We introduce a semi-classical approximation for calculating generalized multi-time correlation functions based on Matsubara dynamics, a classical dynamics approach that conserves the quantum Boltzmann distribution. This method is exact for the zero time and harmonic limits and reduces to classical dynamics when only one Matsubara mode is considered (i.e., the centroid). Generalized multi-time correlation functions can be expressed as canonical phase-space integrals, involving classically evolved observables coupled through Poisson brackets in a smooth Matsubara space. Numerical tests on a simple potential show that the Matsubara approximation exhibits better agreement with exact results than classical dynamics, providing a bridge between the purely quantum and classical descriptions of multi-time correlation functions. Despite the phase problem that prevents practical applications of Matsubara dynamics, the reported work provides a benchmark theory for the future development of quantum-Boltzmann-preserving semi-classical approximations for studies of chemical dynamics in condensed phase systems.
more »
« less
An exact imaginary-time path-integral phase-space formulation of multi-time correlation functions
An exact representation of quantum mechanics using the language of phase-space variables provides a natural starting point to introduce and develop semiclassical approximations for the calculation of time correlation functions. Here, we introduce an exact path-integral formalism for calculations of multi-time quantum correlation functions as canonical averages over ring-polymer dynamics in imaginary time. The formulation provides a general formalism that exploits the symmetry of path integrals with respect to permutations in imaginary time, expressing correlations as products of imaginary-time-translation-invariant phase-space functions coupled through Poisson bracket operators. The method naturally recovers the classical limit of multi-time correlation functions and provides an interpretation of quantum dynamics in terms of “interfering trajectories” of the ring-polymer in phase space. The introduced phase-space formulation provides a rigorous framework for the future development of quantum dynamics methods that exploit the invariance of imaginary time path integrals to cyclic permutations.
more » « less- Award ID(s):
- 1900160
- NSF-PAR ID:
- 10399691
- Publisher / Repository:
- American Institute of Physics
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 158
- Issue:
- 9
- ISSN:
- 0021-9606
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Quantum time correlation functions (TCFs) involving two states are important for describing nonadiabatic dynamical processes such as charge transfer (CT). Based on a previous single-state method, we propose an imaginary-time open-chain path-integral (OCPI) approach for evaluating the two-state symmetrized TCFs. Expressing the forward and backward propagation on different electronic potential energy surfaces as a complex-time path integral, we then transform the path variables to average and difference variables such that the integration over the difference variables up to the second order can be performed analytically. The resulting expression for the symmetrized TCF is equivalent to sampling the open-chain configurations in an effective potential that corresponds to the average surface. Using importance sampling over the extended OCPI space via open path-integral molecular dynamics, we tested the resulting path-integral approximation by calculating the Fermi’s golden rule CT rate constant within a widely used spin-boson model. Comparing with the real-time linearized semiclassical method and analytical result, we show that the imaginary-time OCPI provides an accurate two-state symmetrized TCF and rate constant in the typical turnover region. It is shown that the first bead of the open chain corresponds to physical zero-time and that the endpoint bead corresponds to final time t; oscillations of the end-to-end distance perfectly match the nuclear mode frequency. The two-state OCPI scheme is seen to capture the tested model’s electronic quantum coherence and nuclear quantum effects accurately.more » « less
-
Persistent Homology Metrics Reveal Quantum Fluctuations and Reactive Atoms in Path Integral Dynamicsnull (Ed.)Nuclear quantum effects (NQEs) are known to impact a number of features associated with chemical reactivity and physicochemical properties, particularly for light atoms and at low temperatures. In the imaginary time path integral formalism, each atom is mapped onto a “ring polymer” whose spread is related to the quantum mechanical uncertainty in the particle’s position, i.e., its thermal wavelength. A number of metrics have previously been used to investigate and characterize this spread and explain effects arising from quantum delocalization, zero-point energy, and tunneling. Many of these shape metrics consider just the instantaneous structure of the ring polymers. However, given the significant interest in methods such as centroid molecular dynamics and ring polymer molecular dynamics that link the molecular dynamics of these ring polymers to real time properties, there exists significant opportunity to exploit metrics that also allow for the study of the fluctuations of the atom delocalization in time. Here we consider the ring polymer delocalization from the perspective of computational topology, specifically persistent homology, which describes the 3-dimensional arrangement of point cloud data, (i.e. atomic positions). We employ the Betti sequence probability distribution to define the ensemble of shapes adopted by the ring polymer. The Wasserstein distances of Betti sequences adjacent in time are used to characterize fluctuations in shape, where the Fourier transform and associated principal components provides added information differentiating atoms with different NQEs based on their dynamic properties. We demonstrate this methodology on two representative systems, a glassy system consisting of two atom types with dramatically different de Broglie thermal wavelengths, and ab initio molecular dynamics simulation of an aqueous 4 M HCl solution where the H-atoms are differentiated based on their participation in proton transfer reactions.more » « less
-
more » « less
DL_POLY Quantum 2.0, a vastly expanded software based on DL_POLY Classic 1.10, is a highly parallelized computational suite written in FORTRAN77 with a modular structure for incorporating nuclear quantum effects into large-scale/long-time molecular dynamics simulations. This is achieved by presenting users with a wide selection of state-of-the-art dynamics methods that utilize the isomorphism between a classical ring polymer and Feynman’s path integral formalism of quantum mechanics. The flexible and user-friendly input/output handling system allows the control of methodology, integration schemes, and thermostatting. DL_POLY Quantum is equipped with a module specifically assigned for calculating correlation functions and printing out the values for sought-after quantities, such as dipole moments and center-of-mass velocities, with packaged tools for calculating infrared absorption spectra and diffusion coefficients.
-
The third-order response lies at the heart of simulating and interpreting nonlinear spectroscopies ranging from two-dimensional infrared (2D-IR) to 2D electronic (2D-ES), and 2D sum frequency generation (2D-SFG). The extra time and frequency dimensions in these spectroscopic techniques provide access to rich information on the electronic and vibrational states present, the coupling between them, and the resulting rates at which they exchange energy that are obscured in linear spectroscopy, particularly for condensed phase systems that usually contain many overlapping features. While the exact quantum expression for the third-order response is well established, it is incompatible with the methods that are practical for calculating the atomistic dynamics of large condensed phase systems. These methods, which include both classical mechanics and quantum dynamics methods that retain quantum statistical properties while obeying the symmetries of classical dynamics, such as LSC-IVR, centroid molecular dynamics, and Ring Polymer Molecular Dynamics (RPMD), naturally provide short-time approximations to the multi-time symmetrized Kubo transformed correlation function. Here, we show how the third-order response can be formulated in terms of equilibrium symmetrized Kubo transformed correlation functions. We demonstrate the utility and accuracy of our approach by showing how it can be used to obtain the third-order response of a series of model systems using both classical dynamics and RPMD. In particular, we show that this approach captures features such as anharmonically induced vertical splittings and peak shifts while providing a physically transparent framework for understanding multidimensional spectroscopies.more » « less
