scholarly journals Noncovalent Interactions by QMC: Speedup by One-Particle Basis-Set Size Reduction

2016 ◽  
pp. 119-126
Author(s):  
Matúš Dubecký
Keyword(s):  
Noncovalent Interactions ◽  
Size Reduction ◽  
Basis Set ◽  
Set Size

Convergence of Breit–Pauli spin–orbit matrix elements with basis set size and configuration interaction space: The halogen atoms F, Cl, and Br

2000 ◽  
Vol 112 (13) ◽  
pp. 5624-5632 ◽  
Author(s):  
Andreas Nicklass ◽  
Kirk A. Peterson ◽  
Andreas Berning ◽  
Hans-Joachim Werner ◽  
Peter J. Knowles
Keyword(s):  
Configuration Interaction ◽  
Interaction Space ◽  
Basis Set ◽  
Spin Orbit ◽  
Matrix Elements ◽  
Set Size ◽  
Halogen Atoms

scholarly journals r2SCAN-3c: An Efficient “Swiss Army Knife” Composite Electronic-Structure Method

2020 ◽  
Author(s):  
Stefan Grimme ◽  
Andreas Hansen ◽  
Sebastian Ehlert ◽  
Jan-Michael Mewes
Keyword(s):  
Electronic Structure ◽  
Density Functional ◽  
Chemical Space ◽  
Noncovalent Interactions ◽  
New Method ◽  
Basis Set ◽  
Basis Set Superposition Error ◽  
Benchmark Database ◽  
The Cost ◽  
Conformational Energies

The recently proposed second revision of the SCAN meta-GGA density-functional approximation (DFA) {Furness et al., J. Phys. Chem. Lett. 2020, 11, 8208-8215, termed r<sup>2</sup>SCAN} is used to construct an efficient composite electronic-structure method termed r<sup>2</sup>SCAN-3c, expanding the "3c'' series (hybrid: HSE/PBEh-3c, GGA: B97-3c, HF: HF-3c) to themGGA level. To this end, the unaltered r<sup>2</sup>SCAN functional is combined with a tailor-made <br>triple-zeta Gaussian AO-basis as well as with refitted D4 and gCP corrections for London-dispersion and basis-set superposition error. The performance of the new method is evaluated for the GMTKN55 thermochemical database covering large parts of chemical space with about 1500 <br>data points, as well as additional benchmarks for noncovalent interactions, organometallic reactions, lattice energies of organic molecules and ices, as well as for the adsorption on polar salt and non-polar coinage-metal surfaces. These comprehensive tests reveal a spectacular performance and robustness of r<sup>2</sup>SCAN-3c for reaction energies and noncovalent interactions in molecular and periodic systems, as well as outstanding conformational energies, and consistent structures. At just one tenth of the cost, r<sup>2</sup>SCAN-3c provides one of the best results of all semi-local DFT/QZ methods ever tested for the GMTKN55 benchmark database. Specifically for reaction and conformational energies as well as for noncovalent interactions, the new method outperforms hybrid-DFT/QZ approaches, compared to which the computational savings are even larger (factor 100-1000).<br>In relation to other "3c'' methods, r<sup>2</sup>SCAN-3c by far surpasses the accuracy of its predecessor B97-3c at only about twice the cost. The perhaps most relevant remaining systematic deviation of r<sup>2</sup>SCAN-3c is due to self-interaction-error, owing to its mGGA nature. However, SIE is notably reduced compared to other (m)GGAs, as is demonstrated for several examples. After all, this remarkably efficient and robust method is chosen as our new group default, replacing previous low-level DFT and partially even expensive high-level methods in most standard applications for systems with up to several hundreds of atoms.<br><br>

scholarly journals r2SCAN-3c: An Efficient “Swiss Army Knife” Composite Electronic-Structure Method

2020 ◽  
Author(s):  
Stefan Grimme ◽  
Andreas Hansen ◽  
Sebastian Ehlert ◽  
Jan-Michael Mewes
Keyword(s):  
Electronic Structure ◽  
Density Functional ◽  
Chemical Space ◽  
Noncovalent Interactions ◽  
New Method ◽  
Basis Set ◽  
Basis Set Superposition Error ◽  
Benchmark Database ◽  
The Cost ◽  
Conformational Energies

The recently proposed second revision of the SCAN meta-GGA density-functional approximation (DFA) {Furness et al., J. Phys. Chem. Lett. 2020, 11, 8208-8215, termed r<sup>2</sup>SCAN} is used to construct an efficient composite electronic-structure method termed r<sup>2</sup>SCAN-3c, expanding the "3c'' series (hybrid: HSE/PBEh-3c, GGA: B97-3c, HF: HF-3c) to themGGA level. To this end, the unaltered r<sup>2</sup>SCAN functional is combined with a tailor-made <br>triple-zeta Gaussian AO-basis as well as with refitted D4 and gCP corrections for London-dispersion and basis-set superposition error. The performance of the new method is evaluated for the GMTKN55 thermochemical database covering large parts of chemical space with about 1500 <br>data points, as well as additional benchmarks for noncovalent interactions, organometallic reactions, lattice energies of organic molecules and ices, as well as for the adsorption on polar salt and non-polar coinage-metal surfaces. These comprehensive tests reveal a spectacular performance and robustness of r<sup>2</sup>SCAN-3c for reaction energies and noncovalent interactions in molecular and periodic systems, as well as outstanding conformational energies, and consistent structures. At just one tenth of the cost, r<sup>2</sup>SCAN-3c provides one of the best results of all semi-local DFT/QZ methods ever tested for the GMTKN55 benchmark database. Specifically for reaction and conformational energies as well as for noncovalent interactions, the new method outperforms hybrid-DFT/QZ approaches, compared to which the computational savings are even larger (factor 100-1000).<br>In relation to other "3c'' methods, r<sup>2</sup>SCAN-3c by far surpasses the accuracy of its predecessor B97-3c at only about twice the cost. The perhaps most relevant remaining systematic deviation of r<sup>2</sup>SCAN-3c is due to self-interaction-error, owing to its mGGA nature. However, SIE is notably reduced compared to other (m)GGAs, as is demonstrated for several examples. After all, this remarkably efficient and robust method is chosen as our new group default, replacing previous low-level DFT and partially even expensive high-level methods in most standard applications for systems with up to several hundreds of atoms.<br><br>

Selecting DFT methods for use in optimizations of enzyme active sites: applications to ONIOM treatments of DNA glycosylases

2013 ◽  
Vol 91 (7) ◽  
pp. 559-572 ◽  
Author(s):  
Jennifer L. Kellie ◽  
Stacey D. Wetmore
Keyword(s):  
Active Sites ◽  
Noncovalent Interactions ◽  
Single Point ◽  
Enzymatic Reaction ◽  
Basis Set ◽  
Basis Sets ◽  
Dna Glycosylases ◽  
Dft Methods ◽  
Primary Focus ◽  
High Level

When using a hybrid methodology to treat an enzymatic reaction, many factors contribute to selecting the method for the high-level region, which can be complicated by the presence of dispersion-driven interactions such as π–π stacking. In addition, the proper treatment of the reaction center often requires a large number of heavy atoms to be included in the high-level region, precluding the use of ab initio methods such as MP2 as well as large basis sets, in the optimization step. In the present work, popular DFT methods were tested to identify an appropriate functional for treating the high-level region in ONIOM optimizations of reactions catalyzed by nonmetalloenzymes. Eight different DFT methods (B3LYP, B97-2, MPW1K, MPWB1K, BB1K, B1B95, M06-2X, and ωB97X-D) in combination with four double-ζ quality Pople basis sets were tested for their ability to optimize noncovalent interactions (hydrogen bonding and π–π) and characterize reactions (proton transfer, SN2 hydrolysis, and unimolecular cleavage). Although the primary focus of this study is accurate structure determination, energetics were also examined at both the optimization level of theory, and with triple-ζ quality basis set and select (M06-2X or ωB97X-D) methods. If dispersion-driven interactions exist within the active site, then MPWB1K/6-31G(d,p) or M06-2X/6-31+G(d,p) are recommended for the optimization step with subsequent triple-ζ quality single-point energies. However, since dispersion-corrected functionals (M06-2X and ωB97X-D) generally require diffuse functions to yield appropriate geometries, the possible size of the high-level region is greatly limited with these methods. In contrast, if the model is large enough to recover steric constraints on π–π interactions, then B3LYP with a small basis set performs comparatively well for the optimization step and is significantly less computationally expensive. Interestingly, the functionals that afford the best geometries often do not yield the best energetics, which emphasizes the importance of structural benchmark studies.

Ab initio molecular orbital study of the effects of basis set size on the calculated structure and acidity of hydroxyl groups in framework molecular sieves

1992 ◽  
Vol 96 (25) ◽  
pp. 10247-10257 ◽  
Author(s):  
John B. Nicholas ◽  
Randall E. Winans ◽  
Robert J. Harrison ◽  
Lennox E. Iton ◽  
Larry A. Curtiss ◽  
...  
Keyword(s):  
Ab Initio ◽  
Molecular Orbital ◽  
Molecular Sieves ◽  
Basis Set ◽  
Hydroxyl Groups ◽  
Set Size ◽  
Molecular Orbital Study ◽  
Orbital Study

scholarly journals r2SCAN-3c: An Efficient “Swiss Army Knife” Composite Electronic-Structure Method

2020 ◽  
Author(s):  
Stefan Grimme ◽  
Andreas Hansen ◽  
Sebastian Ehlert ◽  
Jan-Michael Mewes
Keyword(s):  
Electronic Structure ◽  
Density Functional ◽  
Chemical Space ◽  
Noncovalent Interactions ◽  
New Method ◽  
Basis Set ◽  
Basis Set Superposition Error ◽  
Benchmark Database ◽  
The Cost ◽  
Conformational Energies

The recently proposed second revision of the SCAN meta-GGA density-functional approximation (DFA) {Furness et al., J. Phys. Chem. Lett. 2020, 11, 8208-8215, termed r<sup>2</sup>SCAN} is used to construct an efficient composite electronic-structure method termed r<sup>2</sup>SCAN-3c, expanding the "3c'' series (hybrid: HSE/PBEh-3c, GGA: B97-3c, HF: HF-3c) to themGGA level. To this end, the unaltered r<sup>2</sup>SCAN functional is combined with a tailor-made <br>triple-zeta Gaussian AO-basis as well as with refitted D4 and gCP corrections for London-dispersion and basis-set superposition error. The performance of the new method is evaluated for the GMTKN55 thermochemical database covering large parts of chemical space with about 1500 <br>data points, as well as additional benchmarks for noncovalent interactions, organometallic reactions, lattice energies of organic molecules and ices, as well as for the adsorption on polar salt and non-polar coinage-metal surfaces. These comprehensive tests reveal a spectacular performance and robustness of r<sup>2</sup>SCAN-3c for reaction energies and noncovalent interactions in molecular and periodic systems, as well as outstanding conformational energies, and consistent structures. At just one tenth of the cost, r<sup>2</sup>SCAN-3c provides one of the best results of all semi-local DFT/QZ methods ever tested for the GMTKN55 benchmark database. Specifically for reaction and conformational energies as well as for noncovalent interactions, the new method outperforms hybrid-DFT/QZ approaches, compared to which the computational savings are even larger (factor 100-1000).<br>In relation to other "3c'' methods, r<sup>2</sup>SCAN-3c by far surpasses the accuracy of its predecessor B97-3c at only about twice the cost. The perhaps most relevant remaining systematic deviation of r<sup>2</sup>SCAN-3c is due to self-interaction-error, owing to its mGGA nature. However, SIE is notably reduced compared to other (m)GGAs, as is demonstrated for several examples. After all, this remarkably efficient and robust method is chosen as our new group default, replacing previous low-level DFT and partially even expensive high-level methods in most standard applications for systems with up to several hundreds of atoms.<br><br>

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