Competition between electron detachment and monomer evaporation in the thermal destruction of hydrated electron clusters

Arnold, Susan T.; Morris, Robert; Viggiano, Albert A.

doi:10.1063/1.470035

Cited by 51 publications

(45 citation statements)

References 22 publications

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“…For n o 30, blackbody radiation induced electron detachment occurs, which interferes with the quantitative analysis. 33,44 Thus all quantitative fits are stopped when the lower end of the cluster size distribution reaches n = 30. Fig.…”

Section: Methodsmentioning

confidence: 99%

The reaction of CF₂Cl₂ with gas-phase hydrated electrons

Lengyel

Linde

Fárnı́k

et al. 2016

Phys. Chem. Chem. Phys.

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The reaction of dichlorodifluoromethane (CF2Cl2) with hydrated electrons (H2O)n(-) (n = 30-86) in the gas phase was studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. The hydrated electron reacts with CF2Cl2, forming (H2O)mCl(-) with a rate constant of (8.6 ± 2.2) × 10(-10) cm(3) s(-1), corresponding to an efficiency of 57 ± 15%. The reaction enthalpy was determined using nanocalorimetry, revealing a strongly exothermic reaction with ΔHr(CF2Cl2, 298 K) = -208 ± 41 kJ mol(-1). The combination of the measured reaction enthalpy with thermochemical data from the condensed phase yields a C-Cl bond dissociation enthalpy (BDE) ΔHC-Cl(CF2Cl2, 298 K) = 355 ± 41 kJ mol(-1) that agrees within error limits with the predicted values from quantum chemical calculations and published BDEs.

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Section: Methodsmentioning

confidence: 99%

The reaction of CF₂Cl₂ with gas-phase hydrated electrons

Lengyel

Linde

Fárnı́k

et al. 2016

Phys. Chem. Chem. Phys.

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“…Since the adiabatic electron affinity of (H 2 O) 6 is much smaller than the OH stretching quanta, 17 the IR spectrum in this region can be acquired by vibrational autodetachment spectroscopy 18 as reported earlier. 9 Unfortunately, since the vertical detachment energy ͑VDE͒ of (H 2 O) 6 Ϫ is only 3900 cm Ϫ1 , 10,11 the low energy electron continuum can also be directly accessed upon excitation throughout the 3000-4000 cm Ϫ1 region due to the large breadth of the binding energy distribution as displayed by the width ͑Ϸ0.4 eV͒ of the photoelectron band.…”

Section: Methodsmentioning

confidence: 99%

Vibrational predissociation spectroscopy of the (H2O)6−⋅Arn, n⩾6, clusters

Ayotte¹,

Bailey²,

Kim³

et al. 1998

The Journal of Chemical Physics

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Solvation of (H2O)6− with several argon atoms suppresses the strong direct photodetachment background in the bare hexamer anion, allowing vibrational predissociation spectroscopy to be carried out in a background-free regime. In addition to the previously reported autodetaching resonances [C. G. Bailey, J. Kim, and M. A. Johnson, J. Phys. Chem. 100, 16782 (1996)] in the single donor hydrogen bonding region (∼3300 cm−1), the predissociation spectra reveal many weak bands scattered throughout the mid infrared (3200–3750 cm−1). Most of these new bands are evident in the bare hexamer spectrum after signal averaging, indicating that they are isolated using predissociation but not induced by solvation. The most intense bands display much stronger redshifts (>30 cm−1 by n=15) than the matrix shifts typically found for the neutral water clusters, indicating that these bands are unique to the negative ion.

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“…9 Briefly, ions were formed by expanding a mixture of H 2 O and Ar, held at about 4 atm, through a 25 µm orifice and then ionizing the gas just downstream of the expansion with an electron filament (ThO 2 / Ir). To form larger clusters, the source was heated to 60-70°C to increase the percentage of H 2 O vapor in the expansion.…”

Section: Methodsmentioning

confidence: 99%

“…9 In this paper we report on various effects of solvation, isotopic substitution, and temperature on the reactions of OH -(H 2 O) n)0-4 with CH 3 Br. We have studied the temperature dependence of the rate constant and the branching fraction for n ) 0-2.…”

Section: Introductionmentioning

confidence: 99%

Temperature Dependences of the Rate Constants and Branching Ratios for the Reactions of OH^-(H₂O)₀_-₄ + CH₃Br

Viggiano¹,

Arnold²,

Morris³

et al. 1996

J. Phys. Chem.

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Various effects of solvation, isotopic substitution, and temperature on the reactions of OH -(H 2 O) n)0-4 with CH 3 Br are reported. Increasing solvation is found to decrease reactivity dramatically as has been observed previously. For n ) 0 the rate constant is large, and the temperature dependence is small, T -0.58 ; Br -is the only product. For n ) 1 the rate constant is about a factor of 1.5 smaller than that for the n ) 0 reaction, and the temperature dependence is T -1.6 . This reaction produces about 90% Br -and 10% Br -(H 2 O), with this ratio roughly independent of temperature. The rate constant for the n ) 2 reaction is almost 2 orders of magnitude lower than that for n ) 1. The n ) 2 reaction is complicated in that the low-temperature behavior depends on the identity of the buffer gas. In a He buffer at all temperatures, only Br -and Br -(H 2 O) products are observed, while in a H 2 buffer another product, OH(H 2 O) 2 CH 3 Br -, is observed at low temperatures in addition to the above products. The temperature dependence of this reaction is flat in a He buffer over the entire experimental temperature range and in a H 2 buffer in the range 300 K and above. The temperature dependence in a H 2 buffer is about T -4 for temperatures below 300 K. The n ) 3 reaction is about a factor of 10 slower than the n ) 2 reaction at 163 K and proceeds entirely by association. For n ) 4 an upper limit for the rate constant of k e 2 × 10 -13 cm 3 s -1 is found at 163 K. For the reaction of OH -(H 2 O) with CH 3 Br eight isotopic variants were studied: OH -(H 2 O) with 0-3 deuterium atoms and both CH 3 Br and CD 3 Br. No isotopic effect was found between CD 3 Br and CH 3 Br. For OH -(H 2 O) isotopic substitution, the reactivity order was H 2 DO 2 -g HD 2 O 2 -> H 3 O 2 -g D 3 O 2 -. The ions group into two categories: those incorporating both hydrogen and deuterium and those with only hydrogen or deuterium. The former group was found to react about 10% more rapidly than the latter group.

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Competition between electron detachment and monomer evaporation in the thermal destruction of hydrated electron clusters

Cited by 51 publications

References 22 publications

The reaction of CF₂Cl₂ with gas-phase hydrated electrons

The reaction of CF₂Cl₂ with gas-phase hydrated electrons

Vibrational predissociation spectroscopy of the (H2O)6−⋅Arn, n⩾6, clusters

Temperature Dependences of the Rate Constants and Branching Ratios for the Reactions of OH^-(H₂O)₀_-₄ + CH₃Br

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Competition between electron detachment and monomer evaporation in the thermal destruction of hydrated electron clusters

Cited by 51 publications

References 22 publications

The reaction of CF2Cl2 with gas-phase hydrated electrons

The reaction of CF2Cl2 with gas-phase hydrated electrons

Vibrational predissociation spectroscopy of the (H2O)6−⋅Arn, n⩾6, clusters

Temperature Dependences of the Rate Constants and Branching Ratios for the Reactions of OH-(H2O)0-4 + CH3Br

Contact Info

Product

Resources

About

The reaction of CF₂Cl₂ with gas-phase hydrated electrons

The reaction of CF₂Cl₂ with gas-phase hydrated electrons

Temperature Dependences of the Rate Constants and Branching Ratios for the Reactions of OH^-(H₂O)₀_-₄ + CH₃Br