Energy landscapes of the water hexamer and octamer for the MB-pol and TIP4P/2005 potentials.

Among the numerous interaction potentials available for water, MB-pol and TIP4P/2005 are popular choices to model both gas and condensed phases. Here, we examine the intermediate case of finite clusters for 6 and 8 molecules, with a thorough survey of the energy landscapes using a combination of basin-hopping global optimization and discrete path sampling methods. The two potentials predict qualitatively similar energy landscapes for both the hexamer and octamer. However, important differences arise due to changes in the energetic ordering of corresponding minima, including the global minimum itself. Differences in the classical heat capacities are relatively modest and mostly occur at low temperatures as a result of transitions between competing isomers. The heat capacity peaks can be assigned and interpreted using the temperature gradient of the occupation probabilities and involve only a few minima. The polarizable and flexible MB-pol model is more sophisticated than the rigid, non-polarizable TIP4P/2005 model and produces different intermediates in the isomerization pathways between low-energy configurations of the hexamer. In contrast, the pathways connecting low-lying cubic isomers of the octamer agree quantitatively between the two models, aside from some energetic reordering.

• Publication year

  2026

• Venue

  Journal of Chemical Physics

• Publication date

  2026-02-09

• Fields of study

  Medicine, Physics, Chemistry

• Identifiers
  DOI 10.1063/5.0317247PMID 41661044
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar

• No claims are published for this paper.

• No concepts are published for this paper.

• Global properties of the energy landscape: a testing and training arena for machine learned potentials

  2025cited by this paper
• Nuclear Quantum Effects in Neutral Water Clusters at Finite Temperature: Structural Evolution from Two to Three Dimensions.

  2025cited by this paper
• Solid-State 2H NMR Analysis for Hierarchical Water Clusters Confined to Quasi-One-Dimensional Molecular Nanoporous Crystals

  2025cited by this paper
• Applications of the density functional method combined with the electron-positron correlation-polarization potential to positron binding to hydrocarbons and water clusters.

  2025cited by this paper
• From all-atom to rigid monomer treatment of molecular clusters.

  2025cited by this paper
• Stability of drop-like water cluster

  2024cited by this paper
• An extensive assessment of the performance of pairwise and many-body interaction potentials in reproducing ab initio benchmark binding energies for water clusters n = 2-25.

  2023cited by this paper
• Comparing machine learning potentials for water: Kernel-based regression and Behler-Parrinello neural networks.

  2023cited by this paper
• Exact electronic states with shallow quantum circuits from global optimisation

  2023cited by this paper
• MB-pol(2023): Sub-chemical Accuracy for Water Simulations from the Gas to the Liquid Phase.

  2023cited by this paper
• Many-Body Contributions in Water Nanoclusters

  2022cited by this paper
• Review on the clustering behavior in aqueous solutions

  2022cited by this paper
• Water clusters and density fluctuations in liquid water based on extended hierarchical clustering methods

  2022cited by this paper
• A high-accuracy machine-learning water model for exploring water nanocluster structures.

  2021cited by this paper
• Temperature and Nuclear Quantum Effects on the Stretching Modes of the Water Hexamer

  2020cited by this paper
• Tunneling Splittings in Water Clusters from Path Integral Molecular Dynamics.

  2019cited by this paper
• Mutational Basin-Hopping: Combined Structure and Sequence Optimization for Biomolecules.

  2018cited by this paper
• Path Integral Energy Landscapes for Water Clusters.

  2018cited by this paper
• Self-optimized construction of transition rate matrices from accelerated atomistic simulations with Bayesian uncertainty quantification

  2018cited by this paper
• Machine learning prediction of interaction energies in rigid water clusters.

  2018cited by this paper
• Decoding heat capacity features from the energy landscape.

  2017cited by this paper
• Monitoring Water Clusters "Melt" Through Vibrational Spectroscopy.

  2017cited by this paper
• Analytic dynamical corrections to transition state theory

  2016cited by this paper
• Quasi-combinatorial energy landscapes for nanoalloy structure optimisation.

  2015cited by this paper
• Free energy basin-hopping

  2015cited by this paper
• Grand and Semigrand Canonical Basin-Hopping

  2015cited by this paper
• Development of a "First Principles" Water Potential with Flexible Monomers: Dimer Potential Energy Surface, VRT Spectrum, and Second Virial Coefficient.

  2014cited by this paper
• Communication: optimal parameters for basin-hopping global optimization based on Tsallis statistics.

  2014cited by this paper
• Building Water Models: A Different Approach

  2014cited by this paper
• Structure prediction for multicomponent materials using biminima.

  2014cited by this paper
• Basin constrained κ-dimer method for saddle point finding.

  2014cited by this paper
• Investigation of terahertz vibration-rotation tunneling spectra for the water octamer.

  2013cited by this paper
• Nuclear quantum effects on the structure and the dynamics of [H2O]8 at low temperatures.

  2013cited by this paper
• The curious case of the water hexamer: Cage vs. Prism

  2013cited by this paper
• Optimal geometries and harmonic vibrational frequencies of the global minima of water clusters (H2O)n, n = 2-6, and several hexamer local minima at the CCSD(T) level of theory.

  2013cited by this paper
• A Local Rigid Body Framework for Global Optimization of Biomolecules.

  2012cited by this paper
• A neural network potential-energy surface for the water dimer based on environment-dependent atomic energies and charges.

  2012cited by this paper
• Instanton calculations of tunneling splittings for water dimer and trimer.

  2011cited by this paper
• Ab initio theoretical calculations of the electronic excitation energies of small water clusters.

  2011cited by this paper
• A flexible model for water based on TIP4P/2005.

  2011cited by this paper
• Nuclear quantum effects in water clusters: the role of the molecular flexibility.

  2010cited by this paper
• Transmembrane structures for Alzheimer's Aβ(1-42) oligomers.

  2010cited by this paper
• High-Level Ab Initio Electronic Structure Calculations of Water Clusters (H2O)16 and (H2O)17: A New Global Minimum for (H2O)16

  2010cited by this paper
• Communication: κ-dynamics--an exact method for accelerating rare event classical molecular dynamics.

  2010cited by this paper
• Calculating rate constants and committor probabilities for transition networks by graph transformation.

  2009cited by this paper
• Development of transferable interaction potentials for water. V. Extension of the flexible, polarizable, Thole-type model potential (TTM3-F, v. 3.0) to describe the vibrational spectra of water clusters and liquid water.

  2008cited by this paper
• Optimization methods for finding minimum energy paths.

  2008cited by this paper
• Free energy surfaces from an extended harmonic superposition approach and kinetics for alanine dipeptide

  2008cited by this paper
• The performance of minima hopping and evolutionary algorithms for cluster structure prediction.

  2008cited by this paper
• Graph transformation method for calculating waiting times in Markov chains.

  2006cited by this paper
• Protonated water clusters described by an empirical valence bond potential.

  2005cited by this paper
• A general purpose model for the condensed phases of water: TIP4P/2005.

  2005cited by this paper
• Finding pathways between distant local minima.

  2005cited by this paper
• Global minima for water clusters (H2O)n, n ⩽ 21, described by a five-site empirical potential

  2005cited by this paper
• Minima hopping: an efficient search method for the global minimum of the potential energy surface of complex molecular systems.

  2004cited by this paper
• A doubly nudged elastic band method for finding transition states.

  2004cited by this paper
• Some further applications of discrete path sampling to cluster isomerization

  2004cited by this paper
• Evolving better nanoparticles: Genetic algorithms for optimising cluster geometries

  2003cited by this paper
• A reappraisal of what we have learnt during three decades of computer simulations on water

  2002cited by this paper
• Discrete path sampling

  2002cited by this paper
• Isomerization and melting-like transition of size-selected water nonamers

  2002cited by this paper
• Dynamical Aspects of Isomerization and Melting Transitions in (H2O)8

  2001cited by this paper
• A climbing image nudged elastic band method for finding saddle points and minimum energy paths

  2000cited by this paper
• A five-site model for liquid water and the reproduction of the density anomaly by rigid, nonpolarizable potential functions

  2000cited by this paper
• Temperature-accelerated dynamics for simulation of infrequent events

  2000cited by this paper
• Global minima of protonated water clusters

  2000cited by this paper
• Solvated excess protons in water: quantum effects on the hydration structure

  2000cited by this paper
• Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points

  2000cited by this paper
• Tetrahedral global minimum for the 98-atom Lennard-Jones cluster.

  1999cited by this paper
• ISOMERIZATION, MELTING, AND POLARITY OF MODEL WATER CLUSTERS : (H2O)6 AND (H2O)8

  1999cited by this paper
• The nature of the hydrated excess proton in water

  1999cited by this paper
• DEFECT MIGRATION IN CRYSTALLINE SILICON

  1999cited by this paper
• A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives

  1999cited by this paper
• Global minima of water clusters (H2O)n, n≤21, described by an empirical potential

  1998cited by this paper
• Archetypal energy landscapes

  1998cited by this paper
• Description of the potential energy surface of the water dimer with an artificial neural network

  1997cited by this paper
• The topology of multidimensional potential energy surfaces: Theory and application to peptide structure and kinetics

  1997cited by this paper
• On the Quantum Nature of the Shared Proton in Hydrogen Bonds

  1997cited by this paper
• Global Optimization by Basin-Hopping and the Lowest Energy Structures of Lennard-Jones Clusters Containing up to 110 Atoms

  1997cited by this paper
• Contribution of Many-Body Terms to the Energy for Small Water Clusters: A Comparison of ab Initio Calculations and Accurate Model Potentials

  1997cited by this paper
• MOLECULAR DYNAMICS STUDY OF WATER CLUSTERS, LIQUID, AND LIQUID-VAPOR INTERFACE OF WATER WITH MANY-BODY POTENTIALS

  1997cited by this paper
• Reversible work transition state theory: application to dissociative adsorption of hydrogen

  1994cited by this paper
• Monte Carlo-minimization approach to the multiple-minima problem in protein folding.

  1987cited by this paper
• Packing Structures and Transitions in Liquids and Solids

  1984cited by this paper
• Comparison of simple potential functions for simulating liquid water

  1983cited by this paper
• Statistical mechanics and morphology of very small atomic clusters

  1976cited by this paper
• Some applications of the transition state method to the calculation of reaction velocities, especially in solution

  1935cited by this paper
• The Activated Complex and the Absolute Rate of Chemical Reactions.

  1935cited by this paper
• Über die Geschwindigkeitskonstante von Austauschreaktionen

  1932cited by this paper

• No citing papers are available for this paper.