Similarity transformed equation-of-motion coupled-cluster theory: Details, examples, and comparisons

Nooijen, Marcel; Bartlett, Rodney J.

doi:10.1063/1.474922

Cited by 336 publications

(295 citation statements)

References 68 publications

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“…This aspect is the reason one can solve the non-linear equations defining the S-amplitudes by using a stable diagonalization procedure instead [49]. In DIP-STEOM one diagonalizes over 2h configurations, while in DEA-STEOM one diagonalizes over 2p determinants.…”

Section: Theorymentioning

confidence: 99%

“…This implies it is size-intensive, such that excitation energies on a chromophore are unaffected by a distant fragment. Moreover STEOM satisfies charge transfer separability, meaning that it follows the proper limit of 1 IP EA R + − for a separated particle-hole pair excitation [49]. This property is violated by EOM-CCSD, and this likely affects the accuracy of the EOM-CC approach for valence excitations.…”

Section: Introductionmentioning

confidence: 99%

“…Currently, canonical orbital based EOM-CC and CCLRT approaches are still the state of the art, and these methods are computationally demanding. One of the authors has long advocated a somewhat different approach to excited states: the Similarity Transformed Equation of Motion Coupled Cluster (STEOM-CC) method [47][48][49][50]. This method was developed in the late 1990's and its design was strongly influenced by the work on Fock Space Coupled Cluster (FSCC) Theory [51][52][53][54][55][56][57], in particular by the beautiful paper by Leszek Stolarczyk and Henk Monkhorst on their version of Fock Space Coupled Cluster [58], which was based on the use of similarity transformations in second quantization (or Fock space).…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Similarity transformed equation of motion coupled cluster theory revisited: a benchmark study of valence excited states

2013

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The Similarity Transformed Equation of Motion Coupled Cluster (STEOM-CC) method is benchmarked against CC3 and EOM-CCSDT-3 for a large test set of valence excited states of organic molecules studied by Schreiber et al. [M. Schreiber, M.R. Silva-Junior, S.P. Sauer, and W. Thiel, J. Chem. Phys. 128, 134110 (2008)]. STEOM-CC is found to behave quite satisfactorily and provides significant improvement over EOM-CCSD, CASPT2, and NEVPT2 for singlet excited states; lowering standard deviations of these methods by almost a factor of two. Triplet excited states are found to be described less accurately, however. Besides the parent version of STEOM-CC additional variations are considered. STEOM-D includes a perturbative correction from doubly excited determinants. The novel STEOM-H ( ) approach presents a sophisticated technique to render the STEOM-CC transformed Hamiltonian hermitian. In STEOM-PT the expensive CCSD step is replaced by MBPT(2), while Extended STEOM (EXT-STEOM) provides access to doubly excited states. To study orbital invariance in STEOM, we investigate orbital rotation in the STEOM-ORB approach.Comparison of theses variations of STEOM for the large test set provides a comprehensive statistical basis to gauge the usefulness of these approaches.

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Section: Theorymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Similarity transformed equation of motion coupled cluster theory revisited: a benchmark study of valence excited states

2013

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“…The standard routes to circumvent this are either to compute increasingly higher-order corrections (such as through the explicit inclusion of triple and higher excitations), or make use of a multi-determinant a) Electronic mail: knowlespj@cardiff.ac.uk. reference wavefunction from the outset, although other approaches to the treatment of non-dynamical correlation have been proposed, such as the active-space CC methods of HeadGordon, [21][22][23] and the spin-flip 24,25 and double-ionizationpotential 26,27 Equation of Motion (EOM) methods.…”

Section: Introductionmentioning

confidence: 99%

Quasi-variational coupled cluster theory

Robinson

Knowles

2012

The Journal of Chemical Physics

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Interaction-induced dipoles of hydrogen molecules colliding with helium atoms: A new ab initio dipole surface for high-temperature applications JCP: BioChem. Phys. 6, 01B616 (2012) Interaction-induced dipoles of hydrogen molecules colliding with helium atoms: A new ab initio dipole surface for high-temperature applications J. Chem. Phys. 136, 044320 (2012) A theoretical study of the CX2N radicals (X = F, Cl, Br): The effect of halogen substitution on structure, isomerization, and energetics J. Chem. Phys. 136, 044316 (2012) Molecular properties via a subsystem density functional theory formulation: A common framework for electronic embedding J. Chem. Phys. 136, 044104 (2012) Statistical thermodynamics of 1-butanol, 2-methyl-1-propanol, and butanal J. Chem. Phys. 136, 034306 (2012) Additional information on J. Chem. Phys. We extend our previous work on the construction of new approximations of the variational coupled cluster method. By combining several linked pair functional transformations in such a way as to give appropriately balanced infinite-order contributions, in order to approximate eT †Ĥ eT L well at all orders, we formulate a new quantum chemical method, which we name quasi-variational coupled cluster. We demonstrate this method to be particularly robust in the regime of strong static electron correlation, improving significantly on our earlier approximate variational coupled cluster approach.

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“…However, the corresponding equations for two particle attached/removed have seen very few applications in quantum chemistry [32,33] and are new in nuclear physics. In this article, we will thus extend the range of the EOM-CC methods to include open-shell nuclei with A = ±2 nucleons outside a closed shell core.…”

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confidence: 99%

Toward open-shell nuclei with coupled-cluster theory

et al. 2011

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We develop a new method based on equation-of-motion coupled-cluster theory to describe properties of open-shell nuclei with A ± 2 nucleons outside a closed shell. We perform proof-of-principle calculations for the ground states of the helium isotopes 3−6 He and the first excited 2 + state in 6 He. The comparison with exact results from matrix diagonalization in small model spaces demonstrates the accuracy of the coupled-cluster methods. Three-particle-one-hole excitations of 4 He play an important role for the accurate description of 6 He. For the open-shell nucleus 6 He, the computational cost of the method is comparable with the coupled-cluster singles-and-doubles approximation while its accuracy is similar to coupled-cluster with singles, doubles and triples excitations.

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Similarity transformed equation-of-motion coupled-cluster theory: Details, examples, and comparisons

Cited by 336 publications

References 68 publications

Similarity transformed equation of motion coupled cluster theory revisited: a benchmark study of valence excited states

Similarity transformed equation of motion coupled cluster theory revisited: a benchmark study of valence excited states

Quasi-variational coupled cluster theory

Toward open-shell nuclei with coupled-cluster theory

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