On the applicability of centroid and ring polymer path integral molecular dynamics for vibrational spectroscopy

Witt, Alexander; Ivanov, Sergei D.; Shiga, Motoyuki; Forbert, Harald; Marx, Dominik

doi:10.1063/1.3125009

Cited by 227 publications

(292 citation statements)

References 73 publications

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“…That said, several methods inspired by PIMD (such as centroid molecular dynamics, CMD 53,54 and ring polymer molecular dynamics, RPMD 8,55 ) have been proposed to approximately estimate diffusion coefficients, vibrational spectra and other time-dependent quantities. For these benchmarks we will focus on thermostatted RPMD (TRPMD) 48 , a simple approach that can be seen as combining elements of CMD and RPMD, alleviating some of their most severe artifacts 56 , at the price however of a broadening of highfrequency peaks 57 . The idea is just to attach a Langevin thermostat to ring-polymer modes, with a damping coefficient adjusted to be proportional to the frequency of the mode in the free-particle limit.…”

Section: E Vibrational Density Of Statesmentioning

confidence: 99%

High order path integrals made easy

Kapil

Behler

Ceriotti

2016

The Journal of Chemical Physics

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The precise description of quantum nuclear fluctuations in atomistic modelling is possible by employing path integral techniques, which involve a considerable computational overhead due to the need of simulating multiple replicas of the system. Many approaches have been suggested to reduce the required number of replicas. Among these, high-order factorizations of the Boltzmann operator are particularly attractive for high-precision and low-temperature scenarios. Unfortunately, to date several technical challenges have prevented a widespread use of these approaches to study nuclear quantum effects in condensed-phase systems. Here we introduce an inexpensive molecular dynamics scheme that overcomes these limitations, thus making it possible to exploit the improved convergence of high-order path integrals without having to sacrifice the stability, convenience and flexibility of conventional second-order techniques. The capabilities of the method are demonstrated by simulations of liquid water and ice, as described by a neural-network potential fitted to dispersion-corrected hybrid density functional theory calculations.

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Section: E Vibrational Density Of Statesmentioning

confidence: 99%

High order path integrals made easy

Kapil

Behler

Ceriotti

2016

The Journal of Chemical Physics

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“…[4] Neglecting zero-point motion and dynamics may lead to significant discrepancies between computed and experimental data. Plots of calculated 13 C shielding values against experimental chemical shifts generally show slopes that deviate from the ideal value of -1. This complicates the referencing of the calculated shielding values and typically linear regression between calculated and experimentally determined values is used to improve agreement.…”

Section: Introductionmentioning

confidence: 99%

Effects of Quantum Nuclear Delocalisation on NMR Parameters from Path Integral Molecular Dynamics

Dračínský

Hodgkinson

2014

Chemistry A European J

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Citation for published item:hr § ¡ %nsk¡ yD wrtin nd rodgkinsonD ul @PHIRA 9i'ets of quntum nuler delolistion on xw prmeters from pth integrl moleulr dynmisF9D ghemistry X iuropen journlFD PH @VAF ppF PPHIEPPHUF Further information on publisher's website:his is the peer reviewed version of the following rtileX hr § ¡ %nsk¡ yD wF nd rodgkinsonD F @PHIRAD i'ets of untum xuler helolistion on xw rmeters from th sntegrl woleulr hynmisF ghemistry E e iuropen tournlD PH @VAX PPHIEPPHUD whih hs een pulished in (nl form t httpXGGdxFdoiForgGIHFIHHPGhemFPHIQHQRWTF his rtile my e used for nonEommeril purposes in ordne with ileyEgr erms nd gonditions for selfErhivingF Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. AbstractThe influence of nuclear delocalisation on NMR chemical shifts in molecular organic solids is explored using path integral molecular dynamics (PIMD) and density functional theory calculations of shielding tensors. Nuclear quantum effects are shown to explain previously observed systematic deviations in correlations between calculated and experimental chemical shifts, with particularly large PIMD-induced changes (up to 23 ppm) observed for atoms in methyl groups. The PIMD approach also enables isotope substitution effects on chemical shifts and J couplings to be predicted in excellent agreement with experiment for both isolated molecules and molecular crystals. An approach based on convoluting calculated shielding or coupling surfaces with probability distributions of selected bond distances and valence angles obtained from PIMD simulations is used to calculate isotope effects. IntroductionThe gauge-including projector-augmented wave (GIPAW) procedure has been recently developed for the prediction of the magnetic resonance parameters in solids, [1] and the power of

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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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On the applicability of centroid and ring polymer path integral molecular dynamics for vibrational spectroscopy

Cited by 227 publications

References 73 publications

High order path integrals made easy

High order path integrals made easy

Effects of Quantum Nuclear Delocalisation on NMR Parameters from Path Integral Molecular Dynamics

Non-equilibrium dynamics from RPMD and CMD

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