Generalized spin-ratio scaled MP2 method for accurate prediction of intermolecular interactions for neutral and ionic species

Tan, Samuel Y. S.; Acevedo, Santiago Barrera; Izgorodina, Ekaterina I.

doi:10.1063/1.4975326

Cited by 41 publications

(55 citation statements)

References 52 publications

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“…67 Yang et al 68 In both of these papers the fragmentation scheme did not contain an embedding potential, thus requiring the inclusion of up to fourbody contributions in the study of Yang et al 68 to predict the most accurate lattice energy of the benzene crystal to-date. Our group has recently introduced a modified version of MP2, the spin-ratio scaled second-order Møller-Plesset perturbation method (SRS-MP2) 74 intermolecular complexes present in the S22, 76 S66, 77 and IL174 78,79 databases.…”

Section: Introductionmentioning

confidence: 99%

“…71 A spherical approach was applied to predict lat- All FMO calculations were performed with the GAMESS-US software package. 94 The SRS-MP2/cc-pVTZ method 74 was then used to perform a single point calculation on the sphere. For this basis set, the opposite-spin coefficient of 1.64 was used, whereas the same-spin coefficient was set to zero as the spin ratio was found to be >1.0 in benzene dimers.…”

Section: Introductionmentioning

confidence: 99%

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Prediction of lattice energy of benzene crystals: A robust theoretical approach

et al. 2020

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We present an inexpensive and robust theoretical approach based on the fragment molecular orbital methodology and the spin-ratio scaled second-order Møller-Plesset perturbation theory to predict the lattice energy of benzene crystals within 2 kJÁmol −1. Inspired by the Harrison method to estimate the Madelung constant, the proposed approach calculates the lattice energy as a sum of two-and three-body interaction energies between a reference molecule and the surrounding molecules arranged in a sphere. The lattice energy converges rapidly at a radius of 13 Å. Adding the corrections to account for a higher correlated level of theory and basis set superposition for the Hartree Fock (HF) level produced a lattice energy of −57.5 kJÁmol −1 for the benzene crystal structure at 138 K. This estimate is within 1.6 kJÁmol −1 off the best theoretical prediction of −55.9 kJÁmol −1. We applied this approach to calculate lattice energies of the crystal structures of phase I and phase II-polymorphs of benzene-observed at a higher temperature of 295 K. The stability of these polymorphs was correctly predicted, with phase II being energetically preferred by 3.7 kJÁmol −1 over phase I. The proposed approach gives a tremendous potential to predict stability of other molecular crystal polymorphs.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Prediction of lattice energy of benzene crystals: A robust theoretical approach

et al. 2020

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“…For larger clustersof two-and four-ion pairs where CCSD(T)/ CBS is infeasible -DLPNO calculations are compared with SRS-MP2/ cc-pVTZ which scales same and opposite spin energies in order to reproduce CCSD(T)/CBS energies with a mean average error of below 2 kJ mol À1 . 38,48 The scaling also accounts for basis set superposition error meaning additional costly counterpoise correction calculations can be avoided. SRS-MP2 calculations were performed with PSI4 and utilize the efficient RI-MP2.…”

Section: Methodsmentioning

confidence: 99%

“…All energies are given relative to SRS-MP2/cc-pVTZ which has been developed to reproduce CCSD(T)/CBS energies with a mean average error of 2 kJ mol À1 while also correcting for basis set superposition error. 38,48 Analysis of these results clearly indicate that such replacement can be recommended as errors well within chemical accuracy (below 2.1 kJ mol À1 ) were observed for two-and four ionpaired clusters of the two ionic liquids. T A B L E 1 1 Correlation interaction energy errors (in kJ mol À1 ) of DLPNO-CCSD(T 0 )/cc-pVTZ with TightPNO settings for the HBIL dataset.…”

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confidence: 86%

A DLPNO‐CCSD(T) benchmarking study of intermolecular interactions of ionic liquids

Seeger

Izgorodina

2021

J Comput Chem

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The accuracy of correlation energy recovered by coupled cluster single-, double-, and perturbative triple-excitations, CCSD(T), has led to the method being considered the gold standard of computational chemistry. The application of CCSD(T) has been limited to medium-sized molecular systems due to its steep scaling with molecular size.The recent development of alternative domain-based local pair natural orbital coupled-cluster method, DLPNO-CCSD(T), has significantly broadened the range of chemical systems to which CCSD(T) level calculations can be applied. Condensed systems such as ionic liquids (ILs) have a large contribution from London dispersion forces of up to 150 kJ mol À1 in large-scale clusters. Ionic liquids show appreciable charge transfer effects that result in the increased valence orbital delocalization over the entire ionic network, raising the question whether the application of methods based on localized orbitals is reliable for these semi-Coulombic materials. Here the performance of DLPNO-CCSD(T) is validated for the prediction of correlation interaction energies of two data sets incorporating single-ion pairs of protic and aprotic ILs. DLPNO-CCSD(T) produced results within chemical accuracy with tight parameter settings and a non-iterative treatment of triple excitations. To achieve spectroscopic accuracy of 1 kJ mol À1 , especially for hydrogen-bonded ILs and those containing halides, the DLPNO settings had to be increased by two orders of magnitude and include the iterative treatment of triple excitations, resulting in a 2.5-fold increase in computational cost. Two new sets of parameters are put forward to produce the performance of DLPNO-CCSD(T) within chemical and spectroscopic accuracy.

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“…Another approach adapts the spin-component scaling coefficients to each given system on the fly. This has been done via spin-ratio scaled spin components (SRS-MP2) 35 or by machine learning the optimal scaling parameters as in SNS-MP2. 12 Adaptive spin-scaling approaches can be more universal, though care must be taken to ensure that the coefficient adaptations retain smooth and continuous potential energy surfaces.…”

Section: Introductionmentioning

confidence: 99%

Spin-component-scaled and dispersion-corrected second-order Møller-Plesset perturbation theory: A path toward chemical accuracy

Greenwell

Řezáč

Beran

2021

Preprint

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Second-order Møller-Plesset perturbation theory (MP2) provides a valuable alternative to density functional theory for modeing problems in organic and biological chemistry. However, MP2 suffers from known lim- itations in the description of van der Waals dispersion interactions and reaction thermochemistry. Here, a spin-component-scaled, dispersion-corrected MP2 model (SCS-MP2D) is proposed that addresses these weaknesses. The dispersion correction, which is based on Grimme’s D3 formalism, replaces the uncoupled Hartree-Fock dispersion inherent in MP2 with a more robust coupled Kohn-Sham treatment. The spin- component scaling of the residual MP2 correlation energy then reduces the remaining errors in the model. This two-part correction strategy solves the problem found in earlier spin-component-scaled MP2 models where completely different spin-scaling parameters were needed for describing reaction energies versus in- termolecular interactions. Results on 18 benchmark data sets and two challenging potential energy curves demonstrate that SCS-MP2D considerably improves upon the accuracy of MP2 for intermolecular interac- tions, conformational energies, and reaction energies. Its accuracy and computational cost are competitive with state-of-the-art density functionals such as DSD-BLYP-D3(BJ), revDSD-PBEP86-D3(BJ), ωB97X-V, and ωB97M-V for systems with ∼100 atoms.

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Generalized spin-ratio scaled MP2 method for accurate prediction of intermolecular interactions for neutral and ionic species

Cited by 41 publications

References 52 publications

Prediction of lattice energy of benzene crystals: A robust theoretical approach

Prediction of lattice energy of benzene crystals: A robust theoretical approach

A DLPNO‐CCSD(T) benchmarking study of intermolecular interactions of ionic liquids

Spin-component-scaled and dispersion-corrected second-order Møller-Plesset perturbation theory: A path toward chemical accuracy

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