Potential energy surface
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Ab Initio Nonadiabatic Quantum Molecular Dynamics Open
The Born-Oppenheimer approximation underlies much of chemical simulation and provides the framework defining the potential energy surfaces that are used for much of our pictorial understanding of chemical phenomena. However, this approxima…
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SchNet: A continuous-filter convolutional neural network for modeling quantum interactions Open
Deep learning has the potential to revolutionize quantum chemistry as it is ideally suited to learn representations for structured data and speed up the exploration of chemical space. While convolutional neural networks have proven to be t…
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Neural Network Potential Energy Surfaces for Small Molecules and Reactions Open
We review progress in neural network (NN)-based methods for the construction of interatomic potentials from discrete samples (such as ab initio energies) for applications in classical and quantum dynamics including reaction dynamics and co…
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SchNet: A continuous-filter convolutional neural network for modeling\n quantum interactions Open
Deep learning has the potential to revolutionize quantum chemistry as it is\nideally suited to learn representations for structured data and speed up the\nexploration of chemical space. While convolutional neural networks have proven\nto b…
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Phase Diagram of a Deep Potential Water Model Open
Using the Deep Potential methodology, we construct a model that reproduces accurately the potential energy surface of the SCAN approximation of density functional theory for water, from low temperature and pressure to about 2400 K and 50 G…
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Cavity Born–Oppenheimer Approximation for Correlated Electron–Nuclear-Photon Systems Open
In this work, we illustrate the recently introduced concept of the cavity Born-Oppenheimer approximation [ Flick et al. PNAS 2017 , 10.1073/pnas.1615509114 ] for correlated electron-nuclear-photon problems in detail. We demonstrate how an …
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Signatures of a liquid–liquid transition in an ab initio deep neural network model for water Open
Significance Water is central across much of the physical and biological sciences and exhibits physical properties that are qualitatively distinct from those of most other liquids. Understanding the microscopic basis of water’s peculiar pr…
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On-the-Fly CASPT2 Surface-Hopping Dynamics Open
We report the development of programs for on-the-fly surface-hopping dynamics simulations in the gas and condensed phases on the potential energy surfaces computed by multistate multireference perturbation theory (XMS-CASPT2) with full int…
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Accurate Neural Network Description of Surface Phonons in Reactive Gas–Surface Dynamics: N<sub>2</sub> + Ru(0001) Open
Ab initio molecular dynamics (AIMD) simulations enable the accurate description of reactive molecule-surface scattering especially if energy transfer involving surface phonons is important. However, presently, the computational expense of …
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Quinoline derivatives as possible lead compounds for anti-malarial drugs: Spectroscopic, DFT and MD study Open
In this work we report spectroscopic characterization and reactivity study by density functional theory (DFT) and molecular dynamics (MD) simulations of two quinoline derivatives. Collected computational results for the two new derivatives…
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Automated Fitting of Neural Network Potentials at Coupled Cluster Accuracy: Protonated Water Clusters as Testing Ground Open
Highly accurate potential energy surfaces are of key interest for the detailed understanding and predictive modeling of chemical systems. In recent years, several new types of force fields, which are based on machine learning algorithms an…
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Many-Body Coarse-Grained Interactions Using Gaussian Approximation Potentials Open
We introduce a computational framework that is able to describe general many-body coarse-grained (CG) interactions of molecules and use it to model the free energy surface of molecular liquids as a cluster expansion in terms of monomer, di…
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Atomic structure of boron resolved using machine learning and global sampling Open
Here, by combining machine learning with the latest stochastic surface walking (SSW) global optimization, we explore for the first time the potential energy surface of β-B.
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Ab Initio Calculation of Rate Constants for Molecule–Surface Reactions with Chemical Accuracy Open
The ab initio prediction of reaction rate constants for systems with hundreds of atoms with an accuracy that is comparable to experiment is a challenge for computational quantum chemistry. We present a divide‐and‐conquer strategy that depa…
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Linear Atomic Cluster Expansion Force Fields for Organic Molecules: Beyond RMSE Open
We demonstrate that fast and accurate linear force fields can be built for molecules using the atomic cluster expansion (ACE) framework. The ACE models parametrize the potential energy surface in terms of body-ordered symmetric polynomials…
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q-AQUA: A Many-Body CCSD(T) Water Potential, Including Four-Body Interactions, Demonstrates the Quantum Nature of Water from Clusters to the Liquid Phase Open
Many model potential energy surfaces (PESs) have been reported for water; however, none are strictly from "first-principles". Here we report such a potential, based on a many-body representation at the CCSD(T) level of theory up to the fou…
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Comprehensive genetic algorithm for<i>ab initio</i>global optimisation of clusters Open
Cluster, as the aggregate of a few to thousands of atoms or molecules, bridges the microscopic world of atoms and molecules and the macroscopic world of condensed matters. The physical and chemical properties of a cluster are determined by…
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The Quest for Accurate Liquid Water Properties from First Principles Open
Developing accurate ab initio molecular dynamics (AIMD) models that capture both electronic reorganization and nuclear quantum effects associated with hydrogen bonding is key to quantitative understanding of bulk water and its anomalies as…
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Revealing *OOH key intermediates and regulating H <sub>2</sub> O <sub>2</sub> photoactivation by surface relaxation of Fenton-like catalysts Open
Hydrogen peroxide (H 2 O 2 ) molecules play important roles in many green chemical reactions. However, the high activation energy limits their application efficiency, and there is still huge controversy about the activation path of H 2 O 2…
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Constructing High-Dimensional Neural Network Potential Energy Surfaces for Gas–Surface Scattering and Reactions Open
While the ab initio molecular dynamics (AIMD) approach to gas–surface interaction has been instrumental in exploring important issues such as energy transfer and reactivity, it is only amenable to short-time events and a limited number of …
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Elucidating the Nuclear Quantum Dynamics of Intramolecular Double Hydrogen Transfer in Porphycene Open
We address the double hydrogen transfer (DHT) dynamics of the porphycene molecule, a complex paradigmatic system in which the making and breaking of H-bonds in a highly anharmonic potential energy surface require a quantum mechanical treat…
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Taming the Complexity of Donor–Acceptor Stenhouse Adducts: Infrared Motion Pictures of the Complete Switching Pathway Open
Switches that can be actively steered by external stimuli along multiple pathways at the molecular level are the basis for next-generation responsive material systems. The operation of commonly employed molecular photoswitches revolves aro…
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Mechanism of O<sub>2</sub> Activation by α-Ketoglutarate Dependent Oxygenases Revisited. A Quantum Chemical Study Open
Four mechanisms previously proposed for dioxygen activation catalyzed by α-keto acid dependent oxygenases (α-KAO) were studied with dispersion-corrected DFT methods employing B3LYP and TPSSh functionals in combination with triple-ζ basis s…
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Ultrafast X-Ray Scattering Measurements of Coherent Structural Dynamics on the Ground-State Potential Energy Surface of a Diplatinum Molecule Open
We present x-ray free electron laser experiments addressing ground-state structural dynamics of the diplatinum anion Pt2POP4 following photoexcitation. The structural dynamics are tracked with < 100 fs time resolution by x-ray scattering, …
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Selectivity in single-molecule reactions by tip-induced redox chemistry Open
Controlling selectivity of reactions is an ongoing quest in chemistry. In this work, we demonstrate reversible and selective bond formation and dissociation promoted by tip-induced reduction-oxidation reactions on a surface. Molecular rear…
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First-principles quantum dynamical theory for the dissociative chemisorption of H2O on rigid Cu(111) Open
Despite significant progress made in the past decades, it remains extremely challenging to investigate the dissociative chemisorption dynamics of molecular species on surfaces at a full-dimensional quantum mechanical level, in particular f…
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Formation of the prebiotic molecule NH<sub>2</sub>CHO on astronomical amorphous solid water surfaces: accurate tunneling rate calculations Open
Investigating how formamide forms in the interstellar medium is a hot topic in astrochemistry, which can contribute to our understanding of the origin of life on Earth.
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Reaction Mechanisms on Multiwell Potential Energy Surfaces in Combustion (and Atmospheric) Chemistry Open
Chemical reactions occurring on a potential energy surface with multiple wells are ubiquitous in low-temperature combustion and in the oxidation of volatile organic compounds in Earth's atmosphere. The rich variety of structural isomerizat…
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PyFrag 2019—Automating the exploration and analysis of reaction mechanisms Open
We present a substantial update to the PyFrag 2008 program, which was originally designed to perform a fragment‐based activation strain analysis along a provided potential energy surface. The original PyFrag 2008 workflow facilitated the c…
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Density Functional Theory for Molecule–Metal Surface Reactions: When Does the Generalized Gradient Approximation Get It Right, and What to Do If It Does Not Open
While density functional theory (DFT) is perhaps the most used electronic structure theory in chemistry, many of its practical aspects remain poorly understood. For instance, DFT at the generalized gradient approximation (GGA) tends to fai…