Heavy Water Reactions with Atomic Transition-Metal and Main-Group Cations:  Gas Phase Room-Temperature Kinetics and Periodicities in Reactivity

Cheng, Ping; Koyanagi, Gregory K.; Böhme, Diethard K.

doi:10.1021/jp072661p

Cited by 49 publications

(66 citation statements)

References 71 publications

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“…Referring to the computed energetics for these hydrations (Table 4), the first hydration is more energetically favorable, as evaluated by both exothermicity (DH) and exoergicity (DG). Similar results-slower first addition than second addition-were reported and rationalized by Bohme and co-workers for NH 3 and D 2 O association with bare metal cations [47][48][49].…”

Section: Hydration Kineticssupporting

confidence: 89%

“…The reaction energies, enthalpies, . Such a precipitous decrease in binding energy from n = 2 to n = 3 has been observed previously for many transition metal ions, as recently summarized by Cheng et al [46,47]: for example, the Ti ? (H 2 O) n binding energies (in kJ mol -1 ) are 158 ± 6 for n = 1; 136 ± 5 for n = 2; and 69 ± 7 for n = 3.…”

Section: Hydration Energiessupporting

confidence: 73%

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Hydration of gas-phase ytterbium ion complexes studied by experiment and theory

et al. 2011

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Hydration of ytterbium (III) halide/hydroxide ions produced by electrospray ionization was studied in a quadrupole ion trap mass spectrometer and by density functional theory (DFT). Gas-phase YbX 2? and YbX(OH)?(X = OH, Cl, Br, or I) were found to coordinate from one to four water molecules, depending on the ion residence time in the trap. From the time dependence of the hydration steps, relative reaction rates were obtained. It was determined that the second hydration was faster than both the first and third hydrations, and the fourth hydration was the slowest; this ordering reflects a combination of insufficient degrees of freedom for cooling the hot monohydrate ion and decreasing binding energies with increasing hydration number. Hydration energetics and hydrate structures were computed using two approaches of DFT. The relativistic scalar ZORA approach was used with the PBE functional and all-electron TZ2P basis sets; the B3LYP functional was used with the Stuttgart relativistic small-core ANO/ ECP basis sets. The parallel experimental and computational results illuminate fundamental aspects of hydration of f-element ion complexes. The experimental observations-kinetics and extent of hydration-are discussed in relationship to the computed structures and energetics of the hydrates. The absence of pentahydrates is in accord with the DFT results, which indicate that the lowest energy structures have the fifth water molecule in the second shell.

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Section: Hydration Kineticssupporting

confidence: 89%

Section: Hydration Energiessupporting

confidence: 73%

Hydration of gas-phase ytterbium ion complexes studied by experiment and theory

et al. 2011

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“…The Bohme group has reported that As + reacts slowly with D 2 O and produces AsO + in only 10% of reactions. 10 Therefore, the observed AsO + signal requires a water impurity on the order of one part per thousand. A much more likely scenario is an O 2 impurity, which only needs to be present at one ppm to produce the observed AsO + .…”

Section: Impurity Analysesmentioning

confidence: 99%

Comment on “Role of (NO)₂ Dimer in Reactions of Fe⁺ with NO and NO₂ Studied by ICP-SIFT Mass Spectrometry”

et al. 2013

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“…7,15 Their experimental results showed that the reactions proceeded to one of the ensuing channels: (1) …”

Section: -19mentioning

confidence: 99%

“…Among these molecular systems, H 2 O as the simplest molecule having the O-H bond, serves as a good model to understand the O-H bond activation by lanthanide cations. For example, the reactions of H 2 O with many metal mono-cations have been plentifully investigated experimentally 7,14,15 and theoretically.…”

mentioning

confidence: 99%

Theoretical Investigation of the Reaction of Ce⁺with Water in the Gas Phase: Density Functional Theory Calculations

Hong

Kim

Kim³

2013

Bulletin of the Korean Chemical Society

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The importance of rare earth elements is growing in many areas, especially chemical catalysis, 1,2 metallurgy 3 and industrial field.4 Accordingly, gas-phase reactions of various organic compounds with lanthanide cations have been extensively investigated by spectroscopic experiments 5-10 and computational studies [11][12][13] 20,21In addition, the intersystem crossing (ISC) point is estimated by the single-point energy calculations along the reaction pathway. These results correlated to the recent experimental findings. 7,15We calculated the doublet and quartet PESs for the ionmolecule reaction of Ce + with H 2 O using DFT method, since these two states are very close in energy and may interconvert during the reaction. All molecular structures of the reaction species (reactants, intermediates, products, and transition states) were fully optimized using PBE0 hybrid DFT functional, 22 which are frequently used and gives reasonable results for lanthanide molecular systems.23-25 The unrestricted formalism (UPBE0) was used for all spin states. In particular, an open shell structure was used for the singlet spin states. We used the relativistic effective core potential (RECP) to treat the scalar relativistic effect for the lanthanide ion, Ce + . The small-core Stuttgart ECP28MWB 26,27 with the large atomic natural orbital (ANO) valence basis set ([6s6p5d4f 3g]) and 6-311++G(d,p) basis sets were used for the lanthanide ion (Ce + ) and other atoms (H and O), respectively. We also carried out the harmonic vibrational frequency calculation. All transition states were identified by one imaginary frequency and confirmed by using the intrinsic reaction coordinate (IRC) method.28,29 All relative energies included the zero-point energy (ZPE) correction for all reaction species. We also used the natural population analysis (NPA) 30 for characterizing atomic charge and electronic structure. All calculations were carried out using the Gaussian 03 program. 31All optimized geometries of both doublet and quartet spin states and the reaction PESs regarding to the reactions of Ce + with H 2 O are shown in Figures 1 and 2, respectively. The initiation step of the reaction is the association complex formation in both spin states. As shown in Figure 1, Ce + moves toward the electron rich oxygen atom of the water to form an initial intermediate, IM 1 in both spin states. This result can be readily expected due to the electronegativity of

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Heavy Water Reactions with Atomic Transition-Metal and Main-Group Cations: Gas Phase Room-Temperature Kinetics and Periodicities in Reactivity

Cited by 49 publications

References 71 publications

Hydration of gas-phase ytterbium ion complexes studied by experiment and theory

Hydration of gas-phase ytterbium ion complexes studied by experiment and theory

Comment on “Role of (NO)₂ Dimer in Reactions of Fe⁺ with NO and NO₂ Studied by ICP-SIFT Mass Spectrometry”

Theoretical Investigation of the Reaction of Ce⁺with Water in the Gas Phase: Density Functional Theory Calculations

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Heavy Water Reactions with Atomic Transition-Metal and Main-Group Cations: Gas Phase Room-Temperature Kinetics and Periodicities in Reactivity

Cited by 49 publications

References 71 publications

Hydration of gas-phase ytterbium ion complexes studied by experiment and theory

Hydration of gas-phase ytterbium ion complexes studied by experiment and theory

Comment on “Role of (NO)2 Dimer in Reactions of Fe+ with NO and NO2 Studied by ICP-SIFT Mass Spectrometry”

Theoretical Investigation of the Reaction of Ce+with Water in the Gas Phase: Density Functional Theory Calculations

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Comment on “Role of (NO)₂ Dimer in Reactions of Fe⁺ with NO and NO₂ Studied by ICP-SIFT Mass Spectrometry”

Theoretical Investigation of the Reaction of Ce⁺with Water in the Gas Phase: Density Functional Theory Calculations