arXiv subjects

Stuart C. Althorpe

Publications and source records attributed to Stuart C. Althorpe.

18 recordsLinked to original sources

arXiv2026

Equilibrating continuous-variable open quantum systems using stochastic classical trajectories in path-integral space

Beyond the weak-coupling limit, open quantum systems equilibrate to a highly entangled thermal state. For continuous-variable systems, this state can be written explicitly as an imaginary-time phase-space path integral, in which the positions are directly entangled with the bath, and the momenta are correlated with the positions through a phase term. Here, we ask to what extent this state can be reached by propagating stochastic classical trajectories in path-integral phase space. Surprisingly, we find that the trajectories equilibrate to the exact quantum equilibrium state, recovering the purely imaginary momentum-position correlation in the phase term. The trajectories are generated using a recently derived Matsubara generalized Langevin equation, which produces the imaginary correlations by evolving the stochastic variables into the complex plane. This makes the dynamics numerically unstable, but we are nonetheless able to demonstrate the equilibration of a quartic oscillator coupled to a white-noise bath. These unexpected findings could lead to new approximate methodologies for simulating continuous-variable open quantum systems.

quant-ph↗

arXiv2026

Exploiting the path-integral radius of gyration in open quantum dynamics

A major challenge in open quantum dynamics is the inclusion of Matsubara-decay terms in the memory kernel, which arise from the quantum-Boltzmann delocalisation of the bath modes. This delocalisation can be quantified by the radius of gyration squared ${\mathcal R}^2(ω)$ of the imaginary-time Feynman paths of the bath modes as a function of the frequency $ω$. In a Hierarchical Equations of Motion (HEOM) calculation with a Debye--Drude spectral density, ${\mathcal R}^2(ω)$ is the only quantity that is treated approximately (assuming convergence with respect to hierarchy depth). Here, we show that the well-known Ishizaki--Tanimura correction is equivalent to separating smooth from `Brownian' contributions to ${\mathcal R}^2(ω)$, and that modifying the correction leads to a more efficient HEOM in the case of fast baths. We also develop a simple `A4' adaptation of the `AAA' (Adaptive Antoulas--Anderson) algorithm in order to fit ${\mathcal R}^2(ω)$ to a sum over poles, which results in an extremely efficient implementation of the standard HEOM method at low temperatures.

quant-ph↗

arXiv2026

Effective classical potential for quantum statistical averages

We present an effective potential that allows quantum thermal expectation values of a position-dependent observable to be estimated as a classical ensemble average of the corresponding function. We follow the approach of Feynman and Hibbs, but perform the mean-field treatment of quantum fluctuations about the path starting point rather than the path centroid. Furthermore, rather than performing a full variational optimization of the potential, we explore approximate functional forms that yield a numerical robustness. The resulting closed-form potential is exact in the classical and harmonic limits; benchmarks against exact position distributions for one-dimensional quartic, Morse, and double-well potentials, show good agreement for potentials with harmonic support.

quant-ph↗

arXiv2025

On the origin of exponential operator growth in Hilbert space

The question of thermalization in quantum many-body systems has long been studied through the properties of matrix elements of operators corresponding to local observables. More recently, the focus has shifted to the dynamics of operators, which lead to seminal works proposing universal bounds on the rate of operator growth. In this work, we unify these two approaches: we show that exponential operator growth in Hilbert space, as measured by Krylov complexity, is governed by an exponential off-diagonal decay of the operator matrix elements in the system eigenbasis. When this decay is algebraic or slower, the growth rate saturates the universal bound, thereby establishing a microscopic origin of operator growth which is independent of chaos, dimensionality or the presence of many-body interactions.

quant-ph↗

arXiv2024

Quantum rates in dissipative systems with spatially varying friction

We investigate whether making the friction spatially dependent on the reaction coordinate introduces quantum effects into the thermal reaction rates for dissipative reactions. Quantum rates are calculated using the numerically exact multi-configuration time-dependent Hartree (MCTDH) method, as well as the approximate ring-polymer molecular dynamics (RPMD), ring-polymer instanton (RPI) methods, and classical mechanics. By conducting simulations across a wide range of temperatures and friction strengths, we can identify the various regimes that govern the reactive dynamics. At high temperatures, in addition to the spatial-diffusion and energy-diffusion regimes predicted by Kramer's rate theory, a (coherent) tunnelling-dominated regime is identified at low friction. At low temperatures, incoherent tunnelling dominates most of Kramer's curve, except at very low friction when coherent tunnelling becomes dominant. Unlike in classical mechanics, the bath's influence changes the equilibrium time-independent properties of the system, leading to a complex interplay between spatially dependent friction and nuclear quantum effects even at high temperatures. More specifically, a realistic friction profile can lead to an increase (decrease) of the quantum (classical) rates with friction within the spatial-diffusion regime, showing that classical and quantum rates display qualitatively different behaviours. Except at very low frictions, we find that RPMD captures most of the quantum effects in the thermal reaction rates.

physics.chem-ph↗

arXiv2024

Thermal quenching of classical and semiclassical scrambling

Quantum scrambling often gives rise to short-time exponential growth in out-of-time-ordered correlators (OTOCs). The scrambling rate over an isolated saddle point at finite temperature is shown here to be reduced by a hierarchy of quenching processes. Two of these appear in the classical limit, where escape from the neighbourhood of the saddle reduces the rate by a factor of two, and thermal fluctuations around the saddle reduce it further; a third process can be explained semiclassically as arising from quantum thermal fluctuations around the saddle, which are also responsible for imposing the Maldacena-Shenker-Stanford bound.

nlin.CD↗

arXiv2023

Instantons and the quantum bound to chaos

We investigate why the Lyapunov exponents $λ$ of out-of-time-ordered correlators (OTOCs) satisfy a universal bound $λ< 2 πk_B T/{\hbar}$ by probing imaginary-time path-integral space using ring-polymer molecular dynamics (RPMD) for a barrier-crossing model. We find that the RPMD OTOC satisfies the same bound as the quantum OTOC, which is caused by the stability of quantum thermal fluctuations around the instanton on the barrier. We expect that similar instantons (or other delocalised structures) will be found in many other systems with exponentially growing OTOCs.

quant-ph↗

arXiv2022

Improved torque estimator for condensed-phase quasicentroid molecular dynamics

We describe improvements to the quasicentroid molecular dynamics (QCMD) path-integral method, which was developed recently for computing the infrared spectra of condensed-phase systems. The main development is an improved estimator for the intermolecular torque on the quasicentroid. When applied to qTIP4P/F liquid water and ice, the new estimator is found to remove an artificial 25 cm$^{-1}$ red shift from the libration bands, to increase slightly the intensity of the OH stretch band in the liquid, and to reduce small errors noted previously in the QCMD radial distribution functions. We also modify the mass-scaling used in the adiabatic QCMD algorithm, which allows the molecular dynamics timestep to be quadrupled, thus reducing the expense of a QCMD calculation to twice that of Cartesian centroid molecular dynamics for qTIP4P/F liquid water at 300 K, and eight times for ice at 150 K.

physics.chem-ph↗

arXiv2022

Comparison of Matsubara dynamics with exact quantum dynamics for an oscillator coupled to a dissipative bath

Matsubara dynamics is the classical dynamics which results when imaginary-time path-integrals are smoothed; it conserves the quantum Boltzmann distribution and appears in drastically approximated form in path-integral dynamics methods such as (thermostatted) ring-polymer molecular dynamics (T)RPMD and centroid molecular dynamics (CMD). However, it has never been compared directly with exact quantum dynamics for non-linear operators, because the difficulty of treating the phase has limited the number of Matsubara modes to fewer than 10. Here, we treat up to $\sim$200 Matsubara modes in simulations of a Morse oscillator coupled to a dissipative bath of harmonic oscillators. This is done by expressing the Matsubara equations of motion in the form of a generalised Langevin equation, approximating the noise to be real, and analytically continuing the momenta to convert the Matsubara phase into ring-polymer springs. The resulting equations of motion are stable up to a maximum value of modes which increases with bath coupling strength and decreases with system anharmonicity. The dynamics of the tail of highly oscillatory Matsubara modes is found to be harmonic, and can thus be computed efficiently. For a moderately anharmonic oscillator with a strong but subcritical coupling to the bath, the Matsubara simulations yield non-linear $\large\langle{\hat q^2\hat q^2(t)}\large\rangle$ time-correlation functions in almost perfect agreement with the exact quantum results. Reasonable agreement is also obtained for weaker coupling strengths, where errors arise because of the real-noise approximation. These results give strong evidence that Matsubara dynamics correctly explains how classical dynamics arises in quantum systems which are in thermal equilibrium.

physics.chem-ph↗

arXiv2021

Testing the quasicentroid molecular dynamics method on gas-phase ammonia

Quasicentroid molecular dynamics (QCMD) is a path-integral method for approximating nuclear quantum effects in dynamics simulations, which has given promising results for gas- and condensed-phase water. Here, by simulating the infrared spectrum of gas-phase ammonia, we test the feasibility of extending QCMD beyond water. Overall, QCMD works as well for ammonia as for water, reducing or eliminating blue shifts from the classical spectrum without introducing the artificial red-shifts or broadening associated with other imaginary-time path-integral methods. However, QCMD gives only a modest improvement over the classical spectrum for the position of the symmetric bend mode, which is highly anharmonic (since it correlates with the inversion pathway). We expect QCMD to have similar problems with large-amplitude degrees of freedom in other molecules, but otherwise to work as well as for water.

physics.chem-ph↗

arXiv2019

Path-integral dynamics of water using curvilinear centroids

We develop a path-integral dynamics method for water that resembles centroid molecular dynamics (CMD), except that the centroids are averages of curvilinear, rather than cartesian, bead coordinates. The curvilinear coordinates are used explicitly only when computing the potential of mean force, the components of which are re-expressed in terms of cartesian 'quasi-centroids' (so-called because they are close to the cartesian centroids). Cartesian equations of motion are obtained by making small approximations to the quantum Boltzmann distribution. Simulations of the infrared spectra of various water models over 150-600 K show these approximations to be justified: for a two-dimensional OH-bond model, the quasi-centroid molecular dynamics (QCMD) spectra lie close to the exact quantum spectra, and almost on top of the Matsubara dynamics spectra; for gas-phase water, the QCMD spectra are close to the exact quantum spectra; for liquid water and ice (using the q-TIP4P/F surface), the QCMD spectra are close to the CMD spectra at 600 K, and line up with the results of thermostatted ring-polymer molecular dynamics and approximate quantum calculations at 300 and 150 K. The QCMD spectra show no sign of the CMD 'curvature problem' (of erroneous red shifts and broadening). In the liquid and ice simulations, the potential of mean force was evaluated on the fly by generalising an adiabatic CMD algorithm to curvilinear coordinates; the full limit of adiabatic separation needed to be taken, which made the QCMD calculations 8 times more expensive than partially adiabatic CMD at 300 K, and 32 times at 150 K (and the intensities may still not be converged at this temperature). The QCMD method is probably generalisable to many other systems, provided collective bead-coordinates can be identified that yield compact mean-field ring-polymer distributions.

physics.chem-ph↗

arXiv2018

Mean-field Matsubara dynamics: Analysis of path-integral curvature effects in rovibrational spectra

It was shown recently that smooth and continuous "Matsubara" phase-space loops follow a quantum-Boltzmann-conserving classical dynamics when decoupled from non-smooth distributions, which was suggested as the reason that many dynamical observables appear to involve a mixture of classical dynamics and quantum Boltzmann statistics. Here we derive a mean-field version of this "Matsubara dynamics" which sufficiently mitigates its serious phase problem to permit numerical tests on a two-dimensional "champagne-bottle" model of a rotating OH bond. The Matsubara-dynamics rovibrational spectra are found to converge toward close agreement with the exact quantum results at all temperatures tested (200-800 K), the only significant discrepancies being a temperature-independent 22 cm$^{-1}$ blue-shift in the position of the vibrational peak and a slight broadening in its line shape. These results are compared with centroid molecular dynamics (CMD) to assess the importance of non-centroid fluctuations. Above 250 K, only the lowest-frequency non-centroid modes are needed to correct small CMD red-shifts in the vibrational peak; below 250 K, more non-centroid modes are needed to correct large CMD red-shifts and broadening. The transition between these "shallow curvature" and "deep curvature" regimes happens when imaginary-time Feynman paths become able to lower their actions by cutting through the curved potential surface, giving rise to artificial instantons in CMD.

physics.chem-ph↗

arXiv2016

An alternative derivation of ring-polymer molecular dynamics transition-state theory

In a previous article [J. Chem. Phys. 138, 084108 (2013)], we showed that the $t\to 0_+$ limit of ring-polymer molecular dynamics (RPMD) rate-theory is also the $t\to 0_+$ limit of a new type of quantum flux-side time-correlation function, in which the dividing surfaces are invariant to imaginary-time translation; in other words, that RPMD transition-state theory (RPMD-TST) is a $t\to 0_+$ quantum transition-state theory (QTST). Recently, Jang and Voth [J. Chem. Phys. 144, 084110 (2016)] rederived this quantum $t\to 0_+$ limit, and claimed that it gives instead the centroid-density approximation. Here we show that the $t\to 0_+$ limit derived by Jang and Voth is in fact RPMD-TST.

physics.chem-ph↗

arXiv2015

Relation of centroid molecular dynamics and ring-polymer molecular dynamics to exact quantum dynamics

We recently obtained a quantum-Boltzmann-conserving classical dynamics by making a single change to the derivation of the `Classical Wigner' approximation. Here, we show that the further approximation of this `Matsubara dynamics' gives rise to two popular heuristic methods for treating quantum Boltzmann time-correlation functions: centroid molecular dynamics (CMD) and ring-polymer molecular dynamics (RPMD). We show that CMD is a mean-field approximation to Matsubara dynamics, obtained by discarding (classical) fluctuations around the centroid, and that RPMD is the result of discarding a term in the Matsubara Liouvillian which shifts the frequencies of these fluctuations. These findings are consistent with previous numerical results, and give explicit formulae for the terms that CMD and RPMD leave out.

physics.chem-ph↗

arXiv2015

Boltzmann-conserving classical dynamics in quantum time-correlation functions: Matsubara dynamics

We show that a single change in the derivation of the linearized semiclassical-initial value representation (LSC-IVR or classical Wigner approximation) results in a classical dynamics which conserves the quantum Boltzmann distribution. We rederive the (standard) LSC-IVR approach by writing the (exact) quantum time-correlation function in terms of the normal modes of a free ring-polymer (i.e. a discrete imaginary-time Feynman path), taking the limit that the number of polymer beads $N \to \infty$, such that the lowest normal-mode frequencies take their Matsubara values. The change we propose is to truncate the quantum Liouvillian, not explicitly in powers of $\hbar^2$ at $\hbar^0$ (which gives back the standard LSC-IVR approximation), but in the normal-mode derivatives corresponding to the lowest Matsubara frequencies. The resulting Matsubara dynamics is inherently classical (since all terms $\mathcal{O}\left(\hbar^{2}\right)$ disappear from the Matsubara Liouvillian in the limit $N \to \infty$), and conserves the quantum Boltzmann distribution because the Matsubara Hamiltonian is symmetric with respect to imaginary-time translation. Numerical tests show that the Matsubara approximation to the quantum time-correlation function converges with respect to the number of modes, and gives better agreement than LSC- IVR with the exact quantum result. Matsubara dynamics is too computationally expensive to be applied to complex systems, but its further approximation may lead to practical methods.

physics.chem-ph↗

arXiv2013

Derivation of a true (t->0+) quantum transition-state theory. II. Recovery of the exact quantum rate in the absence of recrossing

In Part I [J. Chem. Phys. 138, 084108 (2013)] we derived a quantum transition-state theory by taking the t->0+ (short-time) limit of a new form of quantum flux-side time-correlation function containing a ring-polymer dividing surface. This t->0+ limit appears to be unique in giving positive-definite Boltzmann statistics, and is identical to ring-polymer molecular dynamics (RPMD) TST. Here, we show that quantum TST (i.e. RPMD-TST) is exact if there is no recrossing (by the real-time quantum dynamics) of the ring-polymer dividing surface, nor of any surface orthogonal to it in the space describing fluctuations in the polymer-bead positions along the reaction coordinate. In practice, this means that RPMD-TST gives a good approximation to the exact quantum rate for direct reactions, provided the temperature is not too far below the cross-over to deep tunnelling. We derive these results by comparing the long-time limit of the ring-polymer flux-side time-correlation function with that of a hybrid flux-side time-correlation function (containing a ring-polymer flux operator and a Miller-Schwarz-Tromp side function), and by representing the resulting ring-polymer momentum integrals as hypercubes. Together with Part I, the results of this article validate a large number of RPMD calculations of reaction rates.

physics.chem-ph↗

arXiv2013

On the uniqueness of t->0+ quantum transition-state theory

It was shown recently that there exists a true quantum transition-state theory (QTST) corresponding to the t->0+ limit of a (new form of) quantum flux-side time-correlation function. Remarkably, this QTST is identical to ring-polymer molecular dynamics (RPMD) TST. Here we provide evidence which suggests very strongly that this QTST (= RPMD-TST) is unique, in the sense that the t->0+ limit of any other flux-side time-correlation function gives either non-positive-definite quantum statistics or zero. We introduce a generalized flux-side time-correlation function which includes all other (known) flux-side time-correlation functions as special limiting cases. We find that the only non-zero t->0+ limit of this function that contains positive-definite quantum statistics is RPMD-TST.

physics.chem-ph↗

arXiv2013

Derivation of a true (t->0+) quantum transition-state theory. Part I: Uniqueness and equivalence to ring-polymer molecular dynamics transition-state-theory

Surprisingly, there exists a quantum flux-side time-correlation function which has a non-zero short-time (t->0+) limit, and thus yields a rigorous quantum generalization of classical transition-state theory (TST). In this Part I of two articles, we introduce the new time-correlation function, and derive its short-time limit. The new ingredient is a generalized Kubo transform which allows the flux and side dividing surfaces to be the same function of path-integral space. Choosing this common dividing surface to be a single point gives a short-time limit which is identical to an expression introduced on heuristic grounds by Wigner in 1932, but which does not give positive-definite quantum statistics, causing it to fail while still in the shallow-tunnelling regime. Choosing the dividing surface to be invariant to imaginary-time translation gives, uniquely, a short-time limit that gives the correct positive- definite quantum statistics at all temperatures, and which is identical to ring-polymer molecular dynamics (RPMD) TST. We find that the RPMD-TST rate is not a strict upper bound to the exact quantum rate, but a good approximation to one if real-time coherence effects are small. Part II will show that the RPMD-TST rate is equal to the exact quantum rate in the absence of recrossing.

physics.chem-ph↗