Ponec, Robert, Cooper, David L ORCID: 0000-0003-0639-0794 and Karadakov, Peter B
(2020)
Are Multicentre Bond Indices and Related Quantities Reliable Predictors of Excited-State Aromaticity?
MOLECULES, 25 (20).
E4791-.
This is the latest version of this item.
Text
molecules-949153.pdf - Author Accepted Manuscript Download (533kB) | Preview |
Abstract
Systematic scrutiny is carried out of the ability of multicentre bond indices and the NOEL-based similarity index <i>d</i><sub>AB</sub> to serve as excited-state aromaticity criteria. These indices were calculated using state-optimized complete active-space self-consistent field wavefunctions for several low-lying singlet and triplet states of the paradigmatic molecules of benzene and square cyclobutadiene and the inorganic ring S<sub>2</sub>N<sub>2</sub>. The comparison of the excited-state indices with aromaticity trends for individual excited states suggested by the values of magnetic aromaticity criteria show that whereas the indices work well for aromaticity reversals between the ground singlet and first triplet electronic states, addressed by Baird's rule, there are no straightforward parallels between the two sets of data for singlet excited states. The problems experienced while applying multicentre bond indices and <i>d</i><sub>AB</sub> to singlet excited states are explained by the loss of the information inherently present in wavefunctions and/or pair densities when calculating the first-order density matrix.
Item Type: | Article |
---|---|
Uncontrolled Keywords: | excited-state aromaticity reversals, multicentre bond indices, molecular similarity, magnetic properties of excited states |
Depositing User: | Symplectic Admin |
Date Deposited: | 19 Oct 2020 09:02 |
Last Modified: | 10 Feb 2024 03:15 |
DOI: | 10.3390/molecules25204791 |
Open Access URL: | https://www.mdpi.com/1420-3049/25/20/4791 |
Related URLs: | |
URI: | https://livrepository.liverpool.ac.uk/id/eprint/3104535 |
Available Versions of this Item
-
Are multicentre bond indices and related quantities reliable predictors of excited-state aromaticity? (deposited 16 Oct 2020 07:24)
- Are Multicentre Bond Indices and Related Quantities Reliable Predictors of Excited-State Aromaticity? (deposited 19 Oct 2020 09:02) [Currently Displayed]