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Probing the Structure and Dynamics of Interfacial Water with Scanning Tunneling Microscopy and Spectroscopy

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Published on: May 27, 2018

Ab initio water pair potential with flexible monomers.

Piotr Jankowski^1,2, Garold Murdachaew¹, Robert Bukowski¹

¹†Department of Physics and Astronomy, University of Delaware, Newark, Delaware 19716, United States.

The Journal of Physical Chemistry. A

|February 18, 2015

Summary

A new potential energy surface for water dimers was developed, improving accuracy for molecular simulations. This surface accurately predicts dimer structures and thermodynamic properties, including second virial coefficients.

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Controlling the Size, Shape and Stability of Supramolecular Polymers in Water

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Area of Science:

Computational chemistry
Molecular modeling
Quantum chemistry

Background:

Accurate potential energy surfaces are crucial for understanding molecular interactions.
Previous models for water dimers had limitations in precision and scope.

Purpose of the Study:

To develop a highly accurate potential energy surface for water dimers.
To incorporate explicit monomer flexibility into the surface.
To refine existing computational models for water dimer interactions.

Main Methods:

Fitting interaction energies to a large dataset (over 250,000 points).
Utilizing symmetry-adapted perturbation theory and coupled-cluster methods.
Evaluating the accuracy of the new surface against ab initio calculations and experimental data.

Main Results:

The developed surface exhibits high accuracy, correcting small errors in previous fits.
Minimum and saddle-point structures closely match direct ab initio optimizations.
Computed second virial coefficients show good agreement with experimental values.

Conclusions:

The new potential energy surface provides a more accurate representation of water dimer interactions.
Monomer flexibility has a minor impact on virial coefficients at low temperatures compared to quantum effects.
This work advances the computational study of water clusters and related phenomena.