Quantum Thermal Bath for Path Integral Molecular Dynamics Simulation

Brieuc, Fabien; Dammak, Hichem; Hayoun, Marc

doi:10.1021/acs.jctc.5b01146

Cited by 30 publications

(54 citation statements)

References 41 publications

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“…Meanwhile, hybrid PIMD and QTB schemes have been developed recently that exhibit improved convergence and scalability as compared to PIMD (Ceriotti, Bussi, and Parrinello, 2009;Ceriotti, Manolopoulos, and Parrinello, 2011;Ceriotti and Manolopoulos, 2012;Brieuc, Dammak, and Hayoun, 2016). In Sec.…”

Section: B a Bit Of History And Theorymentioning

confidence: 99%

Simulation and understanding of atomic and molecular quantum crystals

2017

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Quantum crystals abound in the whole range of solid-state species. Below a certain threshold temperature the physical behavior of rare gases ( 4 He and Ne), molecular solids (H 2 and CH 4 ), and some ionic (LiH), covalent (graphite), and metallic (Li) crystals can be only explained in terms of quantum nuclear effects (QNE). A detailed comprehension of the nature of quantum solids is critical for achieving progress in a number of fundamental and applied scientific fields like, for instance, planetary sciences, hydrogen storage, nuclear energy, quantum computing, and nanoelectronics. This review describes the current physical understanding of quantum crystals formed by atoms and small molecules, as well as the wide palette of simulation techniques that are used to investigate them. Relevant aspects in these materials such as phase transformations, structural properties, elasticity, crystalline defects and the effects of reduced dimensionality, are discussed thoroughly. An introduction to quantum Monte Carlo techniques, which in the present context are the simulation methods of choice, and other quantum simulation approaches (e. g., path-integral molecular dynamics and quantum thermal baths) is provided. The overarching objective of this article is twofold. First, to clarify in which crystals and physical situations the disregard of QNE may incur in important bias and erroneous interpretations. And second, to promote the study and appreciation of QNE, a topic that traditionally has been treated in the context of condensed matter physics, within the broad and interdisciplinary areas of materials science.

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Section: B a Bit Of History And Theorymentioning

confidence: 99%

Simulation and understanding of atomic and molecular quantum crystals

2017

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“…These methods ignore real time coherence but include effects arising from equilibrium quantum fluctuations and have been validated on several model systems and small molecules for which exact or highly accurate results are available [15,18,20,22]. While these methods show great promise for accurate determination of spectroscopic properties [23][24][25], their cost remains high when combined with a potential energy surface computed by ab initio electronic structure methods.Among the many methods that have been introduced in the past decade to accelerate the convergence of path integral calculations [26], those that combine path integral molecular dynamics with a generalized Langevin equation [27][28][29] can be applied transparently to empirical, machine learning or first principles simulations. They have been used to evaluate all sorts of thermodynamic properties, including structural observables [30], free energies [31], momentum distributions [28], and quantum kinetic energies [32] with a reduction in computational effort varying between a factor of 5 at ambient conditions to a factor of 100 at cryogenic temperatures [33].…”

mentioning

confidence: 99%

“…Among the many methods that have been introduced in the past decade to accelerate the convergence of path integral calculations [26], those that combine path integral molecular dynamics with a generalized Langevin equation [27][28][29] can be applied transparently to empirical, machine learning or first principles simulations. They have been used to evaluate all sorts of thermodynamic properties, including structural observables [30], free energies [31], momentum distributions [28], and quantum kinetic energies [32] with a reduction in computational effort varying between a factor of 5 at ambient conditions to a factor of 100 at cryogenic temperatures [33].…”

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confidence: 99%

Inexpensive modeling of quantum dynamics using path integral generalized Langevin equation thermostats

Kapil

Wilkins

Lan

et al. 2020

The Journal of Chemical Physics

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The properties of molecules and materials containing light nuclei are affected by their quantum mechanical nature. Modelling these quantum nuclear effects accurately requires computationally demanding path integral techniques. Considerable success has been achieved in reducing the cost of such simulations by using generalized Langevin dynamics to induce frequency-dependent fluctuations. Path integral generalized Langevin equation methods, however, have this far been limited to the study of static, thermodynamic properties due to the large perturbation to the system's dynamics induced by the aggressive thermostatting. Here we introduce a post-processing scheme, based on analytical estimates of the dynamical perturbation induced by the generalized Langevin dynamics, that makes it possible to recover meaningful time correlation properties from a thermostatted trajectory. We show that this approach yields spectroscopic observables for model and realistic systems which have an accuracy comparable to much more demanding approximate quantum dynamics techniques based on full path integral simulations.Vibrational spectroscopic techniques -from conventional infrared (IR) and Raman to advanced femtosecond pump-probe [1, 2], sum-frequency generation, second harmonic scattering [3, 4], and multi-dimensional vibrational spectroscopy [5] -are a cornerstone of chemistry [6]. These techniques have a multitude of applications such as the characterization of functional groups in chemical systems [7], the determination of the atomistic mechanisms of phase transitions through insight into chemical environments [8], and identification of unique structural fingerprints of molecular crystals [9]. The use of atomistic simulations for the computation of spectroscopic properties facilitates the interpretation of these experiments and provides support to the characterization of novel materials.Even neglecting effects that go beyond the Born-Oppenheimer (BO) decoupling of electronic and nuclear degrees of freedom, accurate calculations of the vibrational spectra of materials require an explicit treatment of the quantum dynamics of the nuclear degrees of freedom [10] on the electronic ground state potential energy surface. Quantum dynamics is in principle exactly obtained from the solution of the time dependent Schrödinger equation for the nuclei, but this is only practical for systems containing a handful of degrees of freedom [11,12]. Condensed phase systems can be studied [13] either by an exact treatment of the quantum dynamics of a subset of the nuclear degrees of freedom [14], or through classical dynamics on the quantum free energy surface of the nuclei [15,16]. Among the methods in the latter class, several of the most popular ones are based on the imaginary time path integral framework -such as (thermostatted) ring polymer molecular dynamics [17,18] ((T)RPMD), centroid molec- * venkat.kapil@epfl.ch ular dynamics [19,20] (CMD) and the recently developed quasi-centroid molecular dynamics [21] (QCMD). These methods ignore real time cohe...

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“…4. This can be understood by noticing that the equilibrium QMD algorithm has already been reported to provide approximated results when tunnelling between neighbour wells become predominant [39].…”

Section: Simulationsmentioning

confidence: 99%

Quantum duets working as autonomous thermal motors

Drewsen

Imparato

2019

Phys. Rev. E

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We study the dynamic properties of a thermal autonomous machine made up of two quantum Brownian particles, each of which is in contact with an environment at different temperature and moves on a periodic sinusoidal track. When such tracks are shifted, the center of mass of the system exhibits a non-vanishing velocity, for which we provide an exact expression in the limit of small track undulations. We discuss the role of the broken spatial symmetry in the emergence of directed motion in thermal machines. We then consider the case in which external deterministic forces are applied to the system, and characterize its steady state velocity. If the applied external force opposes the system motion, work can be extracted from such a steady state thermal machine, without any external cyclic protocol. When the two particles are not interacting, our results reduce to those of refs. [1, 2] for a single particle moving in a periodic tilted potential. We finally use our results for the motor velocity to check the validity of the quantum molecular dynamics algorithm in the non-linear, non-equilibrium regime.

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Quantum Thermal Bath for Path Integral Molecular Dynamics Simulation

Cited by 30 publications

References 41 publications

Simulation and understanding of atomic and molecular quantum crystals

Simulation and understanding of atomic and molecular quantum crystals

Inexpensive modeling of quantum dynamics using path integral generalized Langevin equation thermostats

Quantum duets working as autonomous thermal motors

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