Correction to Semi-Experimental Equilibrium Structure Determinations by Employing B3LYP/SNSD Anharmonic Force Fields: Validation and Application to Semirigid Organic Molecules

Piccardo, Matteo; Penocchio, Emanuele; Puzzarini, Cristina; Biczysko, Małgorzata; Barone, Vincenzo

doi:10.1021/acs.jpca.6b04648

Cited by 21 publications

(17 citation statements)

References 1 publication

(1 reference statement)

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“…The performance for the calculation of covalent bond lengths is assessed on benchmark sets that contain light main-group bonds (LMGB35 82 ), heavy main-group bonds (HMGB11 82 ), long main-group bond lengths (LB12 82 ), transition metal complexes (TMC32 83 ), and small semirigid organic molecules (CCse21 84 , 85 ). Rotational constants are evaluated with the ROT34 86 , 87 test set.…”

Section: Resultsmentioning

confidence: 99%

Optimization of the r²SCAN-3c Composite Electronic-Structure Method for Use with Slater-Type Orbital Basis Sets

et al. 2022

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The “Swiss army knife” composite density functional electronic-structure method r 2 SCAN-3c ( J. Chem. Phys. 2021 , 154 , 064103) is extended and optimized for the use with Slater-type orbital basis sets. The meta generalized-gradient approximation (meta-GGA) functional r 2 SCAN by Furness et al. is combined with a tailor-made polarized triple-ζ Slater-type atomic orbital (STO) basis set (mTZ2P), the semiclassical London dispersion correction (D4), and a geometrical counterpoise (gCP) correction. Relativistic effects are treated explicitly with the scalar-relativistic zeroth-order regular approximation (SR-ZORA). The performance of the new implementation is assessed on eight geometry and 74 energy benchmark sets, including the extensive GMTKN55 database as well as recent sets such as ROST61 and IONPI19. In geometry optimizations, the STO-based r 2 SCAN-3c is either on par with or more accurate than the hybrid density functional approximation M06-2X-D3(0)/TZP. In energy calculations, the overall accuracy is similar to the original implementation of r 2 SCAN-3c with Gaussian-type atomic orbitals (GTO), but basic properties, intermolecular noncovalent interactions, and barrier heights are better described with the STO approach, resulting in a lower weighted mean absolute deviation (WTMAD-2(STO) = 7.15 vs 7.50 kcal mol –1 with the original method) for the GMTKN55 database. The STO-optimized r 2 SCAN-3c outperforms many conventional hybrid/QZ approaches in most common applications at a fraction of their cost. The reliable, robust, and accurate r 2 SCAN-3c implementation with STOs is a promising alternative to the original implementation with GTOs and can be generally used for a broad field of quantum chemical problems.

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Section: Resultsmentioning

confidence: 99%

Optimization of the r²SCAN-3c Composite Electronic-Structure Method for Use with Slater-Type Orbital Basis Sets

et al. 2022

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“… a See text. b Reference for N 2 , HCN, and HNC and ref for NCCN. c Reference , using theoretical vibrational corrections from ref . …”

Section: Results and Discussionmentioning

confidence: 99%

“… a Not calculated. b See text. c Reference for NH 3 and HNNH and refs and for benzene. d Reference for NH 3 ( cf . footnote c in Table ), ref for HNNH, and ref for benzene. …”

Section: Results and Discussionmentioning

confidence: 99%

“…Concerning nitrogen-substituted derivatives of benzene, the r e structures of pyridine, pyridazine (1,2-diazine), and pyrimidine (1,3-diazine) have also been determined in recent years − by using a semiexperimental strategy that combines experimental data (ground-state rotational constants) and theoretical data (corrections due to zero-point vibrations).…”

Section: Introductionmentioning

confidence: 99%

“…It has recently been noted that there is still a lack of accurate equilibrium structures of nitrogen-containing heterocyclic molecules . There has been some progress in this field since 2015. − The present study aims at further improving our knowledge about accurate r e structures of N-substituted derivatives of benzene.…”

Section: Introductionmentioning

confidence: 99%

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Equilibrium Structures of Pyrazine, s-Triazine, and s-Tetrazine

Breidung

Thiel

2018

J. Phys. Chem. C

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In recent years, accurate equilibrium (r e ) structures have been determined for pyridine, pyridazine, and pyrimidine. Here, we report accurate r e structures for the structurally related molecules pyrazine, s-triazine, and s-tetrazine, which were obtained using a composite approach based on explicitly correlated coupled-cluster theory (CCSD(T)-F12b) in conjunction with a large correlation-consistent basis set (cc-pCVQZ-F12) to take core− valence electron correlation into account. Additional terms were included to correct for the effects of iterative triple excitations (CCSDT), noniterative quadruple excitations (CCSDT-(Q)), and scalar relativistic contributions (DKH2-CCSD(T)). The performance of this computational procedure was established through test calculations on selected small molecules. For s-triazine, accurate experimental ground-state rotational constants (B 0 ) of the parent molecule and six D 3h isotopologues from the literature were used to determine a semiexperimental r e structure, which was found to be essentially identical with the best estimate from the current composite approach. The presently recommended equilibrium structural parameters of s-triazine are r e (CH) = 108.17 pm, r e (CN) = 133.19 pm, and θ e (NCN) = 125.95°, with estimated uncertainties of ±0.10 pm and ±0.10°, respectively. The predicted equilibrium geometries for pyrazine and s-tetrazine are expected to be of the same accuracy. We recommend for pyrazine: r e (CH) = 108.16 pm, r e (CN) = 133.34 pm, r e (CC) = 139.07 pm, θ e (CNC) = 115.60°, and θ e (HCC) = 120.75°; and for s-tetrazine: r e (CH) = 107.95 pm, r e (CN) = 133.39 pm, r e (NN) = 132.01 pm, and θ e (NCN) = 126.59°.

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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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Correction to Semi-Experimental Equilibrium Structure Determinations by Employing B3LYP/SNSD Anharmonic Force Fields: Validation and Application to Semirigid Organic Molecules

Cited by 21 publications

References 1 publication

Optimization of the r²SCAN-3c Composite Electronic-Structure Method for Use with Slater-Type Orbital Basis Sets

Optimization of the r²SCAN-3c Composite Electronic-Structure Method for Use with Slater-Type Orbital Basis Sets

Equilibrium Structures of Pyrazine, s-Triazine, and s-Tetrazine

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

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Correction to Semi-Experimental Equilibrium Structure Determinations by Employing B3LYP/SNSD Anharmonic Force Fields: Validation and Application to Semirigid Organic Molecules

Cited by 21 publications

References 1 publication

Optimization of the r2SCAN-3c Composite Electronic-Structure Method for Use with Slater-Type Orbital Basis Sets

Optimization of the r2SCAN-3c Composite Electronic-Structure Method for Use with Slater-Type Orbital Basis Sets

Equilibrium Structures of Pyrazine, s-Triazine, and s-Tetrazine

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

Contact Info

Product

Resources

About

Optimization of the r²SCAN-3c Composite Electronic-Structure Method for Use with Slater-Type Orbital Basis Sets

Optimization of the r²SCAN-3c Composite Electronic-Structure Method for Use with Slater-Type Orbital Basis Sets