Gas-phase vibrational spectroscopy and ab initio calculations of Rb+(H2O)n and Rb+(H2O)nAr cluster ions

Nicely, Amy L.; Miller, Dorothy J.; Lisy, James M.

doi:10.1016/j.jms.2009.08.001

Cited by 21 publications

(57 citation statements)

References 19 publications

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“…This can be explained by considering that, due to its higher charge density, Li + is more effective in drawing electrons from the water molecule which, in turns, weakens the OH bonds and thus shifts the bending and (symmetric and asymmetric) stretching frequencies more to the blue and the red, respectively, compared to the other M + ions. In all cases, the LM vibrational frequencies are in good agreement with the available experimental values, [80][81][82] with deviation ranging from 20 to 30 cm −1 , depending on the ion. These differences may be due to a combination of different factors.…”

Section: Resultssupporting

confidence: 83%

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Isomeric Equilibria, Nuclear Quantum Effects, and Vibrational Spectra of M+(H2O)n=1−3 Clusters, with M = Li, Na, K, Rb, and Cs, Through Many-Body Representations

Riera¹,

Brown²,

Paesani³

2018

Preprint

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A quantitative characterization of the molecular mechanisms that regulate ion solvation is key to the microscopic understanding of fundamental processes taking place in aqueous environments, with major implications for different fields, from atmospheric chemistry to materials research and biochemistry. This study presents a systematic analysis of isomeric equilibria for small M + (H 2 O) n clusters, with M = Li, Na, K, Rb, and Cs, from 0 K to 200 K. To determine the relative stability of different isomers of 1 each M + (H 2 O) n cluster as a function of temperature, replica exchange simulations are carried out at both classical and quantum levels with the recently developed many-body MB-nrg potential energy functions, which have been shown to exhibit chemical accuracy. Anharmonic vibrational spectra are then calculated within the local monomer approximation and found to be in agreement with the available experimental data, providing further support for the accuracy of the MB-nrg potential energy functions.The present analysis indicates that nuclear quantum effects become increasingly important for larger M + (H 2 O) n clusters containing the heavier alkali metal ions, which is explained in terms of competing ion-water and water-water interactions along with the interplay between energetic and entropic effects. Directly connecting experimental measurements with molecular properties calculated at the quantum mechanical level, this study represents a further step toward the development of a consistent picture of ion hydration from the gas to the condensed phase.

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Section: Resultssupporting

confidence: 83%

Section: Resultsmentioning

confidence: 92%

Isomeric Equilibria, Nuclear Quantum Effects, and Vibrational Spectra of M+(H2O)n=1−3 Clusters, with M = Li, Na, K, Rb, and Cs, Through Many-Body Representations

Riera¹,

Brown²,

Paesani³

2018

Preprint

View full text Add to dashboard Cite

show abstract

“…Li + is more effective in drawing electrons from the water molecule which, in turns, weakens the OH bonds and thus shifts the bending and (symmetric and asymmetric) stretching frequencies more to the blue and the red, respectively, compared to the other M + ions. In all cases, the LM vibrational frequencies are in good agreement with the available experimental values, [80][81][82] with deviation ranging from 20 to 30 cm −1 , depending on the ion. These differences may be due to a combination of different factors.…”

Section: Computational Detailssupporting

confidence: 83%

“…For all clusters, good agreement is found between anharmonic vibrational spectra calculated within the local monomer approximation and the available experimental data. 41,[80][81][82] Besides providing further support for the accuracy of the MB-nrg PEFs, this level of agreement emphasizes the importance of taking properly into account anharmonic and quantum effects in computer simulations for a correct description of M + (H 2 O) n clusters. Importantly, the possibility to directly connect experimental measurements with computer simulations at the molecular level provides hope for the development of a consistent picture of ion hydration from the gas to the condensed phase.…”

Section: Discussionsupporting

confidence: 53%

“…Minor spectral features associated with "cyclic" isomers appear at temperature higher than 100 K. Overall, the calculated spectra are in agreement with the available experimental data. 41,82 However, it should be noted that the experimental spectra also display minor features above 3750 cm −1 corresponding to ∆K = ±1 rotational subbands of the water asymmetric stretching mode, 80 which, by construction, cannot be reproduced by the LM method. Table 3 shows that the relative Table 3).…”

Section: Computational Detailsmentioning

confidence: 92%

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Isomeric Equilibria, Nuclear Quantum Effects, and Vibrational Spectra of M+(H2O)n=1−3 Clusters, with M = Li, Na, K, Rb, and Cs, Through Many-Body Representations

Riera¹,

Brown²,

Paesani

2018

Preprint

View full text Add to dashboard Cite

<div> <div> <div> <p>A quantitative characterization of the molecular mechanisms that regulate ion solvation is key to the microscopic understanding of fundamental processes taking place in aqueous environments, with major implications for different fields, from atmospheric chemistry to materials research and biochemistry. This study presents a systematic analysis of isomeric equilibria for small M<sup>+</sup>(H<sub>2</sub>O)<sub>n</sub> clusters, with M = Li, Na, K, Rb, and Cs, from 0 K to 200 K. To determine the relative stability of different isomers of each M<sup>+</sup>(H<sub>2</sub>O)<sub>n </sub>cluster as a function of temperature, replica exchange simulations are carried out at both classical and quantum levels with the recently developed many-body MB-nrg potential energy functions, which have been shown to exhibit chemical accuracy. Anharmonic vibrational spectra are then calculated within the local monomer approximation and found to be in agreement with the available experimental data, providing further support for the accuracy of the MB-nrg potential energy functions. The present analysis indicates that nuclear quantum effects become increasingly im- portant for larger M<sup>+</sup>(H<sub>2</sub>O)<sub>n </sub>clusters containing the heavier alkali metal ions, which is explained in terms of competing ion-water and water-water interactions along with the interplay between energetic and entropic effects. Directly connecting experimental measurements with molecular properties calculated at the quantum mechanical level, this study represents a further step toward the development of a consistent picture of ion hydration from the gas to the condensed phase. </p> </div> </div> </div>

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From microhydration to bulk hydration of Rb+ metal ion: DFT, MP2 and AIMD simulation study

Boda

Ali

2013

Journal of Molecular Liquids

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Gas-phase vibrational spectroscopy and ab initio calculations of Rb+(H2O)n and Rb+(H2O)nAr cluster ions

Cited by 21 publications

References 19 publications

Isomeric Equilibria, Nuclear Quantum Effects, and Vibrational Spectra of M+(H2O)n=1−3 Clusters, with M = Li, Na, K, Rb, and Cs, Through Many-Body Representations

Isomeric Equilibria, Nuclear Quantum Effects, and Vibrational Spectra of M+(H2O)n=1−3 Clusters, with M = Li, Na, K, Rb, and Cs, Through Many-Body Representations

Isomeric Equilibria, Nuclear Quantum Effects, and Vibrational Spectra of M+(H2O)n=1−3 Clusters, with M = Li, Na, K, Rb, and Cs, Through Many-Body Representations

From microhydration to bulk hydration of Rb+ metal ion: DFT, MP2 and AIMD simulation study

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