2014
DOI: 10.1063/1.4890117
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Accurate prediction of diradical chemistry from a single-reference density-matrix method: Model application to the bicyclobutane to gauche-1,3-butadiene isomerization

Abstract: Multireference correlation in diradical molecules can be captured by a single-reference 2-electron reduced-density-matrix (2-RDM) calculation with only single and double excitations in the 2-RDM parametrization. The 2-RDM parametrization is determined by N-representability conditions that are non-perturbative in their treatment of the electron correlation. Conventional single-reference wave function methods cannot describe the entanglement within diradical molecules without employing triple- and potentially ev… Show more

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Cited by 3 publications
(1 citation statement)
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“…The p2-RDM method has been previously applied to similar systems that cannot be well-described by singlereference methods, including the prediction of the transition state energy between the cis-and trans-isomers of diazene, 25 the determination of the relative stability of the cage and prism isomers of the water hexamer, 33 the prediction of the energies of the diradical isomers of olympicene, 26 and the computation of the diradical disrotatory transition state in the conversion of gauche-1,3butadiene to bicyclobutane. 34 In each of these cases, the p2-RDM method was seen to return energies and molecular structures comparable to those obtained from multireference methods.…”
Section: Introductionmentioning
confidence: 72%
“…The p2-RDM method has been previously applied to similar systems that cannot be well-described by singlereference methods, including the prediction of the transition state energy between the cis-and trans-isomers of diazene, 25 the determination of the relative stability of the cage and prism isomers of the water hexamer, 33 the prediction of the energies of the diradical isomers of olympicene, 26 and the computation of the diradical disrotatory transition state in the conversion of gauche-1,3butadiene to bicyclobutane. 34 In each of these cases, the p2-RDM method was seen to return energies and molecular structures comparable to those obtained from multireference methods.…”
Section: Introductionmentioning
confidence: 72%