From 5e3a9f457445b848890007e0a904c721e32fe96f Mon Sep 17 00:00:00 2001 From: EnzoMonino Date: Fri, 26 Mar 2021 16:24:52 +0100 Subject: [PATCH] Manuscript --- Manuscript/CBD.bib | 17 +++++++++++++++++ Manuscript/CBD.tex | 2 +- 2 files changed, 18 insertions(+), 1 deletion(-) diff --git a/Manuscript/CBD.bib b/Manuscript/CBD.bib index ec1d135..6e08338 100644 --- a/Manuscript/CBD.bib +++ b/Manuscript/CBD.bib @@ -123,4 +123,21 @@ urldate = {2021-03-25}, date = {1980-01-01}, langid = {english} +} + +@article{whitman_limits_1982, + title = {Limits on the activation parameters for automerization of cyclobutadiene-1,2-d2}, + volume = {104}, + issn = {0002-7863}, + url = {https://doi.org/10.1021/ja00387a065}, + doi = {10.1021/ja00387a065}, + pages = {6473--6474}, + number = {23}, + journaltitle = {Journal of the American Chemical Society}, + shortjournal = {J. Am. Chem. Soc.}, + author = {Whitman, David W. and Carpenter, Barry K.}, + urldate = {2021-03-26}, + date = {1982-11-01}, + note = {Publisher: American Chemical Society}, + file = {ACS Full Text Snapshot:/Users/monino/Zotero/storage/4U7ZD87S/ja00387a065.html:text/html} } \ No newline at end of file diff --git a/Manuscript/CBD.tex b/Manuscript/CBD.tex index 454acc4..33ec5e0 100644 --- a/Manuscript/CBD.tex +++ b/Manuscript/CBD.tex @@ -217,7 +217,7 @@ Write an abstract \label{sec:intro} %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% -Despite the fact that excited states are involved in ubiquitious processes such as photochemistry, catalysis or in solar cell technology, none of the many methods existing is the reference in providing accurate excited states energies. Indeed, each method has its own flaws and there are so many chemical scenario that can occur, so it is still one of the biggest challenge in theoretical chemistry. Speaking of difficult task, cyclobutadiene (CBD) molecule has been a real challenge for experimental and theoretical chemists for many decades \cite{bally_cyclobutadiene_1980}. Due to his antiaromaticity \cite{noauthor_aromaticity_nodate} and his large angular strain \cite{baeyer_ueber_1885} the CBD molecule presents a high reactivity which made the synthesis of this molecule a particularly difficult task. Hückel molecular orbital theory gives a triplet state with square ($D_{4h}$) geometry for the ground state of the CBD,with the two singly occupied frontier orbitals that are degenerated by symmetry. This degeneracy is lifted by the Jahn-Teller effect, meaning by distortion of the molecule (lowering symmetry), and gives a singlet state with rectangular ($D_{2h}$) geometry for the ground state. Indeed, synthetic work from Pettis and co-workers \cite{reeves_further_1969} gives a rectangular geometry to the singlet ground state of CBD and then was confirmed by experimental works \cite{irngartinger_bonding_1983,ermer_three_1983,kreile_uv_1986}. At the ground state structrure ($D_{2h}$), the ${}^1A_g$ state has a weak multi-configurational character because of the well separated frontier orbitals and can be described by single-reference methods. But at the square ($D_{4h}$) geometry, the singlet state (${}^1B_{1g}$) has two singly occupied frontier orbitals that are degenerated so has a two-configurational character and single-reference methods are unreliable to describe it. The singlet ($D_{4h}$) is a transition state in the automerization reaction between the two rectangular structures. +Despite the fact that excited states are involved in ubiquitious processes such as photochemistry, catalysis or in solar cell technology, none of the many methods existing is the reference in providing accurate excited states energies. Indeed, each method has its own flaws and there are so many chemical scenario that can occur, so it is still one of the biggest challenge in theoretical chemistry. Speaking of difficult task, cyclobutadiene (CBD) molecule has been a real challenge for experimental and theoretical chemists for many decades \cite{bally_cyclobutadiene_1980}. Due to his antiaromaticity \cite{noauthor_aromaticity_nodate} and his large angular strain \cite{baeyer_ueber_1885} the CBD molecule presents a high reactivity which made the synthesis of this molecule a particularly difficult task. Hückel molecular orbital theory gives a triplet state with square ($D_{4h}$) geometry for the ground state of the CBD,with the two singly occupied frontier orbitals that are degenerated by symmetry. This degeneracy is lifted by the Jahn-Teller effect, meaning by distortion of the molecule (lowering symmetry), and gives a singlet state with rectangular ($D_{2h}$) geometry for the ground state. Indeed, synthetic work from Pettis and co-workers \cite{reeves_further_1969} gives a rectangular geometry to the singlet ground state of CBD and then was confirmed by experimental works \cite{irngartinger_bonding_1983,ermer_three_1983,kreile_uv_1986}. At the ground state structrure ($D_{2h}$), the ${}^1A_g$ state has a weak multi-configurational character because of the well separated frontier orbitals and can be described by single-reference methods. But at the square ($D_{4h}$) geometry, the singlet state (${}^1B_{1g}$) has two singly occupied frontier orbitals that are degenerated so has a two-configurational character and single-reference methods are unreliable to describe it. The singlet ($D_{4h}$) is a transition state in the automerization reaction between the two rectangular structures. The energy barrier for the automerization of the CBD was predicted, experimentally, in the range of 1.6-10 kcal.mol$^{-1}$ \cite{whitman_limits_1982} and multi-reference calculations gave an energy barrier in the range of 6-7 kcal.mol$^{-1}$ \cite{eckert-maksic_automerization_2006}. All the specificities of the CBD molecule make it a real playground for excited-states methods. In the present work we investigate excitated states and automerization barrier of the CBD using a collection of methods. \begin{figure} \includegraphics[width=0.6\linewidth]{figure2.png}