Basis set superposition problem in interaction energy calculations with explicitly correlated bases: Saturated second‐ and third‐order energies for He2

1996 ◽  
Vol 104 (9) ◽  
pp. 3306-3319 ◽  
Author(s):  
Robert Bukowski ◽  
Bogumil/ Jeziorski ◽  
Krzysztof Szalewicz
Keyword(s):  
Interaction Energy ◽  
Basis Set ◽  
Third Order ◽  
Energy Calculations ◽  
Explicitly Correlated

About the overestimation of the basis set superposition error on interaction energy calculations for van der Waals systems

1986 ◽  
Vol 84 (9) ◽  
pp. 5077-5080 ◽  
Author(s):  
F. J. Olivares del Valle ◽  
S. Tolosa ◽  
J. J. Esperilla ◽  
E. A. Ojalvo ◽  
A. Requena
Keyword(s):  
Interaction Energy ◽  
Van Der Waals ◽  
Basis Set ◽  
Basis Set Superposition Error ◽  
Energy Calculations

Medium-Size Polarized Basis Sets Applicability for Interaction Energy Calculations: He2 and Be2 van der Waals Systems

1993 ◽  
Vol 58 (8) ◽  
pp. 1739-1750
Author(s):  
Andrzej Nowek
Keyword(s):  
Interaction Energy ◽  
Van Der Waals ◽  
Basis Set ◽  
Basis Sets ◽  
Medium Size ◽  
Dispersion Energy ◽  
Energy Calculations ◽  
Polarized Basis Sets ◽  
Standard Energy

Polarized bases set approach has been applied for preparation of medium-size contracted GTO basis sets starting from various standard energy-optimized and even-tempered isotropic atomic basis sets. Their usefulness for calculation of the SCF interaction energy and its components as well as dispersion energy consistently determined within the dimer basis set were studied for He2 and Be2 systems for intermediate internuclear separations. The results obtained with polarized basis sets indicate their good performance in comparison with property oriented ones.

Performance of Electronic Structure Methods for the Description of Hückel-Möbius Interconversions in Extended π-Systems

2019 ◽  
Author(s):  
Tatiana Woller ◽  
Ambar Banerjee ◽  
Nitai Sylvetsky ◽  
Xavier Deraet ◽  
Frank De Proft ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Basis Set ◽  
Dft Methods ◽  
Molecular Switching ◽  
Wide Range ◽  
Electronic Structure Methods ◽  
Explicitly Correlated ◽  
Relative Errors ◽  
The Stability ◽  
Basis Set Expansion

<p>Expanded porphyrins provide a versatile route to molecular switching devices due to their ability to shift between several π-conjugation topologies encoding distinct properties. Taking into account its size and huge conformational flexibility, DFT remains the workhorse for modeling such extended macrocycles. Nevertheless, the stability of Hückel and Möbius conformers depends on a complex interplay of different factors, such as hydrogen bonding, p···p stacking, steric effects, ring strain and electron delocalization. As a consequence, the selection of an exchange-correlation functional for describing the energy profile of topological switches is very difficult. For these reasons, we have examined the performance of a variety of wavefunction methods and density functionals for describing the thermochemistry and kinetics of topology interconversions across a wide range of macrocycles. Especially for hexa- and heptaphyrins, the Möbius structures have a pronouncedly stronger degree of static correlation than the Hückel and figure-eight structures, and as a result the relative energies of singly-twisted structures are a challenging test for electronic structure methods. Comparison of limited orbital space full CI calculations with CCSD(T) calculations within the same active spaces shows that post-CCSD(T) correlation contributions to relative energies are very minor. At the same time, relative energies are weakly sensitive to further basis set expansion, as proven by the minor energy differences between MP2/cc-pVDZ and explicitly correlated MP2-F12/cc-pVDZ-F12 calculations. Hence, our CCSD(T) reference values are reasonably well-converged in both 1-particle and n-particle spaces. While conventional MP2 and MP3 yield very poor results, SCS-MP2 and particularly SOS-MP2 and SCS-MP3 agree to better than 1 kcal mol<sup>-1</sup> with the CCSD(T) relative energies. Regarding DFT methods, only M06-2X provides relative errors close to chemical accuracy with a RMSD of 1.2 kcal mol<sup>-1</sup>. While the original DSD-PBEP86 double hybrid performs fairly poorly for these extended p-systems, the errors drop down to 2 kcal mol<sup>-1</sup> for the revised revDSD-PBEP86-NL, again showing that same-spin MP2-like correlation has a detrimental impact on performance like the SOS-MP2 results. </p>

SAMPL6 Octanol-Water Partition Coefficients from Alchemical Free Energy Calculations with MBIS Atomic Charges

2019 ◽  
Author(s):  
Maximiliano Riquelme ◽  
Esteban Vöhringer-Martinez
Keyword(s):  
Free Energy ◽  
Electron Density ◽  
Free Energy Calculations ◽  
Basis Set ◽  
Energetic Cost ◽  
Atomic Charges ◽  
Free Energies ◽  
Energy Calculations ◽  
Alchemical Free Energy ◽  
Alchemical Free Energy Calculations

In molecular modeling the description of the interactions between molecules forms the basis for a correct prediction of macroscopic observables. Here, we derive atomic charges from the implicitly polarized electron density of eleven molecules in the SAMPL6 challenge using the Hirshfeld-I and Minimal Basis Set Iterative Stockholder(MBIS) partitioning method. These atomic charges combined with other parameters in the GAFF force field and different water/octanol models were then used in alchemical free energy calculations to obtain hydration and solvation free energies, which after correction for the polarization cost, result in the blind prediction of the partition coefficient. From the tested partitioning methods and water models the S-MBIS atomic charges with the TIP3P water model presented the smallest deviation from the experiment. Conformational dependence of the free energies and the energetic cost associated with the polarization of the electron density are discussed.

scholarly journals The S66 Non-Covalent Interactions Benchmark Reconsidered Using Explicitly Correlated Methods Near the Basis Set Limit

2018 ◽  
Vol 71 (4) ◽  
pp. 238 ◽  
Author(s):  
Manoj K. Kesharwani ◽  
Amir Karton ◽  
Nitai Sylvetsky ◽  
Jan M. L. Martin
Keyword(s):  
Computational Cost ◽  
The Other ◽  
Basis Set ◽  
Basis Sets ◽  
Explicitly Correlated ◽  
Non Covalent Interactions ◽  
Explicitly Correlated Methods ◽  
The One ◽  
High Level ◽  
Covalent Interactions

The S66 benchmark for non-covalent interactions has been re-evaluated using explicitly correlated methods with basis sets near the one-particle basis set limit. It is found that post-MP2 ‘high-level corrections’ are treated adequately well using a combination of CCSD(F12*) with (aug-)cc-pVTZ-F12 basis sets on the one hand, and (T) extrapolated from conventional CCSD(T)/heavy-aug-cc-pV{D,T}Z on the other hand. Implications for earlier benchmarks on the larger S66×8 problem set in particular, and for accurate calculations on non-covalent interactions in general, are discussed. At a slight cost in accuracy, (T) can be considerably accelerated by using sano-V{D,T}Z+ basis sets, whereas half-counterpoise CCSD(F12*)(T)/cc-pVDZ-F12 offers the best compromise between accuracy and computational cost.

Atomic and molecular correlation energies with explicitly correlated Gaussian geminals. II. Perturbation treatment through third order for He, Be, H2, and LiH

1983 ◽  
Vol 79 (11) ◽  
pp. 5543-5552 ◽  
Author(s):  
Krzysztof Szalewicz ◽  
Bogumil/ Jeziorski ◽  
Hendrik J. Monkhorst ◽  
John G. Zabolitzky
Keyword(s):  
Third Order ◽  
Molecular Correlation ◽  
Explicitly Correlated

scholarly journals The cc-pV5Z-F12 basis set: reaching the basis set limit in explicitly correlated calculations

2014 ◽  
Vol 113 (13-14) ◽  
pp. 1551-1558 ◽  
Author(s):  
Kirk A. Peterson ◽  
Manoj K. Kesharwani ◽  
Jan M.L. Martin
Keyword(s):  
Basis Set ◽  
Explicitly Correlated

Inelastic scattering of interstellar silyl cyanide (SiH3CN) by helium atoms : cross-sections and rate coefficients for A- and E-SiH3CN

2021 ◽  
Vol 507 (4) ◽  
pp. 5264-5271
Author(s):  
Manel Naouai ◽  
Abdelhak Jrad ◽  
Ayda Badri ◽  
Faouzi Najar
Keyword(s):  
Inelastic Scattering ◽  
Total Energy ◽  
Cross Sections ◽  
Three Dimensional ◽  
Basis Set ◽  
Rate Coefficients ◽  
Close Coupling ◽  
Explicitly Correlated ◽  
Correlation Consistent ◽  
Triple Excitation

ABSTRACT Rotational inelastic scattering of silyl cyanide (SiH3CN) molecule with helium (He) atoms is investigated. Three-dimensional potential energy surface (3D-PES) for the SiH3CN–He interacting system is carried out. The ab initio 3D-PES is computed using explicitly correlated coupled cluster approach with single, double, and perturbative triple excitation CCSD(T)-F12a connected to augmented-correlation consistent-polarized valence triple zeta Gaussian basis set. A global minimum at (R = 6.35 bohr; θ = 90○; ϕ = 60○) with a well depth of 52.99 cm−1 is pointed out. Inelastic rotational cross-sections are emphasized for the 22 first rotational levels for total energy up to 500 cm−1 via close coupling (CC) approach in the case of A-SiH3CN and for the 24 first rotational levels for total energy up to 100 cm−1 via CC and from 100 to 500 cm−1 via coupled states (CS) in the case of E-SiH3CN. Rate coefficients are derived for temperature until 80 K for both A- and E-SiH3CN–He systems. Propensity rules are obtained for |ΔJ| = 2 processes with broken parity for A-SiH3CN and for |ΔJ| = 2 processes with |ΔK| = 0 and unbroken parity for E-SiH3CN.

scholarly journals Crystal structures and Hirshfeld surface analyses of (E)-N′-benzylidene-2-oxo-2H-chromene-3-carbohydrazide and the disordered hemi-DMSO solvate of (E)-2-oxo-N′-(3,4,5-trimethoxybenzylidene)-2H-chromene-3-carbohydrazide: lattice energy and intermolecular interaction energy calculations for the former. Corrigendum

2019 ◽  
Vol 75 (12) ◽  
pp. 1952-1952
Author(s):  
Ligia R. Gomes ◽  
John Nicolson Low ◽  
James L. Wardell ◽  
Camila Capelini ◽  
José Daniel Figueroa Villar ◽  
...  
Keyword(s):  
Interaction Energy ◽  
Crystal Structures ◽  
Intermolecular Interaction ◽  
Lattice Energy ◽  
Hirshfeld Surface ◽  
Intermolecular Interaction Energy ◽  
Acta Cryst ◽  
Energy Calculations

In the paper by Gomes et al. [Acta Cryst. (2019), E75, 1403–1410], there was an error and omission in the author and affiliation list.

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