Revisiting the Hydration of Pb(II): A QMCF MD Approach

Bhattacharjee, Anirban; Hofer, Thomas S.; Pribil, Andreas B.; Randolf, Bernhard R.; Lim, Len Herald V.; Lichtenberger, Andreas; Rode, Bernd M.

doi:10.1021/jp905848x

Cited by 47 publications

(41 citation statements)

References 40 publications

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“…ref. [45][46][47]. EXAFS experiments indicate a hemidirected, six-coordinated structure with an average Pb-O distance of 2.54(1) Å.…”

Section: Pb 2+ Ions In Water Solutionsmentioning

confidence: 99%

“…46 In contrast, the most recent molecular dynamics study of aqueous lead ions predicts a coordination number between seven and ten, with a strong predominance of an eightcoordination structure, followed by a nine-coordination structure. 47 It appears that the observed structure of the Pb 2+ -water complexes may strongly depend on the timescale of the experiment. Thus, in order to estimate the NMR shielding constant for Pb 2+ in aqueous solution, we have considered the Pb 2+ -water clusters with coordination number n c = 6, 7, 8, 9. The geometries of the complexes were optimized using secondorder Møller-Plesset perturbation theory (MP2) using a 60-electron effective core potential cc-pVQZ-PP for Pb 48,49 and the corresponding Dunning's cc-pVQZ basis set 50 for O and H, keeping the oxygen core electrons frozen.…”

Section: Pb 2+ Ions In Water Solutionsmentioning

confidence: 99%

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NMR absolute shielding scale and nuclear magnetic dipole moment of ²⁰⁷Pb

Adrjan

Makulski

Jackowski

et al. 2016

Phys. Chem. Chem. Phys.

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An absolute shielding scale is proposed for (207)Pb nuclear magnetic resonance (NMR) spectroscopy. It is based on ab initio calculations performed on an isolated tetramethyllead Pb(CH3)4 molecule and the assignment of the experimental resonance frequency from the gas-phase NMR spectra of Pb(CH3)4, extrapolated to zero density of the buffer gas to obtain the result for an isolated molecule. The computed (207)Pb shielding constant is 10 790 ppm for the isolated molecule, leading to a shielding of 10799.7 ppm for liquid Pb(CH3)4 which is the accepted reference standard for (207)Pb NMR spectra. The new experimental and theoretical data are used to determine μ((207)Pb), the nuclear magnetic dipole moment of (207)Pb, by applying the standard relationship between NMR frequencies, shielding constants and nuclear moments of two nuclei in the same external magnetic field. Using the gas-phase (207)Pb and (reference) proton results and the theoretical value of the Pb shielding in Pb(CH3)4, we find μ((207)Pb) = 0.59064 μN. The analysis of new experimental and theoretical data obtained for the Pb(2+) ion in water solutions provides similar values of μ((207)Pb), in the range of 0.59000-0.59131 μN.

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“…ref. [45][46][47]. EXAFS experiments indicate a hemidirected, six-coordinated structure with an average Pb-O distance of 2.54(1) Å.…”

Section: Pb 2+ Ions In Water Solutionsmentioning

confidence: 99%

Section: Pb 2+ Ions In Water Solutionsmentioning

confidence: 99%

NMR absolute shielding scale and nuclear magnetic dipole moment of ²⁰⁷Pb

Adrjan

Makulski

Jackowski

et al. 2016

Phys. Chem. Chem. Phys.

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“…The usefulness of a QM description becomes evident when treating systems exhibiting an anisotropic potential such as the transition-metal ions copper(II) [61], palladium(II) [62], and platinum(II) [63] and systems carrying lone-electron pairs, e.g., germanium(II) [64], tin(II) [65], and lead(II) [66] (see Fig. 2a and b).…”

Section: Introductionmentioning

confidence: 99%

Perspectives for hybrid ab initio/molecular mechanical simulations of solutions: from complex chemistry to proton-transfer reactions and interfaces

Hofer

2014

Pure and Applied Chemistry

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As a consequence of the ongoing development of enhanced computational resources, theoretical chemistry has become an increasingly valuable field for the investigation of a variety of chemical systems. Simulations employing a hybrid quantum mechanical/molecular mechanical (QM/MM) molecular dynamics (MD) technique have been shown to be a particularly promising approach, whenever ultrafast (i.e., picosecond) dynamical properties are to be studied, which are in many cases difficult to access via experimental techniques. Details of the quantum mechanical charge field (QMCF) ansatz, an advanced QM/MM protocol, are discussed and simulation results for various systems ranging from simple ionic hydrates to solvated organic molecules and coordination complexes in solution are presented. A particularly challenging application is the description of proton-transfer reactions in chemical simulations, which is a prerequisite to study acidified and basic systems. The methodical requirements for a combination of the QMCF methodology with a dissociative potential model for the description of the solvent are discussed. Furthermore, the possible extension of QM/MM approaches to solid/liquid interfaces is outlined.

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“…[18,19] , 然而众多力场 (compass, pcff, cvff 等)中缺乏 Pb(II)的参数设置, 对于目前涉及元素最广的 universal 力场而言, 在求"全"的同时又失了"精" [20] , 因此, 第一性原理分子动力学成为不可替代的选择之一. 本文采用基于密度泛函理论的第一性原理研究 Pb(H O) [15,17] . [16] 接近, 较 QMCF 方法 [17] 稍低.…”

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“…本文采用基于密度泛函理论的第一性原理研究 Pb(H O) [15,17] . [16] 接近, 较 QMCF 方法 [17] 稍低. 实验方面由 EXAFS 和 LAXS 得出 Pb-O 键长 2.54 Å [13] , 略低于 6 配位的平均 Table 1 Equilibrium geometrical structural parameters and binding energy of 2 2 Pb …”

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