S66x8 noncovalent interactions revisited: new benchmark and performance of composite localized coupled-cluster methods

Santra, Golokesh; Semidalas, Emmanouil; Mehta, Nisha; Karton, Amir; Martin, Jan M. L.

doi:10.1039/d2cp03938a

Cited by 28 publications

(31 citation statements)

References 112 publications

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“…With a MAD of 0.10 kcal/mol, the low-cost three-tier composite scheme, (T 0 )TightPNO/AVQZ + 0.61[(T 0 )TightPNO/AVQZ – (T 0 )TightPNO/AVTZ] + 3.33[(T 1 )TightPNO/AVTZ – (T 0 )TightPNO/AVTZ], is only marginally better than standard DLPNO-CCSD(T 0 , TightPNO)/AVQZ and DLPNO-CCSD(T 1 , TightPNO)/AVQZ. For a specific accuracy threshold and basis set combination, performance of DLPNO-CCSD(T 0 ) and DLPNO-CCSD(T 1 ) is comparable to each other, which is not surprising because none of the conformers of the ACONFL set has significant type A static correlation Employing our previously proposed composite schemes does not offer any advantage over the standard localized orbital methods. …”

Section: Discussionmentioning

confidence: 79%

“…71,72,79 The first three functionals were the best performers in the GMTKN55 general main-group thermochemistry, kinetics, and noncovalent interactions, 55 problem types 37 ) benchmark, 68 while dispersion-corrected dRPA-based functionals performed remarkably well for S66 and S66x8 noncovalent interactions. 50,80 The mean absolute error of the widely used molecular mechanics FFs, UFF 81 and MMFF94, 82,83 was marginally reduced from 2.91 and 3.41 to 2.87 and 3.37 kcal/mol, respectively. Considering the fact that the average conformer energy of ACONFL is 4.56 kcal/mol, these errors remain unacceptable.…”

Section: The Journal Of Physical Chemistrymentioning

confidence: 95%

“…The RMSD, MAD, and MSD statistics of these methods for ACONFL are listed in Table S6 . While using the coefficients from ref ( 50 ), none of the composite schemes outperformed their respective standard methods. On the other hand, optimizing the coefficients of the localized orbital composite methods with respect to the revised ACONFL reference data significantly improved their performance.…”

Section: Introductionmentioning

confidence: 95%

“…Hence, to save us time, we have extracted the conformer energies from the Supporting Information of ref , spliced in our new reference data, and compared the statistics of different DFT, SQM, and FF methods (see the Excel workbook in the Supporting Information). On top of that, we have considered a few additional double hybrid functionals, for example, revDSD-PBEP86-D3BJ, revDSD-PBEP86-D4, ωB97M(2), and dRPA-based fifth rung functionals. ,, The first three functionals were the best performers in the GMTKN55 general main-group thermochemistry, kinetics, and noncovalent interactions, 55 problem types) benchmark, while dispersion-corrected dRPA-based functionals performed remarkably well for S66 and S66x8 noncovalent interactions. , …”

Section: Introductionmentioning

confidence: 99%

“…Additionally, we also considered benchmarking the LNO-, PNO-, and DLPNO-based composite methods optimized for the counterpoise uncorrected (or “raw”) S66x8 noncovalent interactions (see ref ( 50 ) for further details). The RMSD, MAD, and MSD statistics of these methods for ACONFL are listed in Table S6 .…”

Section: Introductionmentioning

confidence: 99%

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Performance of Localized-Orbital Coupled-Cluster Approaches for the Conformational Energies of Longer n-Alkane Chains

Santra

Martin

2022

J. Phys. Chem. A

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We report an update and enhancement of the ACONFL (conformer energies of large alkanes [J. Phys. Chem. A2022,126, 3521−3535]) dataset. For the ACONF12 (ndodecane) subset, we report basis set limit canonical coupledcluster with singles, doubles, and perturbative triples [i.e., CCSD(T)] reference data obtained from the MP2-F12/cc-pV{T,Q}Z-F12 extrapolation, [CCSD(F12*)-MP2-F12]/aug-cc-pVTZ-F12, and a (T) correction from conventional CCSD(T)/ aug-cc-pV{D,T}Z calculations. Then, we explored the performance of a variety of single and composite localized-orbital CCSD(T) approximations, ultimately finding an affordable localized natural orbital CCSD(T) [LNO-CCSD(T)]-based post-MP2 correction that agrees to 0.006 kcal/mol mean absolute deviation with the revised canonical reference data. In tandem with canonical MP2-F12 complete basis set extrapolation, this was then used to reevaluate the ACONF16 and ACONF20 subsets for n-hexadecane and n-icosane, respectively. Combining those with the revised canonical reference data for the dodecane conformers (i.e., ACONF12 subset), a revised ACONFL set was obtained. It was then used to assess the performance of different localized-orbital coupled-cluster approaches, such as pair natural orbital localized CCSD(T) [PNO-LCCSD(T)] as implemented in MOLPRO, DLPNO-CCSD(T 0 ) and DLPNO-CCSD(T 1 ) as implemented in ORCA, and LNO-CCSD(T) as implemented in MRCC, at their respective "Normal", "Tight", "vTight", and "vvTight" accuracy settings. For a given accuracy threshold and basis set, DLPNO-CCSD(T 1 ) and DLPNO-CCSD(T 0 ) perform comparably. With "VeryTightPNO" cutoffs, explicitly correlated DLPNO-CCSD(T 1 )-F12/VDZ-F12 is the best pick among all the DLPNO-based methods tested. To isolate basis set incompleteness from localized-orbital-related truncation errors (domain, LNOs), we have also compared the localized coupled-cluster approaches with canonical DF-CCSD(T)/aug-cc-pVTZ for the ACONF12 set. We found that gradually tightening the cutoffs improves the performance of LNO-CCSD(T), and using a composite scheme such as vTight + 0.50[vTight − Tight] improves things further. For DLPNO-CCSD(T 1 ), "TightPNO" and "VeryTightPNO" offer a statistically similar accuracy, which gets slightly better when T CutPNO is extrapolated to the complete PNO space limit. Similar to Brauer et al.'s [Phys. Chem. Chem. Phys.2016,18 (31), 20905−20925] previous report for the S66x8 noncovalent interactions, the dispersioncorrected direct random phase approximation (dRPA)-based double hybrids perform remarkably well for the ACONFL set. While the revised reference data do not affect any conclusions on the less accurate methods, they may upend orderings for more accurate methods with error statistics on the same order as the difference between reference datasets.

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Section: Discussionmentioning

confidence: 79%

Section: The Journal Of Physical Chemistrymentioning

confidence: 95%

Section: Introductionmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Performance of Localized-Orbital Coupled-Cluster Approaches for the Conformational Energies of Longer n-Alkane Chains

Santra

Martin

2022

J. Phys. Chem. A

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How do spin‐scaled double hybrids designed for excitation energies perform for noncovalent excited‐state interactions? An investigation on aromatic excimer models

Hancock,

Giudici,

Goerigk

2024

J Comput Chem

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Time‐dependent double hybrids with spin‐component or spin‐opposite scaling to their second‐order perturbative correlation correction have demonstrated competitive robustness in the computation of electronic excitation energies. Some of the most robust are those recently published by our group (M. Casanova‐Páez, L. Goerigk, J. Chem. Theory Comput. 2021, 20, 5165). So far, the implementation of these functionals has not allowed correctly calculating their ground‐state total energies. Herein, we define their correct spin‐scaled ground‐state energy expressions which enables us to test our methods on the noncovalent excited‐state interaction energies of four aromatic excimers. A range of 22 double hybrids with and without spin scaling are compared to the reasonably accurate wavefunction reference from our previous work (A. C. Hancock, L. Goerigk, RSC Adv. 2023, 13, 35964). The impact of spin scaling is highly dependent on the underlying functional expression, however, the smallest overall errors belong to spin‐scaled functionals with range separation: SCS‐ and SOS‐PBEPP86, and SCS‐RSX‐QIDH. We additionally determine parameters for DFT‐D3(BJ)/D4 ground‐state dispersion corrections of these functionals, which reduce errors in most cases. We highlight the necessity of dispersion corrections for even the most robust TD‐DFT methods but also point out that ground‐state based corrections are insufficient to completely capture dispersion effects for excited‐state interaction energies.

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Benchmark Accuracy in Thermochemistry, Kinetics, and Noncovalent Interactions

Karton

2024

Comprehensive Computational Chemistry

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S66x8 noncovalent interactions revisited: new benchmark and performance of composite localized coupled-cluster methods

Abstract: The S66x8 noncovalent interactions benchmark has been re-evaluated at the “sterling silver” level, using explicitly correlated MP2-F12 near the complete basis set limit, CCSD(F12*)/aug-cc-pVTZ-F12, and a (T) correction from conventional...

Cited by 28 publications

References 112 publications

Performance of Localized-Orbital Coupled-Cluster Approaches for the Conformational Energies of Longer n-Alkane Chains

Performance of Localized-Orbital Coupled-Cluster Approaches for the Conformational Energies of Longer n-Alkane Chains

How do spin‐scaled double hybrids designed for excitation energies perform for noncovalent excited‐state interactions? An investigation on aromatic excimer models

Benchmark Accuracy in Thermochemistry, Kinetics, and Noncovalent Interactions

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