Xe⋯OCS: relatively straightforward?

Kraus, Peter; Obenchain, Daniel A.; Herbers, Sven; Wachsmuth, Dennis; Frank, Irmgard; Grabow, Jens‐Uwe

doi:10.1039/d0cp00334d

Cited by 4 publications

(5 citation statements)

References 50 publications

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“…Tables , S9, and S10 show the results for the non-augmented cc-pvXz-pp, def2-Xzvp, and pcseg- N basis sets. Note that for modeling non-covalent interactions, the use of basis sets without augmentation by diffuse functions cannot be recommended, even with X > 3 . The performance of the [2,3]-ζ extrapolations in the NCDT benchmark with all three basis set families is in line with the diet100 GMTKN55 results above.…”

Section: Resultssupporting

confidence: 68%

“…Note that for modeling non-covalent interactions, the use of basis sets without augmentation by diffuse functions cannot be recommended, even with X > 3. 67 The performance of the [2,3]-ζ extrapolations in the NCDT benchmark with all three basis set families is in line with the diet100 GMTKN55 results above. The RMSDs of the extrapolated cc-pv[dt]z-pp results are always better than with the cc-pvtz-pp basis set, with the exception of dlDF+D10 where cc-pvtz-pp performs significantly better than cc-pvqz-pp.…”

Section: Performance Of [23]-ζ Extrapolation In Gmtkn55supporting

confidence: 81%

“…In any case, the use of large basis sets without diffuse augmentation is questionable when accurate non-covalent interaction energies are required. [57] For the same reason, I will omit the analysis of pcseg-N with the NCDT dataset; the results for both basis set families are tabulated in the Supplemental material. Upon augmentation with diffuse functions, the performance of def2-[s,t]zvpd extrapolation (also global expsqrt fit) for non-covalent energies is a positive surprise:…”

Section: Automated [23]-ζ Extrapolation Of Non-covalent Interaction mentioning

confidence: 99%

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Basis Set Extrapolations for Density Functional Theory

Kraus

2020

J. Chem. Theory Comput.

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Basis set extrapolation is a common technique in wavefunction theory, used to squeeze better performance out of the highest affordable level of theory by combining it with lower quality calculations. In this work, I present analogous techniques for basis set extrapolation in density functional theory, focusing on [2,3]-ζ calculations, and including double hybrid and dispersion corrected functionals. My recommendations are based on basis set limit data from finite element calculations, estimates of basis set limits for double hybrid corrections, and they are validated using the GMTKN55 and NCDT datasets. A short review of extrapolation methods for Hartree-Fock calculations based on modern finite element data is carried out to inform this work. Extrapolation of [2,3]-ζ calculations in cc-pvXz-pp and def2-Xvpd basis sets with the proposed recipes routinely matches and sometimes outperforms 4-ζ calculations at a fraction of the cost. The methods are implemented in Psi4, allowing for an automated and intuitive application.

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Section: Resultssupporting

confidence: 68%

Section: Performance Of [23]-ζ Extrapolation In Gmtkn55supporting

confidence: 81%

Section: Automated [23]-ζ Extrapolation Of Non-covalent Interaction mentioning

confidence: 99%

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Basis Set Extrapolations for Density Functional Theory

Kraus

2020

J. Chem. Theory Comput.

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“…found this model to be as good as

r_{e}^{S E}

, when compared with high level coupled cluster calculation in the case of ethynylcyclohexane. Kraus et al [32] compared relativistic CCSD(T) structures with

r_{m}^{(2)}

for Xe⋅⋅⋅OCS with an agreement of around 5 mÅ. The 3rd column of Table 3 provides an

r_{m}^{(2)}

structure, where the experimental ground state constants have been fitted.…”

Section: Resultsmentioning

confidence: 99%

Determination of the “Privileged Structure” of 8‐Hydroxyquinoline

Wachsmuth

Kraus

Herbers³

et al. 2021

ChemPhysChem

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An accurate semi-experimental equilibrium structure of 8hydroxyquinoline (8-HQ) has been determined combining experiment and theory. The cm-wave rotational spectrum of 8-HQ was recorded in a pulsed supersonic jet using broadband dual-path reflection and narrowband Fabry-Perot-type resonator Fourier-transform microwave spectrometers. Accurate rotational and quartic centrifugal distortion constants and 14 N quadrupole coupling constants are determined. Rotational constants of all 13 C, 18 O and 15 N singly substituted isotopologues in natural abundance and those of a chemically synthesized OD isotopologue were used to obtain geometric parameters for all the heavy atoms and the hydroxyl hydrogen from a number of structure determination models. Theoretical approaches allowed for the determination of a semi-experimental equilibrium structure, r SE e in which computed rovibrational and electronic corrections were utilized to convert vibrational ground state constants into equilibrium constants. Despite the molecule having only a horizontal plane of symmetry and possessing 11 individual heavy atoms, microwave spectroscopy has allowed for a reliable and accurate structure determination. A mass dependent, r 2 ð Þ m structure was determined and proved to be equally reliable by comparison with the B3LYP-D3(BJ)/aVTZ equilibrium structure.

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“…Differently, our approach leads to the determination of an accurate equilibrium structure by rigorously correcting experimental rotational constants for computed vibrational contributions (examples for intermolecular complexes are available in refs. [ 20i , 20l , 23 ]). The latter have been obtained from anharmonic computations that are expensive for a system as large as BZF–FA.…”

mentioning

confidence: 99%

Stacked but not Stuck: Unveiling the Role of π→π* Interactions with the Help of the Benzofuran–Formaldehyde Complex

Spada

Alessandrini

et al. 2021

Angew Chem Int Ed

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The 1:1 benzofuran–formaldehyde complex has been chosen as model system for analyzing π→π* interactions in supramolecular organizations involving heteroaromatic rings and carbonyl groups. A joint “rotational spectroscopy–quantum chemistry” strategy unveiled the dominant role of π→π* interactions in tuning the intermolecular interactions of such adduct. The exploration of the intermolecular potential energy surface led to the identification of 14 low‐energy minima, with 4 stacked isomers being more stable than those linked by hydrogen bond or lone‐pair→π interactions. All energy minima are separated by loose transition states, thus suggesting an effective relaxation to the global minimum under the experimental conditions. This expectation has been confirmed by the experimental detection of only one species, which was unambiguously assigned owing to the computation of accurate spectroscopic parameters and the characterization of 11 isotopologues. The large number of isotopic species opened the way to the determination of the first semi‐experimental equilibrium structure for a molecular complex of such a dimension.

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Xe⋯OCS: relatively straightforward?

Abstract: Spectroscopy meets theory in a study of Xe⋯OCS complex: accurate near-equilibrium structures, experimental interaction energies, and CCSD(T)/CBS results presented.

Cited by 4 publications

References 50 publications

Basis Set Extrapolations for Density Functional Theory

Basis Set Extrapolations for Density Functional Theory

Determination of the “Privileged Structure” of 8‐Hydroxyquinoline

Stacked but not Stuck: Unveiling the Role of π→π* Interactions with the Help of the Benzofuran–Formaldehyde Complex

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