPAC) to calculate the real time quantum correlation functions at finite temperature. The method is based on the effective action formalism which includes the standard effective potential. The basic notions of the EPAC are presented for a one-dimensional double well system in comparison with the centroid molecular dynamics (CMD) and the exact real time quantum correlation function. It is shown that both the EPAC and the CMD well reproduce the exact short time behavior, while at longer time their results deviate from the exact one. The CMD correlation function damps rapidly with time because of ensemble dephasing. The EPAC correlation function, however, can reproduce the long time oscillation inherent in the quantum double well systems. It is also shown that the EPAC correlation function can be improved toward the exact correlation function by means of the higher order derivative expansion of the effective action.

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Quantum mechanical correlation functions, maximum entropy analytic continuation, and ring polymer molecular dynamics

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The maximum entropy analytic continuation (MEAC) and ring polymer molecular dynamics (RPMD) methods provide complementary approaches to the calculation of real time quantum correlation functions. RPMD becomes exact in the high temperature limit, where the thermal time betavariant Planck's over 2pi tends to zero and the ring polymer collapses to a single classical bead. MEAC becomes most reliable at low temperatures, where betavariant Planck's over 2pi exceeds the correlation time of interest and the numerical imaginary time correlation function contains essentially all of the information that is needed to recover the real time dynamics. We show here that this situation can be exploited by combining the two methods to give an improved approximation that is better than either of its parts. In particular, the MEAC method provides an ideal way to impose exact moment (or sum rule) constraints on a prior RPMD spectrum. The resulting scheme is shown to provide a practical solution to the "nonlinear operator problem" of RPMD, and to give good agreement with recent exact results for the short-time velocity autocorrelation function of liquid parahydrogen. Moreover these improvements are obtained with little extra effort, because the imaginary time correlation function that is used in the MEAC procedure can be computed at the same time as the RPMD approximation to the real time correlation function. However, there are still some problems involving long-time dynamics for which the RPMD+MEAC combination is inadequate, as we illustrate with an example application to the collective density fluctuations in liquid orthodeuterium.

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On the application of numerical analytic continuation methods to the study of quantum mechanical vibrational relaxation processes

Emilio Gallicchio, S. A. Egorov, B. J. Berne

A major problem still confronting molecular simulations is how to determine time-correlation functions of many-body quantum systems. In this paper the results of the maximum entropy (ME) and singular value decomposition (SVD) analytic continuation methods for calculating real time quantum dynamics from path integral Monte Carlo calculations of imaginary time time-correlation functions are compared with analytical results for quantum mechanical vibrational relaxation processes. This system studied is an exactly solvable system: a harmonic oscillator bilinearly coupled to a harmonic bath. The ME and SVD methods are applied to exact imaginary-time correlation functions with various level of added random noise, and also to imaginary-time data from path integral Monte Carlo (PIMC) simulations. The information gathered in the present benchmark study is valuable for the application of the analytic continuation of PIMC data to complex systems.

The Journal of Chemical Physics•Nov 8, 1998•48 citations
We apply the effective potential analytic continuation (EPAC) method to the calculation of real time quantum correlation functions involving operators nonlinear in the position operator hatq\\hat{q}hatq. For a harmonic system the EPAC method provides the exact correlation function at all temperature ranges, while the other quantum dynamics methods, the centroid molecular dynamics and the ring polymer molecular dynamics, become worse at lower temperature. For an asymmetric anharmonic system, the EPAC correlation function is in very good agreement with the exact one at t=0t=0t=0. When the time increases from zero, the EPAC method gives good coincidence with the exact result at lower temperature. Finally, we propose a simplified version of the EPAC method to reduce the computational cost required for the calculation of the standard effective potential.
We apply the effective potential analytic continuation (EPAC) method to the calculation of real time quantum correlation functions involving operators nonlinear in the position operator q. For a harmonic system the EPAC method provides the exact correlation function at all temperature ranges, while the other quantum dynamics methods, the centroid molecular dynamics and the ring polymer molecular dynamics, become worse at lower temperature. For an asymmetric anharmonic system, the EPAC correlation function is in very good agreement with the exact one at t = 0. When the time increases from zero, the EPAC method gives good coincidence with the exact result at lower temperature. Finally, we propose a simplified version of the EPAC method to reduce the computational cost required for the calculation of the standard effective potential.
We apply the effective potential analytic continuation (EPAC) method to one-dimensional asymmetric potential systems to obtain the real time quantum correlation functions at various temperatures. Comparing the EPAC results with the exact results, we find that for an asymmetric anharmonic oscillator the EPAC results are in very good agreement with the exact ones at low temperature, while this agreement becomes worse as the temperature increases. We also show that the EPAC calculation for a certain type of asymmetric potentials can be reduced to that for the corresponding symmetric potentials.
We apply the effective potential analytic continuation (EPAC) method to one-dimensional asymmetric potential systems to obtain the real time quantum correlation functions at various temperatures. Comparing the EPAC results with the exact results, we find that for an asymmetric anharmonic oscillator the EPAC results are in very good agreement with the exact ones at low temperature, while this agreement becomes worse as the temperature increases. We also show that the EPAC calculation for a certain type of asymmetric potentials can be reduced to that for the corresponding symmetric potentials.
We propose a new quantum dynamics method called the effective potential analytic continuation (EPAC) to calculate the real time quantum correlation functions at finite temperature. The method is based on the effective action formalism which includes the standard effective potential. The basic notions of the EPAC are presented for a one-dimensional double well system in comparison with the centroid molecular dynamics (CMD) and the exact real time quantum correlation function. It is shown that both the EPAC and the CMD well reproduce the exact short time behavior, while at longer time their results deviate from the exact one. The CMD correlation function damps rapidly with time because of ensemble dephasing. The EPAC correlation function, however, can reproduce the long time oscillation inherent in the quantum double well systems. It is also shown that the EPAC correlation function can be improved toward the exact correlation function by means of the higher order derivative expansion of the effective action.
The maximum entropy analytic continuation (MEAC) and ring polymer molecular dynamics (RPMD) methods provide complementary approaches to the calculation of real time quantum correlation functions. RPMD becomes exact in the high temperature limit, where the thermal time betavariant Planck's over 2pi tends to zero and the ring polymer collapses to a single classical bead. MEAC becomes most reliable at low temperatures, where betavariant Planck's over 2pi exceeds the correlation time of interest and the numerical imaginary time correlation function contains essentially all of the information that is needed to recover the real time dynamics. We show here that this situation can be exploited by combining the two methods to give an improved approximation that is better than either of its parts. In particular, the MEAC method provides an ideal way to impose exact moment (or sum rule) constraints on a prior RPMD spectrum. The resulting scheme is shown to provide a practical solution to the "nonlinear operator problem" of RPMD, and to give good agreement with recent exact results for the short-time velocity autocorrelation function of liquid parahydrogen. Moreover these improvements are obtained with little extra effort, because the imaginary time correlation function that is used in the MEAC procedure can be computed at the same time as the RPMD approximation to the real time correlation function. However, there are still some problems involving long-time dynamics for which the RPMD+MEAC combination is inadequate, as we illustrate with an example application to the collective density fluctuations in liquid orthodeuterium.
A major problem still confronting molecular simulations is how to determine time-correlation functions of many-body quantum systems. In this paper the results of the maximum entropy (ME) and singular value decomposition (SVD) analytic continuation methods for calculating real time quantum dynamics from path integral Monte Carlo calculations of imaginary time time-correlation functions are compared with analytical results for quantum mechanical vibrational relaxation processes. This system studied is an exactly solvable system: a harmonic oscillator bilinearly coupled to a harmonic bath. The ME and SVD methods are applied to exact imaginary-time correlation functions with various level of added random noise, and also to imaginary-time data from path integral Monte Carlo (PIMC) simulations. The information gathered in the present benchmark study is valuable for the application of the analytic continuation of PIMC data to complex systems.