Magic cluster sizes of cationic and anionic sodium chloride clusters explained by statistical modeling of the complete phase space

Hartmann, Jessica C.; Madlener, Sarah J.; van der Linde, Christian; Ončák, Milan; Beyer, Martin K.

doi:10.1039/d4cp00357h

Cited by 2 publications

(2 citation statements)

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“…( 1). 38 This has the advantage that the channel is defined via the fragment stoichiometry alone. In this way, we connect the modeling directly with the experimental observation, avoiding any arbitrary assignments,…”

Section: Master Equation Modelingmentioning

confidence: 99%

“…The unimolecular dissociation rate constants are now calculated as described in Ref. 38; we call this new ansatz for the calculation of RRKM rates AWATAR for All Wells and All Transition states Are Relevant. It combines the density of states of all wells and the sum of states of all transition states, leading to a specific product in one rate constant.…”

Section: Introductionmentioning

confidence: 99%

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Master equation modeling of blackbody infrared radiative dissociation (BIRD) of hydrated peroxycarbonate radical anions

Salzburger,

Hütter,

van der Linde

et al. 2024

The Journal of Chemical Physics

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Molecular cluster ions, which are stored in an electromagnetic trap under ultra-high vacuum conditions, undergo blackbody infrared radiative dissociation (BIRD). This process can be simulated with master equation modeling (MEM), predicting temperature-dependent dissociation rate constants, which are very sensitive to the dissociation energy. We have recently introduced a multiple-well approach for master equation modeling, where several low-lying isomers are taken into account. Here, we experimentally measure the BIRD of CO4●–(H2O)1,2 and model the results with a slightly modified multiple-well MEM. In the experiment, we exclusively observe loss of water from CO4●–(H2O), while the BIRD of CO4●–(H2O)2 leads predominantly to loss of carbon dioxide, with water loss occurring to a lesser extent. The MEM of two competing reactions requires empirical scaling factors for infrared intensities and the sum of states of the loose transition states employed in the calculation of unimolecular rate constants so that the simulated branching ratio matches the experiment. The experimentally derived binding energies are ΔH0(CO4●––H2O) = 45 ± 3 kJ/mol, ΔH0(CO4●–(H2O)–H2O) = 41 ± 3 kJ/mol, and ΔH0(CO2–O2●–(H2O)2) = 37 ± 3 kJ/mol. Quantum chemical calculations on the CCSD(T)/aug-cc-pVTZ//CCSD/aug-cc-pVDZ level, corrected for the basis set superposition error, yield binding energies that are 2–5 kJ/mol higher than experiment, within error limits of both experiment and theory. The relative activation energies for the two competing loss channels are as well fully consistent with theory.

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Section: Master Equation Modelingmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Master equation modeling of blackbody infrared radiative dissociation (BIRD) of hydrated peroxycarbonate radical anions

Salzburger,

Hütter,

van der Linde

et al. 2024

The Journal of Chemical Physics

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Master equation modeling of water dissociation in small ionic water clusters: Ag⁺(H₂O)_n, n = 4–6

Hütter,

Schöpfer,

Salzburger

et al. 2024

RSC Adv.

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Magic cluster sizes of cationic and anionic sodium chloride clusters explained by statistical modeling of the complete phase space

Abstract: As one of the main components of sea salt aerosols, sodium chloride is involved in numerous atmospheric processes. Gas-phase clusters are ideal models to study fundamental physical and chemical properties...

Cited by 2 publications

References 54 publications

Master equation modeling of blackbody infrared radiative dissociation (BIRD) of hydrated peroxycarbonate radical anions

Master equation modeling of blackbody infrared radiative dissociation (BIRD) of hydrated peroxycarbonate radical anions

Master equation modeling of water dissociation in small ionic water clusters: Ag⁺(H₂O)_n, n = 4–6

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Magic cluster sizes of cationic and anionic sodium chloride clusters explained by statistical modeling of the complete phase space

Abstract: As one of the main components of sea salt aerosols, sodium chloride is involved in numerous atmospheric processes. Gas-phase clusters are ideal models to study fundamental physical and chemical properties...

Cited by 2 publications

References 54 publications

Master equation modeling of blackbody infrared radiative dissociation (BIRD) of hydrated peroxycarbonate radical anions

Master equation modeling of blackbody infrared radiative dissociation (BIRD) of hydrated peroxycarbonate radical anions

Master equation modeling of water dissociation in small ionic water clusters: Ag+(H2O)n, n = 4–6

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Master equation modeling of water dissociation in small ionic water clusters: Ag⁺(H₂O)_n, n = 4–6