Infrared Predissociation Vibrational Spectroscopy of Li+(H2O)3–4Ar0,1 Reanalyzed Using Density Functional Theory Molecular Dynamics

Brites, V.; Lisy, James M.; Gaigeot, Marie‐Pierre

doi:10.1021/jp508699m

Cited by 20 publications

(29 citation statements)

References 39 publications

(92 reference statements)

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“…This spectroscopic comparison is presented in ref. 53 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 …”

Section: Discussionmentioning

confidence: 99%

Stalking Higher Energy Conformers on the Potential Energy Surface of Charged Species

Brites

Cimas

Spezia

et al. 2015

J. Chem. Theory Comput.

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Combined theoretical DFT-MD and RRKM methodologies and experimental spectroscopic infrared predissociation (IRPD) strategies to map potential energy surfaces (PES) of complex ionic clusters are presented, providing lowest and high energy conformers, thresholds to isomerization, and cluster formation pathways. We believe this association not only represents a significant advance in the field of mapping minima and transition states on the PES but also directly measures dynamical pathways for the formation of structural conformers and isomers. Pathways are unraveled over picosecond (DFT-MD) and microsecond (RRKM) time scales while changing the amount of internal energy is experimentally achieved by changing the loss channel for the IRPD measurements, thus directly probing different kinetic and isomerization pathways. Demonstration is provided for Li(+)(H2O)3,4 ionic clusters. Nonstatistical formation of these ionic clusters by both direct and cascade processes, involving isomerization processes that can lead to trapping of high energy conformers along the paths due to evaporative cooling, has been unraveled.

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Section: Discussionmentioning

confidence: 99%

Stalking Higher Energy Conformers on the Potential Energy Surface of Charged Species

Brites

Cimas

Spezia

et al. 2015

J. Chem. Theory Comput.

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“…[1][2][3][4][5][6][7][8][9] Though the minimum energy structure tends to the focus in spectroscopic studies of clusters, the most preferred structure actually depends on the vibrational temperature of the cluster because higher energy structures can be dominant by the temperature-dependent entropy factor in the free energy. [1][2][3][4][5][6][7][8][9] Though the minimum energy structure tends to the focus in spectroscopic studies of clusters, the most preferred structure actually depends on the vibrational temperature of the cluster because higher energy structures can be dominant by the temperature-dependent entropy factor in the free energy.…”

Section: Iintroductionmentioning

confidence: 99%

“…The combination of these two techniques has also recently been employed to obtain a high and constant dissociation yield in dissociation spectroscopy of clusters in a 4 cold ion-trap. 4,[30][31][32][33][34][35][36] Methanol is also a typical protic solvent, and hydrogen-bond (H-bond) network structures of protonated methanol clusters, H + (MeOH) n , have been studied by infrared (IR) spectroscopy and density functional theory (DFT) calculations. 1-5, 8-11, 16-19, 22-29 Unexpected preference of isomer structures, which deviates from the assumption of the simple thermal equilibrium, has been found for the water network with the tagging, and its origin has not yet been fully clarified.…”

Section: Iintroductionmentioning

confidence: 99%

Hydrogen-bonded ring closing and opening of protonated methanol clusters H⁺(CH₃OH)_n (n = 4–8) with the inert gas tagging

Hamashima

Yamazaki

et al. 2015

Phys. Chem. Chem. Phys.

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The preferential hydrogen bond (H-bond) structures of protonated methanol clusters, H(+)(MeOH)n, in the size range of n = 4-8, were studied by size-selective infrared (IR) spectroscopy in conjunction with density functional theory calculations. The IR spectra of bare clusters were compared with those with the inert gas tagging by Ar, Ne, and N2, and remarkable changes in the isomer distribution with the tagging were found for clusters with n≥ 5. The temperature dependence of the isomer distribution of the clusters was calculated by the quantum harmonic superposition approach. The observed spectral changes with the tagging were well interpreted by the fall of the cluster temperature with the tagging, which causes the transfer of the isomer distribution from the open and flexible H-bond network types to the closed and rigid ones. Anomalous isomer distribution with the tagging, which has been recently found for protonated water clusters, was also found for H(+)(MeOH)5. The origin of the anomaly was examined by the experiments on its carrier gas dependence.

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“…65,66 Uncertainties as a result of the harmonic frequency approximation can also affect calculated Gibbs free energies, which may affect the relative energetic ordering of isomers presented here. The positions of water molecules around the strontium ion in these three isomers differ substantially, yet the antisymmetric stretching bands are similar, indicating that the antisymmetric stretching frequencies of these inner shell water molecules are not sensitive to their position around the ion pair.…”

Section: Structures Of [Mno 3 ] + (H 2 O)mentioning

confidence: 99%

Effects of electronic structure on the hydration of PbNO₃⁺ and SrNO₃⁺ ion pairs

Cooper

Heiles

Williams

2015

Phys. Chem. Chem. Phys.

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Hydration of PbNO3(+) and SrNO3(+) with up to 30 water molecules was investigated with infrared photodissociation (IRPD) spectroscopy and with theory. These ions are the same size, yet the IRPD spectra of these ion pairs for n = 2-8 are significantly different. Bands in the bonded O-H region (∼3000-3550 cm(-1)) indicate that the onset of a second hydration shell begins at n = 5 for PbNO3(+) and n = 6 for SrNO3(+). Spectra for [PbNO3](+)(H2O)2-5 and [SrNO3](+)(H2O)3-6 indicate that the structures of clusters with Pb(ii) are hemidirected with a void in the coordinate sphere. A natural bond orbital analysis of [PbNO3](+)(H2O)5 indicates that the anisotropic solvation of the ion is due to a region of asymmetric electron density on Pb(ii) that can be explained by charge transfer from the nitrate and water ligands into unoccupied p-orbitals on Pb(ii). There are differences in the IRPD spectra of PbNO3(+) and SrNO3(+) with up to 25 water molecules attached. IR intensity in the bonded O-H region is blue-shifted by ∼50 cm(-1) in nanodrops containing SrNO3(+) compared to those containing PbNO3(+), indicative of a greater perturbation of the water H-bond network by strontium. The free O-H stretches of surface water molecules in nanodrops containing 10, 15, 20, and 25 water molecules are red-shifted by ∼3-8 cm(-1) for PbNO3(+) compared to those for SrNO3(+), consistent with more charge transfer between water molecules and Pb(ii). These results demonstrate that the different electronic structure of these ions significantly influences how they are solvated.

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Infrared Predissociation Vibrational Spectroscopy of Li⁺(H₂O)_3–4Ar_0,1 Reanalyzed Using Density Functional Theory Molecular Dynamics

Cited by 20 publications

References 39 publications

Stalking Higher Energy Conformers on the Potential Energy Surface of Charged Species

Stalking Higher Energy Conformers on the Potential Energy Surface of Charged Species

Hydrogen-bonded ring closing and opening of protonated methanol clusters H⁺(CH₃OH)_n (n = 4–8) with the inert gas tagging

Effects of electronic structure on the hydration of PbNO₃⁺ and SrNO₃⁺ ion pairs

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Infrared Predissociation Vibrational Spectroscopy of Li+(H2O)3–4Ar0,1 Reanalyzed Using Density Functional Theory Molecular Dynamics

Cited by 20 publications

References 39 publications

Stalking Higher Energy Conformers on the Potential Energy Surface of Charged Species

Stalking Higher Energy Conformers on the Potential Energy Surface of Charged Species

Hydrogen-bonded ring closing and opening of protonated methanol clusters H+(CH3OH)n (n = 4–8) with the inert gas tagging

Effects of electronic structure on the hydration of PbNO3+ and SrNO3+ ion pairs

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Infrared Predissociation Vibrational Spectroscopy of Li⁺(H₂O)_3–4Ar_0,1 Reanalyzed Using Density Functional Theory Molecular Dynamics

Hydrogen-bonded ring closing and opening of protonated methanol clusters H⁺(CH₃OH)_n (n = 4–8) with the inert gas tagging

Effects of electronic structure on the hydration of PbNO₃⁺ and SrNO₃⁺ ion pairs