Hydrocarbon/Water Interactions: Encouraging Energetics and Structures from DFT but Disconcerting Discrepancies for Hessian Indices

Copeland, Kari L.; Tschumper, Gregory S.

doi:10.1021/ct300132e

Cited by 50 publications

(31 citation statements)

References 95 publications

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“…Accordingly, dispersion-corrected DFT is able to accurately describe the mono-hydrated complex. This feature is in line with other studies on hydrated species [34,45]. The LC-ωPBE-GD3BJ/Pop2, that simultaneously reproduces the selected geometric, energetic and spectroscopic features with errors less than 5%, as well as the MP2/aVDZ levels, were selected for the study of larger hydrated complexes.…”

Section: Methods Calibrationsupporting

confidence: 69%

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A theoretical investigation of water–solute interactions: from facial parallel to guest–host structures

2017

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Encapsulation of small (bio-)organic molecules within water cages is governed by a subtle equilibrium between water-water and water-solute interactions. The competition between the formation of exohedral and endohedral complexes is investigated. The first step prior to a theoretical characterization of interactions involved in such complexes lies in the judicious choice of a level of theory. The β-propiolactone (BPL), a solute for which the micro-hydration was recently characterized by means of high resolution microwave spectroscopy (Angew. Chem. 2015, 127, 993), was selected for the present study, and a calibration step is carried out. It is shown that the dispersion-corrected density functional theory (DFT-D) suitably reproduce the geometric, energetic and spectroscopic features of the BPL:(H 2 O) 1-5 complexes. The experimentally-deduced structures of the BPL:(H 2 O) 4,5 species are fully understood in terms of the maximization of interactions between complementary sites in the MESPs. DFT-D calculations followed by the topological analysis within the Quantum Theory of Atoms in Molecules framework have shown that the solute could efficiently interact with (H 2 O) 6,10 clusters in a similar manner that the (H 2 O) 4,5 clusters do. The interaction of the solute with two larger water clusters is further investigated. The exohedral and endohedral BPL:(H 2 O) 20 isomers are close in energy with each other, whereas the formation of an inclusion complex is energetically more favored than the facial interaction in the case of the BPL:(H 2 O) 24 cluster. The topological analysis suggests that the substantial energetic stability is due to interactions between the solute and almost all oxygen atoms of the water cage.

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Section: Methods Calibrationsupporting

confidence: 69%

“…It was shown that dispersion-corrected density functionals may suitably describe such complexes provided that a calibration step is carried out, either with respect to the experimental data or to the results coming from high-level theoretical calculations [14,16,34].…”

Section: Introductionmentioning

confidence: 99%

A theoretical investigation of water–solute interactions: from facial parallel to guest–host structures

2017

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“…In the case of water-methane interactions, we have shown [8] that the repulsive wall of the pairwise interaction potential directs the OH bond of water into the threefold hollow of the methyl group, thereby facilitating closest approach of the molecules. Other studies support this conclusion [9,10,11,12]. Extending this picture to higher hydrocarbons is a goal of our ongoing work, and this letter continues that effort.…”

Section: Introductionsupporting

confidence: 52%

Terahertz vibration-rotation-tunneling spectroscopy of the propane–water dimer: The ortho-state of a 20 cm−1 torsion

Lin¹,

Steyert

Hlavacek

et al. 2014

Chemical Physics Letters

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a b s t r a c tWe report the detailed characterization of a torsional vibration-rotation-tunneling band of the orthostate of the propane-water dimer in the spectral region near 20 cm −1 (0.6 THz). This work extends the previously reported studies with more than one hundred new transitions included in a combined fit with the 155 previously reported transitions in both the microwave and terahertz regions for this torsional band. More than six hundred transitions have now been recorded in the interval 500 and 810 GHz.

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“…The latter six data-sets contain non-covalent (NC) interactions, which are evaluated using the aug-cc-pVTZ basis, except for the X40 data, which used the def2-TZVPPD basis set. The TC data-sets are (1) non-multi-reference total atomisation energies (TAE) [74], (2) atomisation energies of n = 1-8 alkanes (Alk19) [75], (3) diverse barrier heights (DBH24) [76][77][78], (4) adiabatic ionisation potentials (G21IP) [79,80], (5) weak hydrocarbon-water interactions (HW30) [81], (6) hydrogen-bonded and dispersion-bonded complexes (S22) [82,83], (7) interaction energies of relevant biomolecular structures (S66) [84,85], (8) small non-covalent complexes (A24) [86], (9) non-covalent interactions of halogenated molecules (X40) [87], and (10) interactions of complexes containing divalent sulphur (DS14) [88]. The final two columns give the overall RMS errors for the four TC data-sets and six NC data-sets.…”

Section: Density Functional Theory Functionalsmentioning

confidence: 99%

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package

Shao¹,

Gan²,

Epifanovsky³

et al. 2014

Molecular Physics

2,751

2,077

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A summary of the technical advances that are incorporated in the fourth major release of the Q-Chem quantum chemistry program is provided, covering approximately the last seven years. These include developments in density functional theory methods and algorithms, nuclear magnetic resonance (NMR) property evaluation, coupled cluster and perturbation theories, methods for electronically excited and openshell species, tools for treating extended environments, algorithms for walking on potential surfaces, analysis tools, energy and electron transfer modelling, parallel computing capabilities, and graphical user interfaces. In addition, a selection of example case studies that illustrate these capabilities is given. These include extensive benchmarks of the comparative accuracy of modern density functionals for bonded and non-bonded interactions, tests of attenuated second order Møller-Plesset (MP2) methods for intermolecular interactions, a variety of parallel performance benchmarks, and tests of the accuracy of implicit solvation models. Some specific chemical examples include calculations on the strongly correlated Cr 2 dimer, exploring zeolitecatalysed ethane dehydrogenation, energy decomposition analysis of a charged ter-molecular complex arising from glycerol photoionisation, and natural transition orbitals for a Frenkel exciton state in a nine-unit model of a self-assembling nanotube.Keywords quantum chemistry, software, electronic structure theory, density functional theory, electron correlation, computational modelling, Q-Chem Disciplines Chemistry CommentsThis article is from Molecular Physics: An International Journal at the Interface Between Chemistry and Physics 113 (2015): 184, doi:10.1080/00268976.2014. RightsWorks produced by employees of the U.S. Government as part of their official duties are not copyrighted within the U.S. The content of this document is not copyrighted. Authors 185A summary of the technical advances that are incorporated in the fourth major release of the Q-CHEM quantum chemistry program is provided, covering approximately the last seven years. These include developments in density functional theory methods and algorithms, nuclear magnetic resonance (NMR) property evaluation, coupled cluster and perturbation theories, methods for electronically excited and open-shell species, tools for treating extended environments, algorithms for walking on potential surfaces, analysis tools, energy and electron transfer modelling, parallel computing capabilities, and graphical user interfaces. In addition, a selection of example case studies that illustrate these capabilities is given. These include extensive benchmarks of the comparative accuracy of modern density functionals for bonded and non-bonded interactions, tests of attenuated second order Møller-Plesset (MP2) methods for intermolecular interactions, a variety of parallel performance benchmarks, and tests of the accuracy of implicit solvation models. Some specific chemical examples include calculations on the strongly corre...

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Hydrocarbon/Water Interactions: Encouraging Energetics and Structures from DFT but Disconcerting Discrepancies for Hessian Indices

Cited by 50 publications

References 95 publications

A theoretical investigation of water–solute interactions: from facial parallel to guest–host structures

A theoretical investigation of water–solute interactions: from facial parallel to guest–host structures

Terahertz vibration-rotation-tunneling spectroscopy of the propane–water dimer: The ortho-state of a 20 cm−1 torsion

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package

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