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Communication: Multireference equation of motion coupled cluster: A transform and diagonalize approach to electronic structure

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Neese,  Frank
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Citation

Nooijen, M., Demel, O., Datta, D., Kong, L., Shamasundar, K. R., Lotrich, V., et al. (2014). Communication: Multireference equation of motion coupled cluster: A transform and diagonalize approach to electronic structure. The Journal of Chemical Physics, 140(8): 081102. doi:10.1063/1.4866795.


Cite as: http://hdl.handle.net/21.11116/0000-0007-A3A0-B
Abstract
The novel multireference equation-of-motion coupled-cluster (MREOM-CC) approaches provide versatile and accurate access to a large number of electronic states. The methods proceed by a sequence of many-body similarity transformations and a subsequent diagonalization of the transformed Hamiltonian over a compact subspace. The transformed Hamiltonian is a connected entity and preserves spin- and spatial symmetry properties of the original Hamiltonian, but is no longer Hermitean. The final diagonalization spaces are defined in terms of a complete active space (CAS) and limited excitations (1h, 1p, 2h, …) out of the CAS. The methods are invariant to rotations of orbitals within their respective subspaces (inactive, active, external). Applications to first row transition metal atoms (Cr, Mn, and Fe) are presented yielding results for up to 524 electronic states (for Cr) with an rms error compared to experiment of about 0.05 eV. The accuracy of the MREOM family of methods is closely related to its favorable extensivity properties as illustrated by calculations on the O2–O2 dimer. The computational costs of the transformation steps in MREOM are comparable to those of closed-shell Coupled Cluster Singles and Doubles (CCSD) approach.