HE(I) Photoelectron spectra of 1,2-ethanediol in the liquid and gas phases

Ballard, R.E.; Barker, Simon; Gunnell, J.J.; Hagan, W.P.; Pearce, S.J.; West, Robert.; Saunders, A.R.

doi:10.1016/0368-2048(78)80007-3

Cited by 15 publications

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“…Microscopic structures and behaviors of molecules on a liquid surface have been studied by photoelectron spectroscopy. Siegbahn et al have prepared a liquid flow in vacuum and measured a kinetic energy distribution of X-ray photoelectrons. − Delahay et al − and Ballard et al. − have observed electronic structures of the molecules in the vicinity of a liquid surface by ultraviolet photoelectron spectroscopy. Penning electron spectra of the outermost layer of a liquid surface of formamide have also been measured by Morgner et al , On the other hand, Faubel et al have measured a kinetic energy distribution of molecules evaporating from a liquid surface and elucidated that they are forced by a local strain exerted each other. , Nathanson et al have measured a scattering process of rare gas atoms on a liquid surface and argued how atoms stick to, rebound from, and exchange energy with the molecules on the liquid surface. , …”

Section: Introductionmentioning

confidence: 99%

Ion−Molecule Reactions in a Liquid Beam of Methanol, Ethanol, and 1-Propanol following Multiphoton Ionization

1996

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Methanol, ethanol, or 1-propanol was introduced into vacuum as a continuous liquid flow (liquid beam) and was subjected to nonresonant multiphoton ionization under irradiation of a 270 nm laser. Ions ejected into vacuum were mass-analyzed by means of time-of-flight mass spectrometry, where the ions were extracted by a static electric field, or a pulsed electric field with a delay time of ∼1.6 µs with respect to a pulse laser. Ions, H + (ROH) n (n g 1), were dominantly produced by ion-molecule reactions in the liquid beam. On the other hand, H + (CH 3 ) 2 O was interpreted to be produced by unimolecular dissociation of H + (CH 3 OH) 2 in the gas phase, and its rate constant was estimated to be (5 ( 3) × 10 4 s -1 . This small rate constant suggests that the internal energy of the H + (CH 3 OH) 2 is dissipated efficiently into the liquid, so that the rate constant is much smaller than that for the same process in H + (CH 3 OH) 2 produced by ionization of a gas phase cluster. In addition, the fragment ions, H + and C + , having similar kinetic energies of ∼8 eV are considered to be produced by a multiphoton process.

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Section: Introductionmentioning

confidence: 99%

Ion−Molecule Reactions in a Liquid Beam of Methanol, Ethanol, and 1-Propanol following Multiphoton Ionization

1996

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“…2 in [12] yielded the higher value of Et = 9.0 eV. The difference between the energies in [11] and [12] was ascribed in [13] to an inadequate determination of the zero of kinetic energy in [12]. The abscissa of 21.2 eV in Fig.…”

Section: Ionization Energies Energy Distribution Curvesmentioning

confidence: 99%

“…Brodsky has argued [9,10] that experimental EDC's of liquids obtained by the retarding potential method essentially satisfy the foregoing conditions. Table 1 is possible only for ethylene alycol on the basis of the EDC's in [11,12] Table I. Conversely, Fig.…”

Section: Ionization Energies Energy Distribution Curvesmentioning

confidence: 99%

“…The abscissa of 21.2 eV in Fig. 2 of [12] corresponds to the peak of the EDC whereas one would expect the zero of kinetic energy to be at the midpoint of the ascending branch of the EDC. This is indeed the case for Fig.…”

Section: Ionization Energies Energy Distribution Curvesmentioning

confidence: 99%

“…The SDC of 2-ethyl-l-hexanol is comparable to the gas-phase UPS spectrum of pentanol [20] inasmuch as the first peak is followed by a very broad band consisting of overlapping bands typical of alcohols. The SDC of ethylene glycol exhibits two maxima separated by 0.63 eV whereas the first two gas-phase ionization energies differ by 0.67 eV [12,21]. The SDC of tetraglyme may be compared with the gas-phase UPS spectrum of ethylene glycol dimethyl ether because of the similarity in structure, namely H(CH 2 OCH 2 ) 5 H (tetraglyme) and …”

Section: Second Derivative Curves and Correlation With Gas-phase Ups mentioning

confidence: 99%

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Ionization energies of liquids from energy distribution, quantum yield and second derivative curves

Cheung

Watanabe

Dziedzic

et al. 1985

Journal of Electron Spectroscopy and Related Phenomena

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Rearrangement of ethane‐1,2‐diol radical cations: Processes involving dipole‐catalyzed proton shifts and charge transfer

Ruttink

Burgers²

1993

Org. Mass Spectrom.

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Rearrangement and dissociation processes of solitary ethane-1,Zdiol radical cations were investigated by ab in& MO calculations, executed at the SDCI//RHF/DZP level of theory, including Pople-type size-consistency corrections. In order to obtain an accurate description of the chemistry involved, part of the potential energy surface was investigated by using the multi-reference CI method and also by using the valence bond (VB) method followed by SDCI calculations using the natural orbitals of the VB wavefunction. The ethane-l,2diol radical cation is metastable with respect to CH30HZ+ + HCO'; it has been shown recently that the isotopologue DOCH,CH,OD loses (exclusively) H C O to produce CH,DOHD+, not the isotopomer CH30D,+ expected from earlier mechanistic proposals. We have traced a low-energy pathway which explains the observed label distribution and which takes place at the experimentally derived energy level. First, ionized ethane-1,Zdiol collapses to the one-electron bond species [ HOCH, . . + *. . CH,OH I +. which subsequently rearranges to the hydrogen-bonded species CH,=O.*-HO(H)CH:'.Next, transformation to the transient CH,=O.*.HCH,OH+' takes effect and this rearrangement can be viewed as the 1,Zhydrogen shift, CH,OHi' + CH30H+', catalyzed by formaldehyde. Following this, charge transfer takes place from the methanol cation to the formaldehyde molecule which thus becomes charged; because it is now charged, the formaldehyde unit can rotate and donate a proton to the methanol molecule, after which dissociation follows. Our calculations and experimental results can be interpreted in terms of proton shifts rather than hydrogen shifts taking place in ion-molecule (proton-bound) complexes. Ab inilio calculations indicated that these intermediate ion-dipole complexes (hydrogen-bridged structures)enjoy considerable stability (they lie below ions CH20HCH20H+'), making them attractive intermediates. However, attempts to locate the corresponding transition state failed.5A different mechanistic proposal came from the Radom group.7 They showed from ab initio calculations that ethane-1,2-diol ions, 1, produced by vertical ionization (la) spontaneously undergo an intramolecular proton migration to produce the drstonic ion 'OCH2CH20H2+, 2, which was calculated to lie 69 kJ mol-below ions la. The adiabatic ionization energy (IE,) of ethane-1,2-diol' was proposed to correspond to the formation of structure 2.' The latter ions were proposed to dissociate via a 1,2-hydrogen shift to CH,OH,+ + HCO'. Note that both mechanisms

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HE(I) Photoelectron spectra of 1,2-ethanediol in the liquid and gas phases

Cited by 15 publications

References 15 publications

Ion−Molecule Reactions in a Liquid Beam of Methanol, Ethanol, and 1-Propanol following Multiphoton Ionization

Ion−Molecule Reactions in a Liquid Beam of Methanol, Ethanol, and 1-Propanol following Multiphoton Ionization

Ionization energies of liquids from energy distribution, quantum yield and second derivative curves

Rearrangement of ethane‐1,2‐diol radical cations: Processes involving dipole‐catalyzed proton shifts and charge transfer

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