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Title: On the performance of composite schemes in determining equilibrium molecular structures

Journal Article · · Journal of Computational Chemistry
DOI: https://doi.org/10.1002/jcc.27312 · OSTI ID:2320303
ORCiD logo [1];  [1];  [1]
  1. Department of Chemistry University of Florida Gainesvillle Florida USA
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Abstract Determination of equilibrium molecular structures is an essential ingredient in predicting spectroscopic parameters that help in identifying molecular carriers of microwave transitions. Here, the performance of two different ab initio composite approaches for obtaining equilibrium structures, “energy scheme” and “geometry scheme,” is explored and compared to semi‐experimental equilibrium structures. This study is performed for a set of 11 molecules which includes diatomics, linear triatomics, and a few non‐linear molecules. The ab initio calculations were performed using three tiers of composite chemical recipes. The current results show that as the overall rigor of calculation is increased, the semi‐experimental and the ab initio numbers agree to within 0.0003 Å for all molecules in the test set. The composite approach based on correcting the potential energy surface (energy scheme) and the one based on correcting the geometry directly (geometry scheme) show excellent agreement with each other. This work represents a step toward development of efficient and highly accurate procedures for computing ab initio equilibrium structures.

Sponsoring Organization:
USDOE
Grant/Contract Number:
DE‐SC0018164
OSTI ID:
2320303
Journal Information:
Journal of Computational Chemistry, Journal Name: Journal of Computational Chemistry Vol. 45 Journal Issue: 16; ISSN 0192-8651
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
United States
Language:
English

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