Correction: “On-the-fly” coupled cluster path-integral molecular dynamics: impact of nuclear quantum effects on the protonated water dimer

Spura, Thomas; Elgabarty, Hossam; Kühne, Thomas D.

doi:10.1039/c5cp90118a

Cited by 4 publications

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“…In addition, recent developments in electronic structure theory and ongoing increases in computational power have made simulations using MP2 theory possible for condensed-phase water, and recent algorithms have also improved its scaling . For small gas-phase molecules, higher-level methods, such as coupled cluster theory, can also be utilized with PIMD simulations . Furthermore, recent simulations of liquid water using highly accurate quantum Monte Carlo surfaces suggest that PIMD simulations of this kind might soon become practical .…”

Section: Outlook and Ongoing Challengesmentioning

confidence: 99%

Nuclear Quantum Effects in Water and Aqueous Systems: Experiment, Theory, and Current Challenges

et al. 2016

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Nuclear quantum effects influence the structure and dynamics of hydrogen bonded systems, such as water, which impacts their observed properties with widely varying magnitudes. This review highlights the recent significant developments in the experiment, theory and simulation of nuclear quantum effects in water. Novel experimental techniques, such as deep inelastic neutron scattering, now provide a detailed view of the role of nuclear quantum effects in water's 2 properties. These have been combined with theoretical developments such as the introduction of the competing quantum effects principle that allows the subtle interplay of water's quantum effects and their manifestation in experimental observables to be explained. We discuss how this principle has recently been used to explain the apparent dichotomy in water's isotope effects, which can range from very large to almost nonexistent depending on the property and conditions. We then review the latest major developments in simulation algorithms and theory that have enabled the efficient inclusion of nuclear quantum effects in molecular simulations, permitting their combination with on-the-fly evaluation of the potential energy surface using electronic structure theory. Finally, we identify current challenges and future opportunities in the area.3

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Section: Outlook and Ongoing Challengesmentioning

confidence: 99%

Nuclear Quantum Effects in Water and Aqueous Systems: Experiment, Theory, and Current Challenges

et al. 2016

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“…50 shows results from perturbative theory, together with an extensive review of the literature. Recently, effort is being devoted to studying static properties of the protonated water dimer by new methods, employing on-the-fly coupled cluster electronic structure, 51,52 neural network potentials, 53,54 and variational Monte Carlo. 55,56 This paper describes a reduced rovibrational coupling Cartesian dynamics approach for semiclassical calculations that we apply to the vibrational spectrum of the Zundel cation, as a first step towards the study of bigger protonated water clusters.…”

Section: Introductionmentioning

confidence: 99%

Reduced rovibrational coupling Cartesian dynamics for semiclassical calculations: Application to the spectrum of the Zundel cation

Bertaina

Liberto

Ceotto

2019

The Journal of Chemical Physics

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We study the vibrational spectrum of the protonated water dimer, by means of a divide-and-conquer semiclassical initial value representation of the quantum propagator, as a first step in the study of larger protonated water clusters. We use the potential energy surface from [Huang et al., J. Chem. Phys. 122, 044308 (2005)]. To tackle such an anharmonic and floppy molecule, we employ fully Cartesian dynamics and carefully reduce the coupling to global rotations in the definition of normal modes. We apply the time-averaging filter and obtain clean power spectra relative to suitable reference states, that highlight the spectral peaks corresponding to the fundamental excitations of the system. Our trajectory-based approach allows us for physical interpretation of the very challenging proton transfer modes. We find that it is important, for such a floppy molecule, to selectively avoid to initially excite lower energy modes, in order to obtain cleaner spectra. The estimated vibrational energies display a mean absolute error (MAE) of ∼ 29cm −1 with respect to available Multi-Configuration time-dependent Hartree calculations and MAE ∼ 14cm −1 when compared to the optically active experimental excitations of the Ne-tagged Zundel cation. The reasonable scaling in the number of trajectories for Monte Carlo convergence is promising for applications to higher dimensional protonated cluster systems.The Zundel cation is the most representative member of the family of protonated water clusters, towards which many computational efforts are being devoted, mainly motivated by a flourishing of experimental results, 11-16 and the request for higher accuracy. [17][18][19][20][21] In this respect, this molecule is a prototypical example that has been tackled by various approaches, given the great biological relevance of the charge transport mechanism in aqueous solutions. [22][23][24][25][26][27] On the experimental side, the vibrational spectrum of the Zundel cation has been investigated by infrared multiphoton photodissociation spectroscopy 28,29 and noble gases predissociation spectroscopy, in particular Argon and Neon. [30][31][32] The theoretical literature about the vibrational spectrum of the Zundel cation is quite vast, since its strong anharmonicity provides the ideal test-bed for theoretical methods. The PES computed at the level of coupled cluster theory and devised in Ref. 33, has been employed by a plethora of methods for vibrational calculations, such as vibrational configuration interaction (VCI), 34 diffusion Monte Carlo, 32,35 classical molecu-

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Machine Learning Force Fields

et al. 2021

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In recent years, the use of machine learning (ML) in computational chemistry has enabled numerous advances previously out of reach due to the computational complexity of traditional electronic-structure methods. One of the most promising applications is the construction of ML-based force fields (FFs), with the aim to narrow the gap between the accuracy of ab initio methods and the efficiency of classical FFs. The key idea is to learn the statistical relation between chemical structure and potential energy without relying on a preconceived notion of fixed chemical bonds or knowledge about the relevant interactions. Such universal ML approximations are in principle only limited by the quality and quantity of the reference data used to train them. This review gives an overview of applications of ML-FFs and the chemical insights that can be obtained from them. The core concepts underlying ML-FFs are described in detail, and a step-by-step guide for constructing and testing them from scratch is given. The text concludes with a discussion of the challenges that remain to be overcome by the next generation of ML-FFs.

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Correction: “On-the-fly” coupled cluster path-integral molecular dynamics: impact of nuclear quantum effects on the protonated water dimer

Abstract: Correction for “On-the-fly” coupled cluster path-integral molecular dynamics: impact of nuclear quantum effects on the protonated water dimer` by Thomas Spura et al., Phys. Chem. Chem. Phys., 2015, 17, 14355–14359.

Cited by 4 publications

References 1 publication

Nuclear Quantum Effects in Water and Aqueous Systems: Experiment, Theory, and Current Challenges

Nuclear Quantum Effects in Water and Aqueous Systems: Experiment, Theory, and Current Challenges

Reduced rovibrational coupling Cartesian dynamics for semiclassical calculations: Application to the spectrum of the Zundel cation

Machine Learning Force Fields

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