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Title: Global structure search for molecules on surfaces: Efficient sampling with curvilinear coordinates

Efficient structure search is a major challenge in computational materials science. Here, 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 [C. Panosetti et al., Nano Lett. 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-β-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.
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  1. Technical Univ. of Munich, Garching (Germany). Dept. of Chemistry
  2. Univ. of Oxford (United Kingdom). Physical and Theoretical Chemistry Lab. and Dept. of Chemistry
  3. Yale Univ., New Haven, CT (United States). Dept. of Chemistry
Publication Date:
Grant/Contract Number:
FG02-05ER15677; FOR1282; EP/J011185/1
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 8; Journal ID: ISSN 0021-9606
American Institute of Physics (AIP)
Research Org:
Yale Univ., New Haven, CT (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Alexander von Humboldt Foundation; German Research Foundation (DFG); Engineering and Physical Sciences Research Council (EPSRC)
Country of Publication:
United States
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; methane; dissociation; adsorbate structures; optimization; adsorbates; molecular conformation; integrated circuits; acids; chemical bonds
OSTI Identifier:
Alternate Identifier(s):
OSTI ID: 1313244