A quantitative assessment of the accuracy of centroid molecular dynamics for the calculation of the infrared spectrum of liquid water

Paesani, Francesco; Voth, Gregory A.

doi:10.1063/1.3291212

Cited by 68 publications

(73 citation statements)

References 39 publications

(32 reference statements)

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“…[29][30][31][32] Although both methods have known artifacts, such as the spurious-mode effect in RPMD [33][34][35] and the curvature problem 35,36 in CMD, they have proven effective for a vast range of chemical applications including the calculation of thermal rate constants, 30,[37][38][39][40][41][42][43][44][45][46][47][48][49][50][51][52][53][54][55] diffusion coefficients, 31,[56][57][58][59][60][61] and vibrational spectra. [33][34][35][36][62][63][64][65] With only a few exceptions, [66][67][68] RPMD and CMD have been applied for the characterization of processes with thermal equilibrium initial conditions. The aim of this work is to systematically investigate whether RPMD and CMD can also be ...…”

Section: Introductionmentioning

confidence: 99%

Non-equilibrium dynamics from RPMD and CMD

Welsch

Song

Shi

et al. 2016

The Journal of Chemical Physics

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We investigate the calculation of approximate non-equilibrium quantum time correlation functions (TCFs) using two popular path-integral-based molecular dynamics methods, ring-polymer molecular dynamics (RPMD) and centroid molecular dynamics (CMD). It is shown that for the cases of a sudden vertical excitation and an initial momentum impulse, both RPMD and CMD yield non-equilibrium TCFs for linear operators that are exact for high temperatures, in the t = 0 limit, and for harmonic potentials; the subset of these conditions that are preserved for non-equilibrium TCFs of non-linear operators is also discussed. Furthermore, it is shown that for these non-equilibrium initial conditions, both methods retain the connection to Matsubara dynamics that has previously been established for equilibrium initial conditions. Comparison of non-equilibrium TCFs from RPMD and CMD to Matsubara dynamics at short times reveals the orders in time to which the methods agree. Specifically, for the position-autocorrelation function associated with sudden vertical excitation, RPMD and CMD agree with Matsubara dynamics up to O(t4) and O(t1), respectively; for the position-autocorrelation function associated with an initial momentum impulse, RPMD and CMD agree with Matsubara dynamics up to O(t5) and O(t2), respectively. Numerical tests using model potentials for a wide range of non-equilibrium initial conditions show that RPMD and CMD yield non-equilibrium TCFs with an accuracy that is comparable to that for equilibrium TCFs. RPMD is also used to investigate excited-state proton transfer in a system-bath model, and it is compared to numerically exact calculations performed using a recently developed version of the Liouville space hierarchical equation of motion approach; again, similar accuracy is observed for non-equilibrium and equilibrium initial conditions.

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Section: Introductionmentioning

confidence: 99%

Non-equilibrium dynamics from RPMD and CMD

Welsch

Song

Shi

et al. 2016

The Journal of Chemical Physics

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“…6; this is the basis of the PIMD approach to calculating quantum properties in complex systems. In passing, we note that PIMD is only applicable in the calculation of static (time-independent) properties; however, the last two decades has witnessed the development of PI-based methods, including ring-polymer molecular dynamics (RPMD 24,26,[32][33][34][35][36][37]39,41,42,48,62 ), centroid molecular dynamics (CMD [43][44][45][46][47] ) and, most recently, Matsubara dynamics 42,63 which can be used to approximate quantum-mechanical time-dependent properties such as time-correlation functions. Both the RPC methodologies and our new RPI approach are, in general, equally applicable to these dynamic simulation methods, although we focus here on PIMD simulations for clarity of presentation.…”

Section: 6061mentioning

confidence: 99%

“…As a result, PIMD simulations have been employed to investigate systems ranging from structure in liquid and solid water phases 13,16,17,[21][22][23][24][25][26][27] to free energies in enzymecatalyzed proton transfer. [28][29][30][31] More recently, PIMDbased strategies have been proposed which enable calculation of approximate dynamic (time-dependent) properties; these approaches, including ring-polymer molecular dynamics (RPMD 16,25,26,29,[32][33][34][35][36][37][38][39][40][41] ), centroid molecular dynamics (CMD 22,[42][43][44][45][46][47] ) and semiclassical instanton theory 48,49 now provide a useful toolbox for interrogating the influence of quantum effects in complex condensedphase dynamics. a) Electronic mail: S.Habershon@warwick.ac.uk…”

Section: Introductionmentioning

confidence: 99%

Accelerated path-integral simulations using ring-polymer interpolation

Buxton

Habershon

2017

The Journal of Chemical Physics

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Path-integral (PI) molecular simulations can be used to calculate exact quantum statistical mechanical properties for complex systems containing many interacting atoms and molecules. The limiting computational factor in a PI simulation is typically the evaluation of the potential energy surface (PES) and forces at each ring-polymer "bead"; for an n-bead ring-polymer, a PI simulation is typically n times greater than the corresponding classical simulation. To address the increased computational effort of PI simulations, several approaches have been developed recently, most notably based on the idea of ring-polymer contraction (RPC) which exploits either the separation of the PES into short-range and long-range contributions or the availability of a computationally-inexpensive PES which can be incorporated to effectively smooth the ringpolymer PES; neither approach is satisfactory in applications to systems described by ab initio PESs. In this Article, we describe a new method, ring-polymer interpolation (RPI), which can be used to accelerate PI simulations without any prior assumptions about the PES. In simulations of liquid water under ambient conditions, where quantum effects are known to play a subtel role in influencing experimental observables such as diffusion coefficients and radial distribution functions, we find that RPI can accurately reproduce the results of fully-converged PI simulations, albeit with far fewer PES evaluations; this approach therefore opens up the possibility of large-scale PI simulations on ab initio PESs at lower computational effort than current methods.

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“…CMD has been shown to give good spectrum when coupled with a water potential with the correct dipole derivative surface. 30 The experimental spectrum is from ref. 31.…”

Section: Performance Of the Force Fields For Reproducing Propertiesmentioning

confidence: 99%

The quest for the best nonpolarizable water model from the adaptive force matching method

Akin-Ojo

Wang

2010

J Comput Chem

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The recently introduced adaptive force matching (AFM) method is used to develop a significantly improved pair-wise nonpolarizable potential for water. A rigid version of the potential is also presented to enable larger time steps for biological simulations. In this work, it is demonstrated that the AFM method can be used to systematically assess the importance of each functional term during the construction of a force field. For a water potential, it is established that a single off-atom charge center (M) in the plane of water outperforms two out-of-plane charge sites for reproducing intermolecular forces. The four-site pair-wise nonpolarizable force field developed in this work rivals some of the most sophisticated polarizable models in terms of reproducing accurate ab initio forces. The force fields are parameterized to perform best in the temperature range from 0 to 40°C. Equilibrium and dynamical properties calculated with the flexible and rigid force fields are in good agreement with experimental results. For the flexible model, the agreement improves when path integral simulation is performed. These force fields provide high-quality results at a very low computational cost and are thus well suited to atomistic scale biological simulations. The AFM method provides a mechanism for selecting important terms in force field expressions and is a very promising tool for producing accurate force fields in condensed phases.

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A quantitative assessment of the accuracy of centroid molecular dynamics for the calculation of the infrared spectrum of liquid water

Cited by 68 publications

References 39 publications

Non-equilibrium dynamics from RPMD and CMD

Non-equilibrium dynamics from RPMD and CMD

Accelerated path-integral simulations using ring-polymer interpolation

The quest for the best nonpolarizable water model from the adaptive force matching method

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