Recently, parameterization of the two-electron reduced density matrix (2-RDM) has made possible the determination of electronic energies with greater accuracy and lower cost than traditional electron-pair theories including coupled cluster with single and double excitations [D. A. Mazziotti, Phys. Rev. Lett. 101, 253002 (2008)]. We examine the methods performance for strongly correlated barriers to rotation; in particular, we study two distinct pathways in the isomerization of diazene (N 2H 2) from cis to trans: (i) a strongly correlated rotational pathway and (ii) a moderately correlated inversion pathway. While single reference wavefunction methods predict that the rotational barrier is higher than the inversional barrier, the parametric 2-RDM method predicts that the rotational barrier is lower than the inversional barrier by 3.1 kcal/mol in the extrapolated basis set limit. The parametric 2-RDM results are in agreement with those from multireference methods including multireference perturbation theory and the solution to the anti-Hermitian contracted Schrdinger equation. We report energies, optimized structures, and natural orbital occupation numbers for three diazene minima and two transition states.
Bibliographical noteFunding Information:
D.A.M. gratefully acknowledges the NSF, the ARO, the Henry-Camille Dreyfus Foundation, the David-Lucile Packard Foundation, and the Microsoft Corporation for their support.
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