Addressing the System-Size Dependence of the Local Approximation Error in Coupled-Cluster Calculations

Altun, Ahmet; Ghosh, Soumen; Riplinger, Christoph; Neese, Frank; Bistoni, Giovanni

doi:10.1021/acs.jpca.1c09106

Cited by 26 publications

(37 citation statements)

References 93 publications

(143 reference statements)

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“…They showed that this method also decreases the system size dependence of the DLPNO error. 88 We performed two-point extrapolation of the correlation energies, E x and E y , calculated with different T CutPNO thresholds, T CutPNO 1.0 × 10 – x and 1.0 × 10 – y , respectively, according to the following equation: 77 where E ∞ is the correlation energy at the CPS limit and β is a constant. β can be integrated in a parameter F that also depends on the T CutPNO thresholds as follows: and therefore eq 5 can be written as …”

Section: Methodsmentioning

confidence: 99%

Reconciling Local Coupled Cluster with Multireference Approaches for Transition Metal Spin-State Energetics

Δρόσου

Mitsopoulou

Pantazis

2022

J. Chem. Theory Comput.

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Spin-state energetics of transition metal complexes remain one of the most challenging targets for electronic structure methods. Among single-reference wave function approaches, local correlation approximations to coupled cluster theory, most notably the domain-based local pair natural orbital (DLPNO) approach, hold the promise of bringing the accuracy of coupled cluster theory with single, double, and perturbative triple excitations, CCSD(T), to molecular systems of realistic size with acceptable computational cost. However, recent studies on spin-state energetics of iron-containing systems raised doubts about the ability of the DLPNO approach to adequately and systematically approximate energetics obtained by the reference-quality complete active space second-order perturbation theory with coupled-cluster semicore correlation, CASPT2/CC. Here, we revisit this problem using a diverse set of iron complexes and examine several aspects of the application of the DLPNO approach. We show that DLPNO-CCSD(T) can accurately reproduce both CASPT2/CC and canonical CCSD(T) results if two basic principles are followed. These include the consistent use of the improved iterative (T 1 ) versus the semicanonical perturbative triple corrections and, most importantly, a simple two-point extrapolation to the PNO space limit. The latter practically eliminates errors arising from the default truncation of electron-pair correlation spaces and should be viewed as standard practice in applications of the method to transition metal spin-state energetics. Our results show that reference-quality results can be readily achieved with DLPNO-CCSD(T) if these principles are followed. This is important also in view of the applicability of the method to larger single-reference systems and multinuclear clusters, whose treatment of dynamic correlation would be challenging for multireference-based approaches.

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Section: Methodsmentioning

confidence: 99%

Reconciling Local Coupled Cluster with Multireference Approaches for Transition Metal Spin-State Energetics

Δρόσου

Mitsopoulou

Pantazis

2022

J. Chem. Theory Comput.

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“…PM6, ωB97X-D/6-31+G(d,p), ωB97X-D/6-31++G(d,p), and DLPNO-CCSD(T)/aug-cc-pVTZ calculations were employed for the geometry optimization or single-point energy calculations within the multistep sampling scheme. Several studies have shown that the DLPNO-CCSD(T)/aug-cc-pVTZ//ωB97X-D/6-31++G(d,p) level of theory shows excellent performance for investigating the Δ G values of atmospheric molecular clusters. − The ORCA 4.0.0 program was employed to perform the DLPNO-CCSD(T)/aug-cc-pVTZ calculation, where tight SCF and PNO convergence criteria were adopted. The other calculations were performed within the Gaussian 09 program .…”

Section: Computational Detailsmentioning

confidence: 99%

Amine-Enhanced Methanesulfonic Acid-Driven Nucleation: Predictive Model and Cluster Formation Mechanism

Liu

Xie

et al. 2022

Environ. Sci. Technol.

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Atmospheric amines are considered to be an effective enhancer for methanesulfonic acid (MSA)-driven nucleation. However, out of the 195 detected atmospheric amines, the enhancing potential (EP) has so far only been studied for five amines. This severely hinders the understanding of the contribution of amines to MSA-driven nucleation. Herein, a two-step procedure was employed to probe the EP of various amines on MSA-driven nucleation. Initially, the formation free energies (ΔG) of 50 MSA-amine dimer clusters were calculated. Based on the calculated ΔG values, a robust quantitative structure–activity relationship (QSAR) model was built and utilized to predict the ΔG values of the remaining 145 amines. The QSAR model identified two guanidino-containing compounds as the potentially strongest enhancer for MSA-driven nucleation. Second, the EP of guanidino-containing compounds was studied by employing larger clusters and selecting guanidine (Gud) as a representative. The results indicate that Gud indeed has the strongest EP. The Gud–MSA system presents a unique clustering mechanism, proceeding via the initial formation of the (Gud)1(MSA)1 cluster, and subsequently by cluster collisions with either a (Gud)1(MSA)1 or (Gud)2(MSA)2 cluster. The developed QSAR model and the identification of amines with the strongest EP provide a foundation for comprehensively evaluating the contribution of atmospheric amines to MSA-driven nucleation.

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“…CPS(6/7) extrapolation has been shown 74 to provide sub-kJ/mol accuracy on the most challenging subsets of the GMTKN55 superset, 30 and it retains essentially canonical CCSD(T) accuracy also for large systems. 131 For the IB8, TA13, and CARB10 sets, the MAE associated with the DLPNO-CCSD(T)/CPS(6/7)/CBS(3/4) results (with respect to the canonical CCSD(T)/CBS benchmark data described above) is only 0.11, 0.08, and 0.04 kcal/mol, respectively. For the TTF-TCNQ pair, the present DLPNO-CCSD(T)/CPS(6/7)/CBS(3/4) interaction energies (see the TTF-TCNQ-DLPNO sheet in the Supporting Information ) were used as the benchmark energies.…”

Section: Computational Detailsmentioning

confidence: 92%

Open-Shell Variant of the London Dispersion-Corrected Hartree–Fock Method (HFLD) for the Quantification and Analysis of Noncovalent Interaction Energies

Altun

Neese

Bistoni

2022

J. Chem. Theory Comput.

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The London dispersion (LD)-corrected Hartree–Fock (HF) method (HFLD) is an ab initio approach for the quantification and analysis of noncovalent interactions (NCIs) in large systems that is based on the domain-based local pair natural orbital coupled-cluster (DLPNO-CC) theory. In the original HFLD paper, we discussed the implementation, accuracy, and efficiency of its closed-shell variant. Herein, an extension of this method to open-shell molecular systems is presented. Its accuracy is tested on challenging benchmark sets for NCIs, using CCSD(T) energies at the estimated complete basis set limit as reference. The HFLD scheme was found to be as accurate as the best-performing dispersion-corrected exchange-correlation functionals, while being nonempirical and equally efficient. In addition, it can be combined with the well-established local energy decomposition (LED) for the analysis of NCIs, thus yielding additional physical insights.

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Addressing the System-Size Dependence of the Local Approximation Error in Coupled-Cluster Calculations

Cited by 26 publications

References 93 publications

Reconciling Local Coupled Cluster with Multireference Approaches for Transition Metal Spin-State Energetics

Reconciling Local Coupled Cluster with Multireference Approaches for Transition Metal Spin-State Energetics

Amine-Enhanced Methanesulfonic Acid-Driven Nucleation: Predictive Model and Cluster Formation Mechanism

Open-Shell Variant of the London Dispersion-Corrected Hartree–Fock Method (HFLD) for the Quantification and Analysis of Noncovalent Interaction Energies

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