Abstract
The nature of donor-acceptor interactions is important for the understanding of dative bonding and can provide vital insights into many chemical processes. Here, we have performed a computational study to elucidate substantial differences between different types of dative interactions. For this purpose, a data set of 20 molecular complexes stabilized by dative bonds was developed (DAT20). A benchmark study that considers many popular density functionals with respect to accurate quantum chemical interaction energies and geometries revealed two different trends between the complexes of DAT20. This behavior was further explored by means of frontier molecular orbitals, extended-transition-state natural orbitals for chemical valence (ETS-NOCV), and natural energy decomposition analysis (NEDA). These methods revealed the extent of the forward and backdonation between the donor and acceptor molecules and how they influence the total interaction energies and molecular geometries. A new classification of dative bonds is suggested.
| Original language | English |
|---|---|
| Pages (from-to) | 7956-7966 |
| Number of pages | 11 |
| Journal | Journal of Physical Chemistry A |
| Volume | 125 |
| Issue number | 36 |
| DOIs | |
| State | Published - Sep 16 2021 |
Funding
The authors gratefully acknowledge the National Science Foundation (CHE-1800237) for financial support of this work and the Advanced Computer Facility (ACF) of the University of Tennessee for computational resources. The authors would like to thank Dr. Jacob Townsend and Gavin Mccarver for their fruitful discussions on the manuscript.