Photoelectron spectroscopy of small IBr−(CO2)n (n=–3) cluster anions

Sheps, Leonid; Miller, Elisa M.; Lineberger, W. C.

doi:10.1063/1.3200941

Cited by 25 publications

(33 citation statements)

References 46 publications

(66 reference statements)

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“…The heats of formation of all six compounds are well established; however, the electron affinities are not. Only IBr has a clearly determined electron affinity (2.512 ± 0.003 eV) [16], aside from a theoretical result for ClF (2.25 ± 0.10 eV) [17]. The uncertainty in the electron affinities has little effect on the present study, as in all cases dissociative electron attachment is exothermic and there is no possibility of stabilizing the parent anion under the relatively low-pressure conditions used in the present experiments.…”

Section: Introductionmentioning

confidence: 65%

Electron attachment to the interhalogen compounds ClF, ICl, and IBr

et al. 2016

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Thermal electron attachment rate coefficients for three interhalogen compounds (ClF, ICl, IBr) have been measured from 300 to 900 K at pressures of 1-2 Torr using a flowing afterglow-Langmuir probe apparatus. ClF attaches somewhat inefficiently (k = 7.5×10 −9 cm 3 s −1 ) at 300 K, with the rate coefficient rising to 1.7×10 −8 cm 3 s −1 at 700 K. At higher temperatures the apparent rate coefficient falls steeply; however, this is interpreted as an artifact due to decomposition on the walls of the inlet line. ICl attaches with even lower efficiency (k = 9.5×10 −10 cm 3 s −1 at 300 K) and a less steep increase with temperature. Attachment to IBr is too slow to confidently measure with the present experiment, with an upper limit on the rate coefficient of 10 −10 cm 3 s −1 from 300 to 600 K. Both ClF and ICl attach dissociatively to yield Cl − , likely exclusively, though F − or I − may be produced with limits of <2% and <5%, respectively. The ClF attachment was further explored through ab initio calculation of the ClF and ClF − potential energy curves and R-matrix calculations of the resonance parameters which were used then for calculations of the dissociative attachment cross sections and rate coefficients. While the magnitude of the attachment rate coefficient for ClF is similar to those for both Cl 2 and F 2 , the calculated cross sections show qualitatively different threshold behavior due to the s-wave contribution allowed by the lack of inversion symmetry. The v = 1 and 2 vibrational modes of ClF attach about three to four times faster than v = 0 and 3 at energies lower than ∼0.2 eV. The calculated rate coefficients are in good agreement with the experiment at 300 K and increase moderately less steeply with temperature.

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Section: Introductionmentioning

confidence: 65%

Electron attachment to the interhalogen compounds ClF, ICl, and IBr

et al. 2016

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“…47 Briefly, the anions of interest are produced in a dual pulsed valve plasma entrainment source, again from the deprotonation of methylphenol by reaction with OH¯. 48 This source uses two separate pulsed General Valves set perpendicular to each other.…”

Section: Experimental Methodsmentioning

confidence: 99%

Anion photoelectron spectroscopy of deprotonated ortho-, meta-, and para-methylphenol

Nelson

Gichuhi

Miller

et al. 2017

The Journal of Chemical Physics

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The anion photoelectron spectra of ortho-, meta-, and para-methylphenoxide, as well as methyl deprotonated meta-methylphenol, were measured. Using the Slow Electron Velocity Map Imaging (SEVI) technique, the Electron Affinities (EAs) of the o-, m-, and p-methylphenoxyl radicals were measured: 2.1991 ± 0.0014, 2.2177 ± 0.0014, and 2.1199 ± 0.0014 eV, respectively. The EA of mmethylenephenol was also obtained, 1.024 ± 0.008 eV. In all four cases, the dominant vibrational progressions observed are due to several ring distortion vibrational normal modes that were activated upon photodetachment, leading to vibrational progressions spaced by ~500 cm -1 . Using the

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“…The experimental apparatus has been described in detail previously, 25 so only a brief description follows. Anions are generated in a dual pulsed valve plasma entrainment ion source, 26 discussed further below.…”

Section: Experimental Methodsmentioning

confidence: 99%

Photoelectron spectroscopy of the thiazate (NSO−) and thionitrite (SNO−) isomer anions

Lehman

Lineberger

2017

The Journal of Chemical Physics

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Anion photoelectron spectra of the thiazate (NSO -) and thionitrite (SNO -) isomers are reported.The NSO -photoelectron spectrum showed several well resolved vibronic transitions from the anion to the NSO radical neutral. The electron affinity of NSO was determined to be 3.113(1) eV. The fundamental vibrational frequencies of NSO were measured and unambiguously assigned to be 1202(6) cm 1 ( 1 , asymmetric stretch), 1010(10) cm 1 ( 2 , symmetric stretch) and 300 (7) , the SNO -photoelectron spectrum was broad with little structure, indicative of a large geometry change between the anion and neutral radical. In addition to the spectrally congested spectrum, there was evidence of a competition between photodetachment from SNO -and SNO -photodissociation to form S -+ NO. Quantum chemical calculations were used to aid in the interpretation of the experimental data, and agree well with the observed photoelectron spectra, particularly for the NSO -isomer.

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Photoelectron spectroscopy of small IBr−(CO2)n (n=–3) cluster anions

Cited by 25 publications

References 46 publications

Electron attachment to the interhalogen compounds ClF, ICl, and IBr

Electron attachment to the interhalogen compounds ClF, ICl, and IBr

Anion photoelectron spectroscopy of deprotonated ortho-, meta-, and para-methylphenol

Photoelectron spectroscopy of the thiazate (NSO−) and thionitrite (SNO−) isomer anions

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