skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Search for: All records

Creators/Authors contains: "Ochieng, Sharon A"

Note: When clicking on a Digital Object Identifier (DOI) number, you will be taken to an external site maintained by the publisher. Some full text articles may not yet be available without a charge during the embargo (administrative interval).
What is a DOI Number?

Some links on this page may take you to non-federal websites. Their policies may differ from this site.

  1. An impressive collection of accurate two-body interaction energies for small complexes has been assembled into benchmark databases and used to improve the performance of multiple density functional, semiempirical, and machine learning methods. Similar benchmark data on nonadditive three-body energies in molecular trimers are comparatively scarce, and the existing ones are practically limited to homotrimers. In this work, we present a benchmark dataset of 20 equilibrium noncovalent interaction energies for a small but diverse selection of 10 heteromolecular trimers. The new 3BHET dataset presents complexes that combine different interactions including π −π, anion−π, cation−π, and various motifs of hydrogen and halogen bonding in each trimer. A detailed symmetry-adapted perturbation theory (SAPT)-based energy decomposition of the two- and three-body interaction energies shows that 3BHET consists of electrostatics- and dispersion-dominated complexes. The nonadditive three-body contribution is dominated by induction, but its influence on the overall bonding type in the complex (as exemplified by its position on the ternary diagram) is quite small. We also tested the extended SAPT (XSAPT) approach which is capable of including some nonadditive interactions in clusters of any size. The resulting three-body dispersion term (obtained from the many-body dispersion formalism) is mostly in good agreement with the supermolecular CCSD(T)−MP2 values and the nonadditive induction term is similar to the three-body SAPT(DFT) data, but the overall three-body XSAPT energies are not very accurate as they are missing the first-order exchange terms. 
    more » « less