some edition corrections
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@ -537,7 +537,7 @@
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journal = {Chem. Soc. Rev.},
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langid = {english},
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number = {5},
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pages = {321},
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pages = {321-328},
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title = {Potential Energy Surface Crossings in Organic Photochemistry},
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volume = {25},
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year = {1996},
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@ -549,7 +549,7 @@
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date-modified = {2022-03-21 21:52:35 +0100},
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doi = {10.1021/acs.jpclett.0c01875},
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journal = {J. Phys. Chem. Lett.},
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pages = {7371},
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pages = {7371-7382},
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title = {The Bethe-Salpeter Formalism: {{From}} Physics to Chemistry},
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volume = {11},
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year = {2020},
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@ -812,7 +812,7 @@
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date-modified = {2022-03-23 11:46:41 +0100},
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doi = {10.1039/c9cp06507e},
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journal = {Phys. Chem. Chem. Phys.},
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pages = {4326},
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pages = {4326-4342},
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title = {Spin-Flip Methods in Quantum Chemistry},
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volume = {22},
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year = {2020},
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@ -1017,7 +1017,7 @@
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date-modified = {2022-03-23 11:33:09 +0100},
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doi = {10.1021/acs.jctc.8b00849},
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journal = {J. Chem. Theory Comput.},
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pages = {5739},
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pages = {5739-5749},
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title = {Machine Learning Configuration Interaction},
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volume = {14},
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year = {2018},
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@ -1155,7 +1155,7 @@
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journal = {Chem. Comm.},
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langid = {english},
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number = {27},
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pages = {4853},
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pages = {4853-4865},
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shorttitle = {Organic Photovoltaics},
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title = {Organic Photovoltaics: {{A}} Chemical Approach},
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volume = {46},
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@ -2477,7 +2477,7 @@
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date-modified = {2022-03-23 11:33:09 +0100},
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doi = {10.1063/1.463930},
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journal = {J. Chem. Phys.},
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pages = {4282},
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pages = {4282-4288},
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title = {The Coupled-Cluster Single, Double, Triple, and Quadruple Excitation Method},
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volume = {97},
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year = {1992},
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@ -2834,7 +2834,7 @@
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date-modified = {2022-03-23 11:33:09 +0100},
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doi = {10.1021/acs.jctc.9b01216},
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journal = {J. Chem. Theory Comput.},
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pages = {1711},
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pages = {1711-1741},
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title = {A Mountaineering Strategy to Excited States: {{Highly-accurate}} Energies and Benchmarks for Medium Size Molecules,},
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volume = {16},
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year = {2020},
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@ -3037,7 +3037,7 @@
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date-modified = {2022-03-23 11:33:09 +0100},
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doi = {10.1063/1.1651060},
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journal = {J. Chem. Phys.},
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pages = {5932},
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pages = {5932-5937},
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title = {Double Excitations within Time-Dependent Density Functional Theory Linear Response},
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volume = {120},
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year = {2004},
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@ -3349,7 +3349,7 @@
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date-modified = {2022-03-23 11:33:09 +0100},
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doi = {10.1063/1.461534},
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journal = {J. Chem. Phys.},
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pages = {6645},
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pages = {6645-6651},
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title = {Coupled-Cluster Method Truncated at Quadruples},
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volume = {95},
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year = {1991},
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@ -3729,10 +3729,13 @@
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author = {Sarkar, R. and Loos, P. F. and {Boggio-Pasqua}, M. and Jacquemin., D.},
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date-added = {2022-03-24 22:00:41 +0100},
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date-modified = {2022-03-24 22:00:41 +0100},
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doi = {10.1021/acs.jctc.1c01197},
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journal = {J. Chem. Theory Comput.},
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pages = {in press},
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pages = {2418-2436},
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title = {Assessing the Performances of {{CASPT2}} and {{NEVPT2}} for Vertical Excitation Energies,},
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year = {2022}}
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volume={18},
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year = {2022},
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bdsk-url-1 = {https://doi.org/10.1021/acs.jctc.1c01197}}
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@article{Sauer_2009,
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author = {Sauer, Stephan P. A. and Schreiber, Marko and {Silva-Junior}, Mario R. and Thiel, Walter},
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@ -84,6 +84,7 @@
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\affiliation{\LCPQ}
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\begin{abstract}
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\section*{Abstract}
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Cyclobutadiene is a well-known playground for theoretical chemists and is particularly suitable to test ground- and excited-state methods.
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Indeed, due to its high spatial symmetry, especially at the $D_{4h}$ square geometry but also in the $D_{2h}$ rectangular arrangement, the ground and excited states of cyclobutadiene exhibit multi-configurational characters and single-reference methods, such as adiabatic time-dependent density-functional theory (TD-DFT) or equation-of-motion coupled cluster (EOM-CC), are notoriously known to struggle in such situations.
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In this work, using a large panel of methods and basis sets, we provide an extensive computational study of the automerization barrier (defined as the difference between the square and rectangular ground-state energies) and the vertical excitation energies at $D_{2h}$ and $D_{4h}$ equilibrium structures.
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