Global Structure Search for Molecules on Surfaces: Efficient Sampling with Curvilinear Coordinates

TL;DR

This paper introduces a curvilinear coordinate-based global structure search method that improves the efficiency of finding stable structures of molecules on surfaces, outperforming traditional Cartesian-based approaches.

Contribution

The authors extend a curvilinear coordinate approach for global optimization to complex molecules on surfaces, incorporating flexible constraints and local movements for enhanced sampling.

Findings

Superior performance on test systems compared to Cartesian methods

Effective sampling of chemically meaningful structures

Applicable to large adsorbates and complex molecules

Abstract

Efficient structure search is a major challenge in computational materials science. We present a modification of the basin hopping global geometry optimization approach that uses a curvilinear coordinate system to describe global trial moves. This approach has recently been shown to be efficient in structure determination of clusters [Nano Letters 15, 8044-8048 (2015)] and is here extended for its application to covalent, complex molecules and large adsorbates on surfaces. The employed, automatically constructed delocalized internal coordinates are similar to molecular vibrations, which enhances the generation of chemically meaningful trial structures. By introducing flexible constraints and local translation and rotation of independent geometrical subunits we enable the use of this method for molecules adsorbed on surfaces and interfaces. For two test systems, trans-$\beta$-ionylideneacetic acid adsorbed on a Au(111) surface and methane adsorbed on a Ag(111) surface, we obtain superior performance of the method compared to standard optimization moves based on Cartesian coordinates.