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Issue 5, 2012
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Photoexcited tautomerization of vinyl alcohol to acetylaldehydevia a conical intersection from contracted Schrödinger theory

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Abstract

The photoexcited tautomerization of vinyl alcohol to acetylaldehydevia a conical intersection is analyzed through the direct calculation of two-electron reduced density matrices (2-RDMs) from solutions to the anti-Hermitian contracted Schrödinger equation (ACSE). The study utilizes the recent generalization of the ACSE method for the treatment of excited states [G. Gidofalvi and D. A. Mazziotti, Phys. Rev. A, 2009, 80, 022507]. We computed absolute energies of the critical points as well as various intermediate points along the ground- and excited-state potential energy surface of vinyl alcohol and acetylaldehyde. The ACSE, MCSCF, second-order multireference many-body perturbation theory (MRMP2), and various coupled cluster methods all demonstrate the existence of a family of pathways from vinyl alcohol to acetylaldehydevia a conical intersection that are monotonically decreasing in energy. The conical intersection, proposed for the first time in this paper, is both structurally and energetically similar to the ground-state transition state. We observe a relationship between conical intersections and transition states both in this paper and in our previous work on bicyclobutane's ring conical intersection [J. W. Snyder, Jr. and D. A. Mazziotti, J. Chem. Phys., 2011, 135, 024107]. To treat multireference correlation, we seeded the ACSE with an initial 2-RDM guess from a multiconfiguration self-consistent field (MCSCF) calculation. The ACSE recovers more single-reference correlation energy than MRMP2 and more multireference correlation energy than comparable single-reference wave function methods. The 2-RDMs from the ACSE nearly satisfy all necessary N-representability conditions.

Graphical abstract: Photoexcited tautomerization of vinyl alcohol to acetylaldehydevia a conical intersection from contracted Schrödinger theory

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Publication details

The article was received on 27 Sep 2011, accepted on 02 Dec 2011 and first published on 23 Dec 2011


Article type: Paper
DOI: 10.1039/C2CP23065H
Citation: Phys. Chem. Chem. Phys., 2012,14, 1660-1667
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    Photoexcited tautomerization of vinyl alcohol to acetylaldehydevia a conical intersection from contracted Schrödinger theory

    J. W. Snyder Jr. and D. A. Mazziotti, Phys. Chem. Chem. Phys., 2012, 14, 1660
    DOI: 10.1039/C2CP23065H

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