Isomeric [C,H3,N,O]+˙ ions and their neutral counterparts

The isomeric ions [H₂NC(H)O]⁺˙, [H₂NCOH]⁺˙, [H₃CNO]⁺˙ and [H₂CNOH]⁺˙ were examined in the gas phase by mass spectrometry. Ab initio molecular orbital theory was used to calculate the relative stabilities of [H₂NC(H)O]⁺˙, [H₂NCOH]⁺˙, [H₃NCO]⁺˙ and their neutral counterparts. Theory predicted [H₂NC(H)O]⁺˙ to be the most stable ion. [H₂NCOH]⁺˙ ions were generated via a 1,4-hydrogen transfer in [H₂NC(O)OCH₃]⁺˙, [H₂NC(O)C(O)OH]⁺˙ and [H₂NC(O)CH₂CH₃]⁺˙. Its metastable dissociation takes place via [H₃NCO]⁺˙ with the isomerization as the rate-determining step. [H₂CNOH]⁺˙ undergoes a rate-determining isomerization into [H₃CNO]⁺˙ prior to metastable fragmentation. Neutralization-reionization mass spectrometry was used to identify the neutral counterparts of these [H₃,C,N,O]⁺˙ ions as stable species in the gas phase. The ion [H₃NCO]⁺˙ was not independently generated in these experiments; its neutral counterpart was predicted by theory to be only weakly bound.     

Mobilities of some positive and negative hydrogen ions in He and H2

Mobilities of H⁺ and H^? in He and in H₂, and of H⁺₂ and H⁺₃ in He, are calculated from ion-neutral potentials derived from theory and ion-beam scattering. Agreement with experiment is reasonable except for H^? in H₂ and H⁺₂ in He, which present unexplained puzzles.     

Role of radiolytically formed protonating agents in gas phase competitive reactions

Radiolytically formed O₂H⁺, N₂H⁺, and CO₂H⁺ ions were allowed to react with gaseous p-cymene. Dealkylation and isomerization reactions were observed with O₂H⁺ and N₂H⁺ ions, while only the first process occurred when CO₂H⁺ ions were employed. The results show that dealkylation is favored with respect to isomerization as the protonation exothermicity decreases.     

Molecular fragmentations: Part VII. Structures and energies of mass spectral fragments derived from benzene

Molecular structures and energies have been calculated, using MINDO/3, of the mass spectral ions arising from benzene: (C₆H₆)⁺ (three non-valence isomers); (C₆H₅⁺); (C₅H₃⁺) (four isomers); (C₄H₄)⁺ (three isomers); (C₄H₃)⁺ (two isomers); (C₄H₂)⁺ (four isomers); (C₃H₃)⁺; and (C₂H₂)⁺. Calculations have been made for the conjugate neutral fragments, allowing calculation of appearance potentials, and also for the ion (C₆H₇)⁺.     

Theoretical Investigation on Photoionization and Dissociative Photoionization of Toluene

The photoionization and dissociation photoionization of toluene have been studied using quantum chemistry methods.The geometries and frequencies of the reactants,transition states and products have been performed at B3LYP/6-311++G (d,p) level,and single-point energy calculations for all the stationary points were carried out at DFT calculations of the optimized structures with the G3B3 level.The ionization energies of toluene and the appearance energies for major fragment ions,C₇H₇⁺,C₆H₅⁺,C₅H₆⁺,C₅H₅⁺,are determined to be 8.90,11.15 or 11.03,12.72,13.69,16.28 eV,respectively,which are all in good agreement with published experimental data.With the help of available published experimental data and theoretical results,four dissociative photoionization channels have been proposed:C₇H₇⁺+H,C₆H₅⁺+CH₃,C₅H₆⁺+C₂H₂,C₅H₅⁺+C₂H₂+H.Transition structures and intermediates for those isomerization processes are determined in this work.Especially,the structures of C₅H₆⁺ and C₅H₅⁺ produced by dissociative photoionization of toluene have been defined as chain structure in this work with theoretical calculations.     

SiH+5 and the proton affinity of monosilane

Tandem mass spectrometric studies show that SiH⁺₅ is formed in bimolecular reactions of SiH₄ and NH⁺₂, C₂H⁺₃, C₂H⁺₆ and C₃H⁺₈ ions. The dependence of the reaction cross sections on ion energy indicates the formation of SiH⁺₅ from NH⁺₂, C₂H⁺₃, and C₂H⁺₆ to be exothermic reactions, while formation from C₃H⁺₈ is endothermic. Using known thermochemical data, these facts permit the assignment of 150 and 156 kcal/mole to the lower and upper limits of the proton affinity of monosilane.     

The reactions of some interstellar ions with benzene,cyclopropane and cyclohexane

The reactions of the cyclic molecules C₆H₆ (benzene), c-C₃H₆ (cyclopropane) and c-C₆H₁₂ (cyclohexane) with ArH⁺ (ArD⁺), H₃⁺, N₂H⁺, CH₅⁺, HCO⁺, OCSH⁺, C₂H₃⁺, CS₂H⁺ and H₃O⁺ have been studied at 300 K using a SIFT apparatus. All the reactions except those of C₂H₃⁺ proceed via proton transfer and all are fast except the H₃O⁺ and CS₂H⁺ reactions with c-C₆H₁₂ which are endothermic and which establish that the proton affinity of c-C₆H₁₂ is 160 ± 1 kcal mol⁻¹, which is considerably lower than the published value. In the c-C₃H₆ and the c-C₆H₁₂ reactions multiple products are observed and hence “breakdown curves” for the protonated molecules are constructed and the appearance energies of the various ion products are consistent with available thermochemical data. The reactions of C₂H₃⁺ with these cyclic molecules are atypical within this series of reactions in that they appear to proceed largely via hydride ion transfer. The implications of the results of this study to interstellar chemistry are alluded to.     

Transition-metal mediated heteroatom removal by reactions of FeL+ [L=O,C4H6, c-C5H6, c-C5H5, C6H6, C5H4(=CH2)] with furan,thiophene, and pyrrole in the gas phase

Reactions of Fe⁺ and FeL⁺ [L=O, C₄H₆, c-C₅H₆, C₅H₅, C₆H₆, C₅H₄(=CH₂)] with thiophene, furan, and pyrrole in the gas phase by using Fourier transform mass spectrometry are described. Fe⁺, Fe(C₅H₅)⁺, and FeC₆H ₆ ⁺ yield exclusive rapid adduct formation with thiophene, furan, and pyrrole. In addition, the iron-diene complexes [FeC₄H ₆ ⁺ and Fe(c-C₅H₆)⁺], as well as FeC₅H₄(=CH₂)⁺ and FeO⁺, are quite reactive. The most intriguing reaction is the predominant direct extrusion of CO from furan by FeC₄H₆ ⁺, Fe(c-C₅H₆)⁺, and FeC₅H₄(=CH₂)⁺. In addition, FeC₄H ₆ ⁺ and Fe(c-C₅H₆)⁺ cause minor amounts of HCN extrusion from pyrrole. Mechanisms are presented for these CO and HCN extrusion reactions. The absence of CS elimination from thiophene may be due to the higher energy requirements than those for CO extrusion from furan or HCN extrusion from pyrrole. The dominant reaction channel for reaction of Fe(c-C₅H₆)⁺ with pyrrole and thiophene is hydrogen-atom displacement, which implies D^O(Fa(N₅H₅)⁺-C₄H₄X)>D^O(Fe(C₅H₅)⁺-H)=46±5 kcal mol^?1. D^O(Fe⁺-C₄H₄S) and D^O(Fe⁺-C₄H₅N)=D^O(Fe⁺-C₄H₆)=48±5 kcal mol^?1. Finally, 55±5 kcal mol^?1=D^O(Fe⁺-C₆H₆)>D^O(Fe⁺-C₄H₄O)>D^O(Fe⁺-C₂H₄)=39.9±1.4 kcal mol^?1. FeO⁺ reacts rapidly with thiophene, furan, and pyrrole to yield initial loss of CO followed by additional neutral losses. D^O(Fe⁺-CS)>D^O(Fe⁺-C₄H₄S)≈48±5 kcal mol^?1 and D^O(Fe⁺-C₄H₅N)≈48±5 kcal mol^?1>D^O(Fe⁺-HCN)>D^O(Fe⁺-C₂H₄)=39.9±1.4 kcal mil^?1.     

Photoionization and Dissociation Study of 2-Methyl-2-propen-1-ol: Experimental and Theoretical Insights

The photoionization and dissociation of 2-methyl-2-propen-1-ol (MPO) have been investigated by using molecular beam experimental apparatus with tunable vacuum ultravioletsynchrotron radiation in the photon energy region of 8.0-15.5 eV. The photoionization efficiency (PIE) curves for molecule ion and fragment ions: C₄H₈O⁺、C₄H₇O⁺、C₃H₅O⁺、C₄H₇⁺、C₄H₆⁺、C₄H₅⁺、C₂H₄O⁺、C₂H₃O⁺、C₃H₆⁺、C₃H₅⁺、C₃H₃⁺、CH₃O⁺、CHO⁺ have been measured, and the ionization energy (IE) and the appearance energies (AEs) of the fragment ions have been obtained. The stable species and the first order saddle points have been calculated on the CCSD(T)/cc-pvTZ//B3LYP/6-31+G(d,p) level. With combination of theoretical and experimental results, the dissociative photoionization pathways of 2-methyl-2-propen-1-ol are proposed. Hydrogen migrations within the molecule are the dominant processes in most of the fragmentation pathways of MPO.     

Determination of hydrogen ion by ion chromatography (IC) with sulfonated cation-exchange resin as the stationary phase and aqueous EDTA (ethylenediamine-N,N,N′,N′-tetraacetic acid) solution as the mobile phase

An ion chromatographic (IC) method has been developed for determination of hydrogen ion (H⁺). It is based on the use of sulfonated cation-exchange resin as stationary phase, aqueous ethylenediamine-N,N,N′,N′-tetraacetic acid (dipotassium salt, EDTA-2K, written as K₂H₂Y) solution as mobile phase, and conductivity for detection. H⁺ was separated mainly by cation-exchange, but its elution was accelerated by the presence of EDTA. The order of elution for the model cations was H⁺ > Li⁺ > Na⁺ > NH₄ ⁺ > Ca²⁺ > > Mg²⁺. A sharp and highly symmetrical peak was obtained for H⁺ and this was attributed to the capacity of H₂Y₂ ^2– to receive and bind H⁺. H⁺ was detected conductiometrically and detector response (reduction in conductivity as a result of H⁺+H₂Y^2–→H₃Y^–) was linearly proportional to the concentration of H⁺ in the sample. The detection limit for H⁺ with this IC system was better than 4.7 μmol L^–1. A significant advantage of this method was the ability to separate and determine, in one step, H⁺ and other cations. The successful determination of H⁺ and other cation species in real acid-rain samples demonstrated the usefulness of this method.     

Theoretical Study of Isoprene Dissociative Photoionization

Theoretical calculations have been carried out to investigate the possible dissociation channels of isoprene. We focus on the major fragment ions of C₅H₇⁺,C₅H₅⁺,C₄H₅⁺,C₃H₆⁺,C₃H₅⁺,C₃H₄⁺,C₃H₃⁺ and C₂H₃⁺, which were observed experimentally from the isoprene dissociative photoionization. The energy calculations were performed with the CBS-QB3 model. All the geometries and energies of the fragments, intermediates and transition states involved in the dissociations channels were determined. Finally, the mechanisms of the dissociation pathways were discussed on the comparison of theoretical and experimental results.     

Atomisation and chemical ionisation of Si,Ge and Sn in fuel-rich flames

The relationship between atomisation and ionisation for Si, Ge and Sn in fuel-rich C₂H₂ and H₂ flames has been studied by means of flame ionisation mass spectroscopy, thermochemical calculation of burnt gas equilibrium composition, and computer simulation of chemical ionisation kinetics. The mass spectra obtained from C₂H₂/Ar/O₂ flames are similar to those from H₂ diffusion flames: Sn yields Sn⁺ and SnOH⁺, Ge and Si yield GeOH⁺ and SIO⁺. These similarities are in contrast to the substantial differences in calculated atomisation found between the C₂H₂ and H₂ flames. The discrepancies between atomisation and ionisation are reconciled by a chemical ionisation mechanism in which the ions SiH⁺, GeH⁺ and SnH⁺ are important intermediates. The ratios of atomic ions to protonated monoxides, M⁺:MOH⁺ are determined by the thermochemistry for the reaction, MOH⁺ + H ⇌ M⁺ + H₂O.     

Carbon skeletal rearrangements in 2-phenylthiophene and 2,5-diphenylthiophene under conditions of electron-impact

The mass spectra of ¹³C-labelled 2-phenylthiophenes and 2,5-diphenylthiophenes were studied. The label distributions for the [HCS]⁺, [C₂H₂S]^+·, [C₈H₆]^+·, [C₉H₇]⁺ and [C₇H₅]S⁺ ions from 2-phenylthiophene and the [HCS]⁺, [C₉H₇]⁺, [C₇H₅S]^+·, and [C₁₅H₁₁]⁺ ions from 2,5-diphenylthiophene were interpreted in terms of both carbon skeletal rearrangements in the thiophene ring and migration of the phenyl substituent. The degree of carbon scrambling in the thiophene ring appeared to be almost independent of the electron beam energy. The formation of some of the fragment ions studied seems to be so fast that no carbon scrambling could be detected at all; in neither case was complete scrambling of the carbon atoms of the thiophene ring observed.     

Photoelectron—photoion-coincidence measurements on 2,4-hexadiyne

2,4-Hexadiyne cations in their first excited electronic state òE_ureveal a decay by an effective competition between fluorescence and fragmentation. The present photoelectron—photoion-coincidence study of 2,4-hexadiyne cation provides individual breakdown diagrams for the parent ion and the seven dominant fragment ions, C₆H₅⁺, C₆H₄⁺, C₅H₃⁺, C₄H₄⁺, C₄ H₃⁺, C₄H₂⁺, C₃H₃⁺ in the ionisation energy regions populated by He(Iα) excitation. Additional information concerning the rate constants and the kinetic energy released on the formation of C₆H₅⁺ and C₄H₃⁺ are deduced from the time-of-flight (TOF) distributions of these ions. The appearance potentials for the two fragments C₄H₃⁺ and C₄H₂⁺ could also be measured, as these lie well within the third band of the He(Iα)-PE spectrum.     

Reduction of iodine by hydroxylamine within the pH range 0.7–3.5

The reduction of iodine by hydroxylamine within the [H⁺] range 3×10⁻¹–3×10⁻⁴ mol.L⁻¹ was first studied until completion of the reaction. In most cases, the concentration of iodine decreased monotonically. However, within a narrow range of reagent concentrations ([NH₃OH⁺]₀/[I₂]₀ ratio below 15, [H⁺] around 0.1 mol.L⁻¹, and ionic strength around 0.1 mol.L⁻¹), the [I₂] and [I₃⁻] vs. time curves showed 2 and 3 extrema, respectively. This peculiar phenomenon is discussed using a 4 reaction scheme (I₂+I⁻⇔︁I₃⁻, 2 I₂+NH₃OH⁺+H₂O→HNO₂+4 I⁻+5 H⁺, NH₃OH⁺+HNO₂→N₂O+2 H₂O+H⁺, and 2 HNO₂+2 I⁻+2 H⁺→2 NO+I₂+2 H₂O). In a flow reactor, sustained oscillations in redox potential were recorded with an extremely long period (around 24 h). The kinetics of the reaction was then investigated in the starting conditions. The proposed rate equation points out a reinforcement of the inhibition by hydrogen ions when [H⁺] is above 4×10⁻² mol.L⁻¹ at 25°C. A mechanism based on ion-transfer reactions is postulated. It involves both NH₂OH and NH₃OH⁺ as the reducing reactive species. The additional rate suppression by H⁺ at low pH would be connected to the existence of H₂OI⁺ in the reactive medium. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 785–797, 1998     

Vibrational-state-selected ion—molecule reaction cross sections at thermal energies

A method designed to measure relative ion—molecule reaction rates at thermal collision energies for selected reactant ion vibrational states is described. Relative reaction rates are determined for the three endothermic reactions: H₂⁺ (υ)(He,H)HeH⁺, H₂⁺ (υ)(Ne,H)NeH⁺, D₂⁺(υ)(Ne, D)NeD⁺, and for the two exothermic reactions H₂⁺ (υ)(H₂, H)H₃⁺, D₂⁺(υ)(D₂, D)D₃⁺, whereby data are evaluated for υ = 0–8 for H₂⁺ and for υ = 0–12 in the case of D₂⁺. The results are analyzed in terms of a modified statistical model designed for reactions that go through a collision complex. It is found that all data can be satisfactorily described within this model.     

Isomerisation of hydrocarbon ions III–[C8H8]+·, [C8H8]2+, [C6H6]+· AND [C6H5]+ IONS

Collisional activation spectra of [C₈H₈]⁺·, [C₈H₈]²⁺, [C₆H₆]⁺· and [C₆H₅]⁺ ions from fifteen different sources are reported. Decomposing [C₈H₈]⁺· ions of ten of these precursors isomerise to a mixture of mainly the cyclooctatetraene and, to a smaller extent, the styrene structure. Three additional structures are observed with [C₈H₈]⁺· ions from the remaining precursors. [C₈H₈]^2+., [C₈H₈]⁺·, [C₆H₆]⁺· and [C₆H₅]⁺· ions mostly decompose from common structures although some exceptions are reported.     

Cobinamide chemistries for photometric cyanide determination. A merging zone liquid core waveguide cyanide analyzer using cyanoaquacobinamide

Diaquacobinamide (H₂O)₂Cbi²⁺ or its conjugate base hydroxyaquacobinamide (OH(H₂O)Cbi⁺)) can bind up to two cyanide ions, making dicyanocobinamide. This transition is accompanied by a significant change in color, previously exploited for cyanide determination. The reagent OH(H₂O)Cbi⁺ is used in excess; when trace amounts of cyanide are added, CN(H₂O)Cbi⁺ should be formed. But the spectral absorption of CN(H₂O)Cbi⁺ is virtually the same as that of OH(H₂O)Cbi⁺. It has been inexplicable how trace amounts of cyanide are sensitively measured by this reaction. It is shown here that even with excess OH(H₂O)Cbi⁺, (CN)₂Cbi is formed first due to kinetic reasons; this only slowly forms CN(H₂O)Cbi⁺. This understanding implies that CN(H₂O)Cbi⁺ will itself be a better reagent.     

Molecular fragmentations: Part IX. Structures and energies of mass spectral fragments derived from xanthan hydride, 5-amino-1,2,4-dithiazolin-3-thione

Structures and energies have been calculated, in the MNDO approximation, for xanthan hydride (C₂H₂N₂S₃) and its molecular cation, and for the mass spectral fragment ions H₂NCNCS⁺, HNCNCS⁺, CS₂⁺, H₂N₂CS⁺ (two isomers), HN₂CS⁺, S₂⁺, H₂NCS⁺ (three isomers), HNCS⁺ (two isomers), H₃N₂C₂⁺ (four isomers), CS⁺ and HNCS⁺² (two isomers), together with the corresponding neutral fragments.     

Energy and substituent effects on the mass spectra of substituted benzophenones

For two competing decompositions of the same molecular ion to give products [A₁⁺] and [A₂⁺], the ratio [A₁⁺]/[A₂⁺], is equal to the ratio of rate constants for the formation of the stable ions. Thr ratios, [Y C₇H₄O⁺]/[C₇H₅O⁺], were determined for several benzophenones for electron energies from 15 to 70 eV. Plots of log [Y C₇H₄O⁺]/[C₇H₅O⁺] vs.[ω⁺] gave good straight lines at all energies. Similar correlations have been reported for log [Y C₇H₆⁺]/[C₇H₇⁺] from substituted diphenyl ethanes and are also true for substituted acetophenones, log [YøCO⁺]/[CH₃CO⁺]. A few charge exchange data were obtained which showed the same general trend as the electron-impact data and emphasize the contribution of low energy ions in the 70 eV mass spectra. Relatively poor correlations were obtained for the [Y C₆H₄⁺] and [C₆H₅⁺] ions that are formed by both one-step and two-step decompositions.