Perturbative triples correction to domain-based local pair natural orbital variants of Mukherjee's state specific coupled cluster method

Lang, Jakub; Brabec, Jiří; Saitow, Masaaki; Pittner, Jiřı́; Neese, Frank; Demel, Ondřej

doi:10.1039/c8cp03577f

Cited by 13 publications

(14 citation statements)

References 130 publications

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“…Our final example is the TME moleculea paradigm system for multireference methods trying to correctly balance both dynamic and static correlation. − The first challenge stems from disjoint biradical character of TMEtwo radical electrons localize on spatially separated parts of the molecule and the resulting frontier orbitals interact weakly and are nearly degenerate. The second challenge is due to the fact that the molecule may rotate about its central C–C bond and the multireference character of the singlet state is changing along this rotation.…”

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confidence: 99%

Capturing the Dynamic Correlation for Arbitrary Spin-Symmetry CASSCF Reference with Adiabatic Connection Approaches: Insights into the Electronic Structure of the Tetramethyleneethane Diradical

Pastorczak

Hapka

Veis

et al. 2019

J. Phys. Chem. Lett.

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The recently proposed approach to multireference dynamic correlation energy based on the adiabatic connection (AC) is extended to an arbitrary spin symmetry of the reference state. We show that both the spin-free AC approach and its computationally inexpensive approximation, AC0, when combined with a complete active space wave function, constitute viable alternatives to the perturbation-based and density-functional-based multiconfiguration methods. In particular, the AC0 approach, thanks to its favorable scaling with the system size and the size of the active space, allows for treating larger systems than its perturbation-based counterparts while maintaining comparable accuracy. We show the method’s robustness on illustrative chemical systems, including the elusive tetramethyleneethane (TME) diradical, potential energy surfaces of which present a challenge to most computational approaches. For the latter system, AC0 outperforms other methods, staying in close agreement with the full configuration interaction quantum Monte Carlo benchmark. A careful analysis of the contributions to the correlation energy of TME’s lowest singlet and triplet states reveals the subtle interplay of the dynamic and static correlation as the key to understanding the shape of the diradical’s potential energy surfaces.

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confidence: 99%

Capturing the Dynamic Correlation for Arbitrary Spin-Symmetry CASSCF Reference with Adiabatic Connection Approaches: Insights into the Electronic Structure of the Tetramethyleneethane Diradical

Pastorczak

Hapka

Veis

et al. 2019

J. Phys. Chem. Lett.

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“…The latter can be accounted as an “accessible version” of the “golden standard”. Finally, we performed a few benchmark calculations with a computationally expensive DLPNO–MR–CCSD approach (DLPNO–MkCCSD in the notation of developers [ 78 , 79 , 80 , 81 ]). All these calculations were performed as single-points on PBE-optimized molecular geometries ( Figure 2 ).…”

Section: Methodsmentioning

confidence: 99%

The Adsorption of Small Molecules on the Copper Paddle-Wheel: Influence of the Multi-Reference Ground State

2022

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We report a theoretical study of the adsorption of a set of small molecules (C2H2, CO, CO2, O2, H2O, CH3OH, C2H5OH) on the metal centers of the “copper paddle-wheel”—a key structural motif of many MOFs. A systematic comparison between DFT of different rungs, single-reference post-HF methods (MP2, SOS–MP2, MP3, DLPNO–CCSD(T)), and multi-reference approaches (CASSCF, DCD–CAS(2), NEVPT2) is performed in order to find a methodology that correctly describes the complicated electronic structure of paddle-wheel structure together with a reasonable description of non-covalent interactions. Apart from comparison with literature data (experimental values wherever possible), benchmark calculations with DLPNO–MR–CCSD were also performed. Despite tested methods show qualitative agreement in the majority of cases, we showed and discussed reasons for quantitative differences as well as more fundamental problems of specific cases.

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“…Nowadays, the PNO-based approaches are developed in number of groups including Werner [87][88][89][90] and Hättig [91][92][93] and widely applied to various systems of chemical interest [94][95][96][97][98][99][100][101][102][103] . Apart from single-reference methods, the LPNO and DLPNO methodologies were also successfully applied to multireference CC techniques [104][105][106][107]…”

Section: Introductionmentioning

confidence: 99%

Near-Linear Scaling in DMRG-Based Tailored Coupled Clusters: An Implementation of DLPNO-TCCSD and DLPNO-TCCSD(T)

Lang

Antalík

Veis

et al. 2020

J. Chem. Theory Comput.

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We present a new implementation of density matrix renormalization group based tailored coupled clusters method (TCCSD), which employs the domain-based local pair natural orbital approach (DLPNO). Compared to the previous local pair natural orbital (LPNO) version of the method, the new implementation is more accurate, offers more favorable scaling, and provides more consistent behavior across the variety of systems. On top of the singles and doubles, we include the perturbative triples correction (T), which is able to retrieve even more dynamic correlation. The methods were tested on three systems: tetramethyleneethane, oxo-Mn(Salen), and iron(II)–porphyrin model. The first two were revisited to assess the performance with respect to LPNO-TCCSD. For oxo-Mn(Salen), we retrieved between 99.8 and 99.9% of the total canonical correlation energy which is an improvement of 0.2% over the LPNO version in less than 63% of the total LPNO runtime. Similar results were obtained for iron(II)–porphyrin. When the perturbative triples correction was employed, irrespective of the active space size or system, the obtained energy differences between two spin states were within the chemical accuracy of 1 kcal/mol using the default DLPNO settings.

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Perturbative triples correction to domain-based local pair natural orbital variants of Mukherjee's state specific coupled cluster method

Abstract: In this article we report an implementation of the perturbative triples correction to Mukherjee's state-specific multireference coupled cluster method based on the domain-based pair natural orbital approach (DLPNO-MkCC).

Cited by 13 publications

References 130 publications

Capturing the Dynamic Correlation for Arbitrary Spin-Symmetry CASSCF Reference with Adiabatic Connection Approaches: Insights into the Electronic Structure of the Tetramethyleneethane Diradical

Capturing the Dynamic Correlation for Arbitrary Spin-Symmetry CASSCF Reference with Adiabatic Connection Approaches: Insights into the Electronic Structure of the Tetramethyleneethane Diradical

The Adsorption of Small Molecules on the Copper Paddle-Wheel: Influence of the Multi-Reference Ground State

Near-Linear Scaling in DMRG-Based Tailored Coupled Clusters: An Implementation of DLPNO-TCCSD and DLPNO-TCCSD(T)

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