Issue 27, 2020

Comprehending the quadruple bonding conundrum in C2 from excited state potential energy curves

Abstract

The question of quadruple bonding in C2 has emerged as a hot button issue, with opinions sharply divided between the practitioners of Valence Bond (VB) and Molecular Orbital (MO) theory. Here, we have systematically studied the Potential Energy Curves (PECs) of low lying high spin sigma states of C2, N2, Be2 and HC[triple bond, length as m-dash]CH using several MO based techniques such as CASSCF, RASSCF and MRCI. The analyses of the PECs for the 2S+1Σg/u (with 2S + 1 = 1, 3, 5, 7, 9) states of C2 and comparisons with those of relevant dimers and the respective wavefunctions were conducted. We contend that unlike in the case of N2 and HC[triple bond, length as m-dash]CH, the presence of a deep minimum in the 7Σ+ state of C2 and CN+ suggests a latent quadruple bonding nature in these two dimers. Our investigations reveal that the number of bonds in the ground state can be determined for 2nd row dimers by figuring out at what value of spin symmetry a purely dissociative PEC is obtained. For N2 and HC[triple bond, length as m-dash]CH the purely dissociative PEC appears for the septet spin symmetry as compared to that for the nonet in C2. This is indicative of a higher number of bonds between the two 2nd row atoms in C2 as compared to those of N2 and HC[triple bond, length as m-dash]CH. Hence, we have struck a reconciliatory note between the MO and VB approaches. The evidence provided by us can be experimentally verified, thus providing the window so that the narrative can move beyond theoretical conjectures.

Graphical abstract: Comprehending the quadruple bonding conundrum in C2 from excited state potential energy curves

Supplementary files

Article information

Article type
Edge Article
Submitted
24 apr 2020
Accepted
10 iyn 2020
First published
11 iyn 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2020,11, 7009-7014

Comprehending the quadruple bonding conundrum in C2 from excited state potential energy curves

I. Bhattacharjee, D. Ghosh and A. Paul, Chem. Sci., 2020, 11, 7009 DOI: 10.1039/D0SC02336A

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements