Reactivity of molecular clusters in the gas phase:  proton-transfer reaction in neutral phenol-(ammonia)n and phenol-(ethanamine)n

Jouvet, Christophe; Lardeux‐Dedonder, C.; Richard‐Viard, M.; Solgadi, D.; Tramer, A.

doi:10.1021/j100375a051

Cited by 122 publications

(84 citation statements)

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“…The most favorable pathway is expected to be proton transfer to neutral matrix. The thermodynamics of this can be estimated as follows: 44,55 The matrix basicity is typical of several matrices. 14,29,56,57 This reaction will efficiently reduce C2 complexes to the C1 state, but will not neutralize AMe C , because the first and last partial reactions are about half as energetic:…”

Section: 34mentioning

confidence: 99%

Secondary ion-molecule reactions in matrix-assisted laser desorption/ionization

et al. 2000

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Ion-molecule charge- and proton-transfer reactions in the desorption plume are considered for the case of matrix-assisted laser desorption/ionization (MALDI) with ultraviolet laser excitation, and it is proposed that they are major determinants of the observed mass spectrum. Specific MALDI phenomena which are discussed include the dominance of singly charged ions and analyte-matrix or analyte-analyte signal suppression. Should any be formed, highly charged products can be reduced by reaction with neutral matrix, yet singly charged ions cannot generally be neutralized in the same manner. Ion suppression effects can also be explained by similar reactions, which in some cases involve interconversion of dissimilar ion types. The plume is proposed often to be more under thermodynamic rather than kinetic control owing to these secondary reactions. UV/MALDI mass spectra should therefore be largely predictable, given sufficient thermodynamic information, and appropriate experimental conditions of sufficient analyte and plume density. Copyright 2000 John Wiley & Sons, Ltd.

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Section: 34mentioning

confidence: 99%

Secondary ion-molecule reactions in matrix-assisted laser desorption/ionization

et al. 2000

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“…The output of a dye laser (Lumonics, HD-500) pumped by 355 nm radiation of a Nd The principle of picosecond time-resolved UV-IR-UV ion dip spectroscopy has also been described elsewhere. [49][50] Briefly, the FPhOH-(NH 3 ) 3 cluster is excited to S 1 by a picosecond UV laser, n UV , and the hydrogen transfer starts (Figure 1 b). The final reaction product, ·NH 4 (NH 3 ) 2 , is ionized by a nanosecond UV laser, n ion , which is irradiated 50 ns after n UV and the population of the reaction product is monitored as the mass peak of NH 4 + (NH 3 ) 2 .…”

Section: Methodsmentioning

confidence: 99%

“…It was found from the generation of a long-lived neutral species after photoexcitation of phenol-(NH 3 ) n clusters. [16][17] The electronic and vibrational transitions of the long-lived species have been measured by UVnear IR-UV and UV-IR-UV ion dip spectroscopy, and the generation of a neutral radical cluster ·NH 4 (NH 3 ) nÀ1 has been assigned without ambiguity. [18][19][20] The mass spectrometric studies of delayed ionization, [16] vacuum UV ionization, [17] and spectroscopy on the reaction products [18][19][20] have been employed to establish the existence of ESHT.…”

Section: Introductionmentioning

confidence: 99%

“…[46] So far, FPhOH-(NH 3 ) n clusters show relatively moderate change in electronic states, however a significant change of the ESHT reaction rate is expected. Therefore, FPhOH-(NH 3 ) n clusters provide a good benchmark to understand the ESHT reaction mechanism in detail. The time evolution of ESHT in the FPhOH-(NH 3 ) n clusters must be measured to understand the reaction mechanism.…”

Section: Introductionmentioning

confidence: 99%

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Hole‐Burning Spectra of m‐Fluorophenol/Ammonia (1:3) Clusters and Their Excited State Hydrogen Transfer Dynamics

et al. 2011

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Hole-burning spectra of m-fluorophenol/ammonia (1:3) clusters are measured by four-color UV-near IR-UV-UV hole-burning spectroscopy. Cis and trans isomers of the cluster are clearly distinguished in the (1:3) cluster. Picosecond time evolutions of the excited state hydrogen transfer (ESHT) reaction in the (1:3) clusters are measured by the ion depletion due to 3p-3s Rydberg transition of reaction products ⋅NH(4)(NH(3))(2) lying in the near infrared region. From the wavelength dependence of the time evolution, we have concluded 1) the initial formation of a metastable ⋅NH(4)-NH(3)-NH(3) radical and 2) successive isomerization to the most stable NH(3)-⋅NH(4) -NH(3) radical in both cis and trans isomers. The reaction lifetimes of ESHT are determined by the rate equation analysis as 32.4 and 31.8 ps for the cis and trans isomer, respectively, and the isomerization and its back-reaction lifetime of both isomers are determined to be 3.3 ps and 11.2 ps. The almost same reaction rates are consistent with the similarity of the hydrogen bond networks in both clusters.

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“…Recently it has been shown that the reaction proton transfer takes place in the electronically excited state of the neutral clusters formed in free jetcooled supersonic expansion [3] or isolated in low temperature rare gas matrices [4]. Besides, recent studies in matrices showed that a large class of hydrogen bonded systems involving HI as proton donor were IR photosensitive (Refs [5,6] and others cited therein).…”

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confidence: 99%

Infrared induced conformational change in the two strong hydrogen bonded complexes 2-1 between dimethyl ether and hydrogen iodide in nitrogen matrix

Schriver¹,

Racine²,

Schrems³

et al. 1994

Spectrochimica Acta Part A: Molecular Spectroscopy

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Ahatraet-The IR spectra of the complexes between dimethylether (DME) and hydrogen iodide in nitrogen matrices were reinvestigated with careful attention to the temperature and IR radiation effects upon the higher aggregates. Irradiation using a broad band IR source was found weakly active leading to a nearly stationary population of the two (DME)r HT species. Irradiation with CO* laser lines induced a conformational interconversion of both aggregates to non-hydrogen-bonded forms. The breaking of the strong hydrogen bond was principally governed by irradiation in the range 2600-15OOcn-' corresponding to the dCHp region whereas the reverse process was observed by increasing temperature above 27 K under the annealing limit or irradiation below llOOcm-'. No accurate evidence was found for the occurrence of photochemical proton transfer between the centrosymmetrical and asymmetrical cations characterizing the two investigated complexes.THE PROTON transfer process between two interacting molecules is one of the most interesting problems in the hydrogen bonding phenomenon. It is governed both by the proton affinities of the opposing groups (Ref.[l] and others cited therein) and by environmental effects [2]. Recently it has been shown that the reaction proton transfer takes place in the electronically excited state of the neutral clusters formed in free jetcooled supersonic expansion [3] or isolated in low temperature rare gas matrices [4]. Besides, recent studies in matrices showed that a large class of hydrogen bonded systems involving HI as proton donor were IR photosensitive (Refs [5,6] and others cited therein). In this view, it could be expected that a single quantum of excitation of a (B),(HI), cluster vibrational mode could induce proton motion by a structural change in a part of the cluster as was recognized by the end of the 1970s [7,8]. In this paper, we explore this idea showing the effects of monochromatic CO* laser or broad band (globar) irradiation on the two strong hydrogen bonded 2-l complexes involving dimethylether (DME) and hydrogen iodide, previously identified in nitrogen matrices as ion pairs (DME)*H+I- [9]. The first one, IR photosensitive, was characterized by a centrosymmetrical potential function for the proton, whereas the second one showed a proton potential function probably of the symmetrical double minimum type. The one-to-one complex was not accurately identified but it was not surprising as since that time it has been observed that complexes of HI with weak to medium strength bases quickly dissociate in the beam of the spectrometer at low temperature [6]. Also we briefly reinvestigated the DME-HI system trapped in nitrogen, and then we give results on the irradiation of the two cations (DME)*H+I-.

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Reactivity of molecular clusters in the gas phase: proton-transfer reaction in neutral phenol-(ammonia)n and phenol-(ethanamine)n

Cited by 122 publications

References 0 publications

Secondary ion-molecule reactions in matrix-assisted laser desorption/ionization

Secondary ion-molecule reactions in matrix-assisted laser desorption/ionization

Hole‐Burning Spectra of m‐Fluorophenol/Ammonia (1:3) Clusters and Their Excited State Hydrogen Transfer Dynamics

Infrared induced conformational change in the two strong hydrogen bonded complexes 2-1 between dimethyl ether and hydrogen iodide in nitrogen matrix

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