Classical to Path-Integral Adaptive Resolution in Molecular Simulation: Towards a Smooth Quantum-Classical Coupling

Poma, Adolfo B.; Site, Luigi Delle

doi:10.1103/physrevlett.104.250201

Cited by 69 publications

(69 citation statements)

References 42 publications

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“…Ideas involving spatial partitions of systems in order to treat different regions with different methods have been previously proposed in the literature. 37 For example, in the approach by Kreis et. al 38 a position dependent mass Hamiltonian is used, which allows the definition of a quantum, a hybrid and a classical region.…”

Section: Spatially Localized Contractionmentioning

confidence: 99%

Decisive role of nuclear quantum effects on surface mediated water dissociation at finite temperature

Litman

Donadio

Ceriotti

et al. 2017

The Journal of Chemical Physics

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Water molecules adsorbed on inorganic substrates play an important role in several technological applications. In the presence of light atoms in adsorbates, nuclear quantum effects (NQE) influence the structural stability and the dynamical properties of these systems. In this work, we explore the impact of NQE on the dissociation of water wires on stepped Pt(221) surfaces. By performing ab initio molecular dynamics simulations with van der Waals corrected density functional theory, we note that several competing minima for both intact and dissociated structures are accessible at finite temperatures, making it important to assess whether harmonic estimates of the quantum free energy are sufficient to determine the relative stability of the different states. We thus perform ab initio path integral molecular dynamics (PIMD) in order to calculate these contributions taking into account conformational entropy and anharmonicities at finite temperatures. We propose that when when adsorption is weak and NQE on the substrate are negligible, PIMD simulations can be performed through a simple partition of the system, resulting in considerable computational savings. We then calculate the full contribution of NQE to the free energies, including also anharmonic terms. We find that they result in an increase of up to 20% of the quantum contribution to the dissociation free energy compared to the harmonic estimates. We also find that the dissociation process has a negligible contribution from tunneling, but is dominated by ZPE, which can enhance the rate of dissociation by three orders of magnitude. Finally we highlight how both temperature and NQE indirectly impact dipoles and the redistribution of electron density, causing work function to changes of up to 0.4 eV with respect to static estimates. This quantitative determination of the change in work function provides a possible approach to determine experimentally the most stable configurations of water oligomers on the stepped surfaces.

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Section: Spatially Localized Contractionmentioning

confidence: 99%

Decisive role of nuclear quantum effects on surface mediated water dissociation at finite temperature

Litman

Donadio

Ceriotti

et al. 2017

The Journal of Chemical Physics

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“…With this idea of mixed resolution in mind the AdResS (Adaptive Resolution Scheme) method was developed, in which one can dynamically couple specific regions of a simulation box at different levels of resolution, while maintaining the correct thermodynamic equilibrium between them [14,[20][21][22][23][24][25][26]. The particles move from one region to the other through a hybrid resolution zone ( Fig.…”

mentioning

confidence: 99%

Hamiltonian Adaptive Resolution Simulation for Molecular Liquids

et al. 2013

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Adaptive resolution schemes allow the simulation of a molecular fluid treating simultaneously different subregions of the system at different levels of resolution. In this work we present a new scheme formulated in terms of a global Hamiltonian. Within this approach equilibrium states corresponding to well defined statistical ensembles can be generated making use of all standard Molecular Dynamics or Monte Carlo methods. Models at different resolutions can thus be coupled, and thermodynamic equilibrium can be modulated keeping each region at desired pressure or density without disrupting the Hamiltonian framework.

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“…This excess energy can be removed with a local thermostat, such as Langevin thermostat: in this way, the temperature of the system is kept constant everywhere. The equilibrium state of the system is then dynamical: the thermostat takes care of absorbing the extra heat produced in the transition region by non-conservative forces, and the system samples equilibrium configurations according to Boltzmann's distribution [24][25][26][27][28][29][30][31][32].…”

Section: The Adaptive Resolution Simulation Schemementioning

confidence: 99%

“…These two problems are obviously interconnected, since the way the high-and low-resolution regions interact at the interface naturally depends on the specific properties of the models used in each of them; a thorough discussion of these aspects will be carried out in the context of the Adaptive Resolution Simulation (AdResS) [24][25][26][27][28][29][30][31][32] and Hamiltonian AdResS [33,34] (H-AdResS) methods.…”

Section: Introductionmentioning

confidence: 99%

“…Adaptive resolution simulations methods [24][25][26][27][28][29][30][31][32][33][34] were developed to solve the contradiction between the necessity of simulating all parts of the system and the fact that, eventually, the detailed information from a large subgroup of them will be neglected. The underlying idea is to replace these "non-interesting" degrees of freedom of the system with a simpler, coarse-grained representation, such that a sensibly smaller number of computations (e.g., force calculations) is required, while the "interesting" region is treated at a higher resolution.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Computer Simulations of Soft Matter: Linking the Scales

Potestio

Peter

Kremer

2014

Entropy

102

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Abstract:In the last few decades, computer simulations have become a fundamental tool in the field of soft matter science, allowing researchers to investigate the properties of a large variety of systems. Nonetheless, even the most powerful computational resources presently available are, in general, sufficient to simulate complex biomolecules only for a few nanoseconds. This limitation is often circumvented by using coarse-grained models, in which only a subset of the system's degrees of freedom is retained; for an effective and insightful use of these simplified models; however, an appropriate parametrization of the interactions is of fundamental importance. Additionally, in many cases the removal of fine-grained details in a specific, small region of the system would destroy relevant features; such cases can be treated using dual-resolution simulation methods, where a subregion of the system is described with high resolution, and a coarse-grained representation is employed in the rest of the simulation domain. In this review we discuss the basic notions of coarse-graining theory, presenting the most common methodologies employed to build low-resolution descriptions of a system and putting particular emphasis on their similarities and differences. The AdResS and H-AdResS adaptive resolution simulation schemes are reported as examples of dual-resolution approaches, especially focusing in particular on their theoretical background.

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Classical to Path-Integral Adaptive Resolution in Molecular Simulation: Towards a Smooth Quantum-Classical Coupling

Cited by 69 publications

References 42 publications

Decisive role of nuclear quantum effects on surface mediated water dissociation at finite temperature

Decisive role of nuclear quantum effects on surface mediated water dissociation at finite temperature

Hamiltonian Adaptive Resolution Simulation for Molecular Liquids

Computer Simulations of Soft Matter: Linking the Scales

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