A Vector-Based Representation of the Chemical Bond for the Substituted Torsion of Biphenyl

TL;DR

This paper introduces a vector-based representation of chemical bonds within QTAIM to analyze torsion in substituted biphenyl molecules, revealing insights into bond interactions and charge density directions.

Contribution

It presents a novel vector-based bond description within QTAIM for analyzing torsion in substituted biphenyl, including considerations of H---H interactions and charge density eigenvector paths.

Findings

H---H bond lengths vary with substitution and torsion angle.

Charge density accumulation directions influence bond length preferences.

Vector-based bond representation provides new insights into molecular torsion.

Abstract

We use a new interpretation of the chemical bond within QTAIM. The bond-path framework set $\mathbb{B} = \{p, q, r\}$ with associated linkages with lengths $\mathbb{H}^*,m\mathbb{H}$ and the familiar bond-path length is used to describe a torsion $\theta$, $0.0^{\circ} \leq \theta \lt 22.0^{\circ}$ of \emph{para}-substituted biphenyl, $\mathrm{C}_{12}\mathrm{H}_{9-x}$, $x = \mathrm{N}(\mathrm{CH}_3)_2$, $\mathrm{NH}_2$, $\mathrm{CH}_3$, CHO, CN, $\mathrm{NO}_{2}$. We include consideration of the H---H bonding interactions and find that the lengths $\mathbb{H} \gt \mathbb{H}^{*}$ that we explain in terms of the most and least preferred directions of charge density accumulation. We also consider the fractional eigenvector-following path lengths $\mathbb{H}_f$ and $\mathbb{H}_{f{\theta_{\rm min}}}$.