An ab initio study of beryllium(II) hydration

Pye, Cory C.

doi:10.1016/j.theochem.2009.07.045

Cited by 9 publications

(7 citation statements)

References 32 publications

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“…Geometry optimizations of the [Be(H 2 O) 4 ] 2+ ·8H 2 O system were carried out using different density functionals (Table ). All optimized geometries present nearly undistorted S 4 symmetries very similar to those reported by Pye (Figure ) . Four water molecules are coordinated to the Be 2+ ion providing a fairly regular tetrahedral coordination environment.…”

Section: Resultssupporting

confidence: 76%

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Water exchange rates and mechanisms in tetrahedral [Be(H₂O)₄]²⁺ and [Li(H₂O)₄]⁺ complexes using DFT methods and cluster‐continuum models

Regueiro‐Figueroa

Esteban‐Gómez

Pujales‐Paradela

et al. 2016

Int J of Quantum Chemistry

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The water exchange reactions in aquated Li 1 and Be 21 ions were investigated with density functional theory calculations performed using the [Li(H 2 O) 4 ] 1 Á14H 2 O and [Be(H 2 O) 4 ] 21 Á8H 2 O systems and a cluster-continuum approach. A range of commonly used functionals predict water exchange rates several orders of magnitude lower than the experimental ones. This effect is attributed to the overstabilization of coordination number four by these functionals with respect to the five-coordinated transition states responsible for the associative (A) or associative interchange (I a ) water exchange mechanisms. However, the M06 and M062X functionals provide results in good agreement with the experimental data: M062X/TZVP calculations yield a concerted I a mechanism for the water exchange in [Be(H 2 O) 4 ] 21 Á8H 2 O that gives an average residence time of water molecules in the first coordination sphere of 260 ls. For [Li(H 2 O) 4 ] 1 Á14H 2 O the water exchange reaction is predicted to follow an A mechanism with a residence time of inner-sphere water molecules of 25 ps. K E Y W O R D S berylium, density functional calculations, lithium, water exchange

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Section: Resultssupporting

confidence: 76%

“…In a series of papers Pye et al reported vibrational (IR and Raman) and computational (MP2 and B3LYP) studies on the hydration of Li + and Be 2+ in aqueous solutions. These investigations demonstrated that both cations are four‐coordinated in diluted aqueous solutions.…”

Section: Resultsmentioning

confidence: 99%

Water exchange rates and mechanisms in tetrahedral [Be(H₂O)₄]²⁺ and [Li(H₂O)₄]⁺ complexes using DFT methods and cluster‐continuum models

Regueiro‐Figueroa

Esteban‐Gómez

Pujales‐Paradela

et al. 2016

Int J of Quantum Chemistry

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“…23 A table summarizing Be−O distances calculated using different methods and basis sets can be found in the paper by Pye. 51 Also listed in Table 1 are the total interaction energy per water and successive binding energies for each cluster size which are in good agreement with other ab initio literature values. 19,52,53…”

Section: Methodssupporting

confidence: 84%

“…The resulting Be–O distances for all the clusters are listed in Table and are similar to previous ab initio results . A table summarizing Be–O distances calculated using different methods and basis sets can be found in the paper by Pye . Also listed in Table are the total interaction energy per water and successive binding energies for each cluster size which are in good agreement with other ab initio literature values. ,, The last column in Table lists Δ E many‑body which gives the difference in binding energy per water in the cluster and the binding energy of water in a Be 2+ –H 2 O complex with the same Be–O distance minus the water–water repulsion: This value quantifies the error introduced by assuming pairwise additivity of the interactions and the importance of including many-body terms .…”

Section: Methodssupporting

confidence: 60%

Many-Body Potentials for Aqueous Be²⁺ Derived from ab Initio Calculations

Winter

2016

J. Phys. Chem. B

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An effective three-body potential for the aqueous Be ion has been constructed from a large number of high-level ab initio cluster calculations. The new potential was validated in subsequent molecular dynamics simulations of both gas phase ion-water clusters and bulk liquid. The structures of the first and second solvation shells were studied using radial distribution functions and angular distribution functions. The vibrational spectrum of Be and first shell waters was examined by computing power spectra from the molecular dynamics simulations. The observed bands showed reasonable agreement with experimental spectroscopic frequencies. The potential of mean force for water exchange between the first and second solvation shells was calculated and the energy barrier for exchange was found to have improved agreement with experiment relative to two-body force fields. Examination of the solvation structure near the transition state yielded results consistent with an associative mechanism.

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“…While periodic DFT-GGA is well-suited for the description of the interface and the formation of Pb(II) surface complexes, it is not an ideal methodology for describing the properties of the solvated cation. Furthermore, theoretical descriptions of the hydration properties of aqueous Pb(II) and other geochemically relevant metals are still active research topics. − This leads to complications that include disagreement between theoretical studies on fundamental factors such as the number of water molecules in the first coordination shell of divalent lead. ,, Therefore, we find it to be advantageous in the present study to circumvent explicit treatment of the cation hydration, especially since the adsorption energy can be partitioned such that this information could be added in at a later time.…”

Section: Methodology and Computational Detailsmentioning

confidence: 99%

Hybridization-reactivity relationship in Pb(II) adsorption on α-Al₂O₃-water interfaces: A DFT Study

2011

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We report on a density functional theory study aimed at comparing the reactivity of differently structured R-Al 2 O 3 -water interfaces as probed through adsorption of the Pb(II) cation. We assign the Pb-O bonding in Pb(II)/Al 2 O 3 geometries to in-plane and out-of-plane orbital contributions. From our analysis, the empirically known greater Pb(II) reactivity of R-Al 2 O 3 (1102) over R-Al 2 O 3 ( 0001) is ascribed to the ability of oxygen functional groups in the corrugated (1102) interface to hybridize more effectively with Pb(II) electronic states than oxygen functional groups in the topographically flat (0001) interface. The theoretical evidence of a Pb-O hybridization-reactivity relationship goes beyond bondvalence predictions that cite oxygen functional group coordination as a key predictor of mineral-water interface reactivity. We also report the details of adsorption-induced surface relaxations, including an example of surface hydrogen bond rearrangement, as well as evidence of long-range Pb-O interaction. To further assess the bonding saturation of lead in the optimized Pb(II)/Al 2 O 3 structures, molecular H 2 O adsorption studies are carried out and shown to support that the cation coordination is largely satisfied through interactions with surface functional groups.

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An ab initio study of beryllium(II) hydration

Cited by 9 publications

References 32 publications

Water exchange rates and mechanisms in tetrahedral [Be(H₂O)₄]²⁺ and [Li(H₂O)₄]⁺ complexes using DFT methods and cluster‐continuum models

Water exchange rates and mechanisms in tetrahedral [Be(H₂O)₄]²⁺ and [Li(H₂O)₄]⁺ complexes using DFT methods and cluster‐continuum models

Many-Body Potentials for Aqueous Be²⁺ Derived from ab Initio Calculations

Hybridization-reactivity relationship in Pb(II) adsorption on α-Al₂O₃-water interfaces: A DFT Study

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An ab initio study of beryllium(II) hydration

Cited by 9 publications

References 32 publications

Water exchange rates and mechanisms in tetrahedral [Be(H2O)4]2+ and [Li(H2O)4]+ complexes using DFT methods and cluster‐continuum models

Water exchange rates and mechanisms in tetrahedral [Be(H2O)4]2+ and [Li(H2O)4]+ complexes using DFT methods and cluster‐continuum models

Many-Body Potentials for Aqueous Be2+ Derived from ab Initio Calculations

Hybridization-reactivity relationship in Pb(II) adsorption on α-Al2O3-water interfaces: A DFT Study

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Water exchange rates and mechanisms in tetrahedral [Be(H₂O)₄]²⁺ and [Li(H₂O)₄]⁺ complexes using DFT methods and cluster‐continuum models

Water exchange rates and mechanisms in tetrahedral [Be(H₂O)₄]²⁺ and [Li(H₂O)₄]⁺ complexes using DFT methods and cluster‐continuum models

Many-Body Potentials for Aqueous Be²⁺ Derived from ab Initio Calculations

Hybridization-reactivity relationship in Pb(II) adsorption on α-Al₂O₃-water interfaces: A DFT Study