Exploring the Rich Energy Landscape of Sulfate–Water Clusters SO42– (H2O)n=3–7: An Electronic Structure Approach

Lambrecht, Daniel S.; Clark, Gary F.; Head‐Gordon, Teresa; Head‐Gordon, Martin

doi:10.1021/jp206064n

Cited by 40 publications

(53 citation statements)

References 53 publications

(120 reference statements)

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“…The 3350-3650 cm −1 feature arises largely from O H bonds engaged in water-water interactions, although some combinations of O H stretches toward the sulfate also have relatively high frequencies. Water molecules residing in the second hydration shell of the ion induce significant spectral differences in comparison to small clusters in which all molecules are expected to interact directly with the sulfate ion, as has been amply characterized for n = 3-6 [12][13][14][15][16][17][18][19][20][21]. Thus, the change in the relative intensities of the two broad spectral features, with the blue part growing relative to the red part when the cluster size increases, is consistent with the rise of the second hydration shell.…”

Section: Experimental Spectra For N = 9-13mentioning

confidence: 60%

“…As described previously for clusters with n = 3-7 [16], the energy ordering is modified by inclusion of zero-point vibrational energy (ZPE). Thus, all results below include ZPE computed at the M11 level.…”

Section: Methodsmentioning

confidence: 99%

“…Small clusters in the n = 3-7 range have been extensively characterized [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21]. In particular, computational investigations by Head-Gordon and coworkers provide both a comprehensive picture of the low-energy structure manifold [16] and a thorough calibration of the performances of quantum chemical methods [17]. Many density functionals were compared to ab initio results at the current accuracy limit [18].…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Hydration of the sulfate dianion in size-selected water clusters: From SO42−(H2O)9 to SO42−(H2O)13

Thaunay

Hassan

Cooper

et al. 2017

International Journal of Mass Spectrometry

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Section: Experimental Spectra For N = 9-13mentioning

confidence: 60%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Hydration of the sulfate dianion in size-selected water clusters: From SO42−(H2O)9 to SO42−(H2O)13

Thaunay

Hassan

Cooper

et al. 2017

International Journal of Mass Spectrometry

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“…We fitted several plausible cluster structures to the derived pair distribution functions (PDFs), and show that the proposed family of solutions has to fulfill three conditions: (1) the clusters are rod-shaped; (2) a single structural unit in the cross-section of the rod does not expand beyond a single Ca-Ca distance, with either of 2 or 3 Ca ions per unit; (3) the cluster structure are "internally" anhydrous and bound water is only present at their "surface". The dynamic 20 properties of the plausible structures derived from PDF analysis were tested using unbiased MD based on both rigid-ion and polarizable force-fields. Of the suite of clusters tested, the one with a simple 2-member square-shaped Ca-SO4-Ca-SO4 unit, where 6 stacks are arranged in an AB pattern and each Ca is coordinated by two in-plane water molecules, resulted to be the only structure stable throughout the whole MD simulation (5 ns).…”

Section: Discussionmentioning

confidence: 99%

The Structure of CaSO₄ Nanorods: The Precursor of Gypsum

et al. 2019

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Understanding the gypsum (CaSO4·2H2O) formation pathway from aqueous solution has been the subject of intensive research in the past years. This interest stems from the fact that gypsum appears to fall into a broader category of crystalline materials whose formation does not follow classical nucleation and growth theories. The pathways involve transitory precursor cluster species, yet the actual structural properties of such clusters are not very well understood. Here, we show how in situ high-energy X-ray diffraction experiments and molecular dynamics (MD) simulations can be combined to derive the structure of small CaSO4 clusters, which are precursors of crystalline gypsum. We fitted several plausible structures to the derived pair distribution functions and explored their dynamic properties using unbiased MD simulations based on both rigid ion and polarizable force fields.Determination of the structure and (meta)stability of the primary species is important from both a fundamental and applied perspective; for example, this will allow for an improved design of additives for greater control of the nucleation pathway.

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“…Only equilibrium geometries were examined from the divalent sulphur database [154]. Complete basis set estimates (CBS) for MP2 were taken from references for the divalent sulphur, SW49 [155][156][157], ACONF [158], CYCONF [159], and SCONF [160] databases. MP2/CBS results for the S22 [82,83], S66 [84,85], L7 [161], and P76 [162] databases were obtained from the Benchmark Energy and Geometry DataBase (BEGDB) [163].…”

Section: Perturbative Methodsmentioning

confidence: 99%

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

Shao¹,

Gan²,

Epifanovsky³

et al. 2014

Molecular Physics

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2,698

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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Exploring the Rich Energy Landscape of Sulfate–Water Clusters SO₄^2– (H₂O)_n=3–7: An Electronic Structure Approach

Cited by 40 publications

References 53 publications

Hydration of the sulfate dianion in size-selected water clusters: From SO42−(H2O)9 to SO42−(H2O)13

Hydration of the sulfate dianion in size-selected water clusters: From SO42−(H2O)9 to SO42−(H2O)13

The Structure of CaSO₄ Nanorods: The Precursor of Gypsum

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

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Exploring the Rich Energy Landscape of Sulfate–Water Clusters SO42– (H2O)n=3–7: An Electronic Structure Approach

Cited by 40 publications

References 53 publications

Hydration of the sulfate dianion in size-selected water clusters: From SO42−(H2O)9 to SO42−(H2O)13

Hydration of the sulfate dianion in size-selected water clusters: From SO42−(H2O)9 to SO42−(H2O)13

The Structure of CaSO4 Nanorods: The Precursor of Gypsum

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

Contact Info

Product

Resources

About

Exploring the Rich Energy Landscape of Sulfate–Water Clusters SO₄^2– (H₂O)_n=3–7: An Electronic Structure Approach

The Structure of CaSO₄ Nanorods: The Precursor of Gypsum