The Jahn–Teller and pseudo‐Jahn–Teller effects in the anion photoelectron spectroscopy of B₃ cluster

Abstract

The photodetachment spectroscopy of B3- anion is theoretically studied with the aid of a quantum dynamical approach. The theoretical results are compared with the available experimental photoelectron spectra of B3-. Both B3- and B3 possess D(3h) symmetry at the equilibrium configuration of their electronic ground state. Distortion of B3 along its degenerate vibrational mode nu2 splits the degeneracy of its excited C2E' electronic manifold and exhibits (E [symbol: see text] e)-Jahn-Teller (JT) activity. The components of the JT split potential energy surface form conical intersections, and they can also undergo pseudo-Jahn-Teller (PJT) crossings with the X2A1' electronic ground state of B3 via the degenerate nu2 vibrational mode. The impact of the JT and PJT interactions on the nuclear dynamics of B3 in its X2A1'-C2E' electronic states is examined here by establishing a diabatic model Hamiltonian. The parameters of the electronic part of this Hamiltonian are calculated by performing electronic structure calculations and the nuclear dynamics on it is simulated by solving quantum eigenvalue equation. The theoretical results are in good accord with the experimental data.

Thermochemistry and Electronic Structure of Small Boron and Boron Oxide Clusters and Their Anions

“…Photoelectron spectroscopy studies of the B 3 anion determined the vertical position of the lowest doublet and quartet states of have been analyzed in detail. 85 The calculated VDE is in excellent agreement with the photoelectron spectroscopy 84 VDE. The VAE and VDE are essentially the same.…”

“…The singlet−triplet gap in B 3 − is 34.3 kcal/mol, comparable to the doublet−quartet gap in B 3 . The Jahn−Teller effects accompanying the photodetachment of B 3 − have been analyzed in detail . The calculated VDE is in excellent agreement with the photoelectron spectroscopy VDE.…”

Structural transformations in boron clusters induced by metal doping

“…Recently, some reports of clusters formed by three B atoms showed intriguing bonding and aromaticity. 35–40,44,46 However, since doping B 3 does not lead to any significant modification but rather to an energetic exchange between its two isomers, the linear and the triangular, we begin by describing clusters from four B atoms and, from the lowest to the highest, in our perspective, structural transformation degree. While most experimental techniques have favored the characterization of mainly anionic boron clusters, and in most cases, preceded the characterization of the neutral or cationic counterparts, the order shown for the bare systems is from cations to anions, since the former are the first to show a distortion of the boron skeleton, namely, the 2D to 3D transition.…”

Understanding of the Photodetachment Spectrum of Anionic Mixed Carbon–Boron Cluster C3B5– Following Adiabatic and Nonadiabatic Quantum Chemistry Approaches

“…Carbon–boron [C–B] mixed clusters (or boron carbides) have earned enormous attention in recent years, especially because of their consolidated construction and phenomenal range of stable stoichiometry. − Over the decades, the kaizen approach of continued betterment confirmed some salient findings. In particular, one of the boron atoms in these clusters occupies a central location (otherwise possessed by a carbon atom) and exhibits hypercoordination.…”

“…In the present paper, we attempt to advance the understanding of the photodetachment spectrum for C 3 B 5 – following a combination of quantum dynamics methods. It is noted that the structural confirmations of the bare boron clusters and their structural cousins using nuclear dynamics study were first initiated by Mahapatra and co-workers. − We request the interested reader to go to the recent review of Mahapatra in order to access more details about nuclear dynamics. The success of the method has been remarkable and was employed to unravel intriguing features in the photodetachment spectra of many molecules.…”