Ring-hydrogen participation in the keto--enol isomerization of the acetophenone radical cation

Molecular ions obtained from acetophenone have been observed to undergo proton transfer reactions in competition with unimolecular blackbody dissociation in a Fourier transform ion cyclotron resonance spectrometer provided with an in situ high temperature blackbody source. The ionizing energy dependence of these two processes and generation of the enol molecular ion by fragmentation of butyrophenone reveal that the keto ion undergoes blackbody dissociation exclusively while the enol ion promotes fast proton transfer reactions and undergoes very slow blackbody induced dissociation. Experiments with labeled acetophenone either on the methyl group or on the ring reveal that the enol ions can transfer both H+ and D+ suggesting that the mechanism responsible for the tautomerization process of these radical cations may involve scrambling of the methyl and ring hydrogens, or more than one mechanism. Theoretical calculations at the B3LYP level predict that the most favorable pathway for unimolecular isomerization of the keto ion involves initial migration of an ortho hydrogen to the carbonyl. The subsequent rearrangement to the enol form is calculated to require enough internal energy that would allow hydrogen walk around the benzene ring in agreement with the experimental results. The possibility that isomerization may also occur by a direct 1,3-hydrogen migration is also explored in terms of possible excited electronic states of the ion.     

Dissociation dynamics of propargyl chloride molecular ion near the reaction threshold: manifestation of quantum mechanical tunneling

The Cl loss from the propargyl chloride molecular ion has been investigated using mass-analyzed ion kinetic energy spectrometry (MIKES). The kinetic energy release distribution in the unimolecular dissociation has been determined. The potential energy surface for the mechanistic pathway has been calculated at the B3LYP/6-311G** density functional theory level. The calculated potential energy surface suggested that the threshold dissociation of the propargyl chloride molecular ion produces the C(3)H(3)(+) ion, only with the cyclopropenium structure, and with the release of a large amount of kinetic energy. This is in agreement with experimental results. Also, calculation of the rate constants with statistical rate models predicted that the reaction observed on a microsecond time scale occurs via tunneling through the rate-determining isomerization barrier for H-atom transfer. It has been found that a broad lifetime distribution is a manifestation of quantum mechanical tunneling of a precursor prepared under thermal conditions. Reinterpretation of previous photoelectron-photoion coincidence results taking into account the tunneling effect necessitated raising the critical energy to 0.64 eV from the energy of 0.34 eV reported previously. Copyright 2000 John Wiley & Sons, Ltd.     

Tunneling in the loss of hydrogen chloride from isopropyl chloride cation

The unimolecular dissociation of isopropyl chloride cation has been investigated using mass-analyzed ion kinetic energy spectrometry. The C3H6*+ ion was the only product ion in the metastable dissociation. The kinetic energy release distribution for the HCl loss was determined. Ab initio molecular orbital calculations were performed at the MP2/6-311++G(d,p) level together with single point energy calculations at the QCSID(T)/6-311++G(2d,2p) level. The calculations show that the molecular ion rearranges to an ion-dipole complex prior to loss of HCl via a transition state containing a four-membered ring. The rearrangement involves H atom transfer. On the basis of the potential energy surface obtained for the loss of HCl and Cl*, the rate constants were calculated by transition-state statistical theories with considering tunneling effect. From the calculated result, it is proposed that the observed HCl loss would occur via tunneling through the barrier for isomerization to the ion-dipole complex, CH3CHCH2*+...HCl.     

Unimolecular dissociations of excited C3H6O+: A comparative photoelectron—photoion coincidence study of 1,2-epoxypropane and acetone

The unimolecular fragmentation of internal energy selected 1,2-epoxypropane cations has been studied by fixed-wavelength photoelectron—photoion coincidence spectroscopy. Branching ratios for the prominent fragment ions are reported up to an ionization energy of I = 14 eV. It is shown that 1,2-epoxypropane cations initially formed with none or only little vibrational excitation in the electronic ground state do not dissociate, though their excess energy with respect to the lowest energetic fragmentation pathway is 1.25 eV. As the internal energy is increased, slow fragmentation into several dissociation channels is observed. This is used to explain a comparably slow dissociation process observed in the case of acetone molecular ions initially excited to their electronic à state. CH₂C(OH)CH₃⁺ and/or CH₃CHCHOH⁺ are proposed as precursors for these low-rate unimolecular reactions.     

Decompositions of odd- and even-electron anions derived from deoxy-polyadenylates

Radical anions have been formed via electron transfer from multiply charged 5′-d(AAA)-3′ and 5′-d(AAAA)-3′ anions to CCl₃ ⁺. These ions have been isolated in a quadrupole ion trap operated with helium bath gas at a pressure of 1 mtorr and subjected to resonance excitation (i. e., conventional ion trap collisional activation). Collisional activation of the even-electron species of the same charge state formed directly via electrospray was also performed by using essentially identical conditions. The collisional activation data can be compared directly without ambiguity arising from differences in parent ion internal energies and/or dissociation time frames. Both the odd- and even-electron anions yield extensive sequence-informative fragmentation but show significant differences in the extent of nucleobase loss and in the relative contributions from the various sequence diagnostic dissociation channels. The results of this study indicate that radical anions derived from multiply deprotonated oligo-deoxynucleotides that survive the electron transfer process are stable with respect to fragmentation in the ion trap environment under normal storage conditions and that the unimolecular dissociation behavior of these ions differs from the even-electron anions of the same charge state. These findings suggest, therefore, that odd- and even-electron anions might be used to provide complementary sequence information in cases in which neither ion type provides the full sequence.     

The Chemistry of Isolated Cations

Organic ions decompose in the field-free regions of a mass spectrometer after a relatively well-defined lifetime (t ≈ 10^?5s). This lifetime is very long compared with the time-scale of molecular bond vibrations and consequently the excess internal energy (“non fixed” energy) present in the transition state for dissociation is comparable with that found in solution experiments. In general, only the energetically most favorable decay routes are able to compete. Moreover, information concerning kinetic energy release (T) accompanying unimolecular decomposition may be obtained from a consideration of the metastable peak for the process; these extremely valuable data are inaccessible to solution experiments because of the effects of collisions. The chemistry of ions may therefore be investigated conveniently by generating the ions of interest in a mass spectrometer and analyzing the reactions which occur in metastable transitions.     

Fragmentation of singly charged adenine induced by neutral fluorine beam impact at 3 keV

The fragmentation scheme of singly charged adenine molecule (H(5)C(5)N(5)(+)) has been studied via neutral fluorine impact at 3 keV. By analyzing in correlation the kinetic energy loss of the scattered projectile F(-) produced in single charge transfer process and the mass of the charged fragments, the excitation energy distribution of the parent adenine molecular ions has been determined for each of the main dissociation channels. Several fragmentation pathways unrevealed in standard mass spectra or in appearance energy measurements are investigated. Regarding the well-known hydrogen cyanide (HCN) loss sequence, we demonstrate that although the loss of a HCN is the dominant decay channel for the parent H(5)C(5)N(5)(+) (m = 135), the decay of the first daughter ion H(4)C(4)N(4)(+) (m = 108) involves not only the HNC (m = 27) loss but also the symmetric breakdown into two dimers of HCN.     

C~6F~6^+→C~6F~5^++F气相单分子分解及碰撞诱导分解 反应研究

用质量分析离子动能谱(MIKES)研究了C~6F~6^+→C~6F~5^++F的气相单分子分解及其与Ar和He的碰撞诱导分解(CID)反应。实验结果表明,C~6F~6^+在电离室中获得足够能量而被激发到某一长效激发态,而CID是诱导其分解的必要步骤,且该分解过程有两条能量不同的反应途径。当碰撞气体为Ar时,两条途径所对应的能量变化分别为0eV和+9.8eV(将多余能量转化为动能),而当碰撞气体为He时,则分别为0eV和-17eV(将多余能量转化为内能)。CID/Ar诱导该长效激发态在C-F键断裂之前将多余能量转化为动能,而在CID/He中则将多余能量转化为内能。     

Dissociation channels of the 1-buten-2-yl radical and its photolytic precursor 2-bromo-1-butene

The work presented here is the first in a series of studies that use a molecular beam scattering technique to investigate the unimolecular reaction dynamics of C(4)H(7) radical isomers. Photodissociation of the halogenated precursor 2-bromo-1-butene at 193 nm under collisionless conditions produced 1-buten-2-yl radicals with a range of internal energies spanning the predicted barriers to the unimolecular reaction channels of the radical. Resolving the velocities of the stable C(4)H(7) radicals, as well as those of the products, allows for the identification of the energetic onset of each dissociation channel. The data show that radicals with at least 30.7 +/- 2 kcal/mol of internal energy underwent C-C fission to form allene + methyl, and radicals with at least 36.7 +/- 4 kcal/mol of internal energy underwent C-H fission to form H + 1-butyne and H + 1,2-butadiene; both of these observed barriers agree well with the G3//B3LYP calculations of Miller. HBr elimination from the parent molecule was observed, producing vibrationally excited 1-butyne and 1,2-butadiene. In the subsequent dissociation of these C(4)H(6) isomers, the major channel was C-C fission to form propargyl + methyl, and there is also evidence of at least one of the possible H + C(4)H(5) channels. A minor C-Br fission channel produces 1-buten-2-yl radicals in an excited electronic state and with low kinetic energy; these radicals exhibit markedly different dissociation dynamics than do the radicals produced in their ground electronic state.     

氯代甲苯双电荷离子的单分子解离反应研究

研究了在70 eV电子轰击电离条件下，氯代甲苯及氯化苄产生的双电荷离子[C_7H_7Cl]~(2＋)、[C_7H_6Cl]~(2＋·)和[C_7H_5Cl]~(2＋)为母体的两种类型单分子解离反应．主要讨论了亚稳双电荷离子的异构化反应、失H解高的“偶电子规则”以及单分子电荷分离过渡态的结构．     

Dissociation of the tertiary butanol radical cation

The ionzation and lowest energy unimolecular dissociation of tert-butanol were modelled by ab initio molecular orbital methods. The ion is formed on a repulsive surface and gives a methyl radical and protonated acetone as products with the liberation of 0.54 eV of energy. The calculations predict the formation of an electrostatically bound ion-neutral complex which is also subject to steric constraints.     

Probing centrifugal barriers in unimolecular dissociation of the allyl radical

Time-resolved photoionization of the hydrogen atom product from the allyl radical, C3H5, dissociation with 115 kcal/mol total energy provides information on the unimolecular dissociation dynamics. Vibrationally hot ground-state allyl radicals in both low and high J-states are prepared by electronic excitation to selected rovibrational states of C-state allyl followed by internal conversion. The measured dissociation rates and kinetic energy release are independent of the allyl parent rotational energy and suggest that centrifugal effects are unimportant in allyl radical dissociation at 115 kcal/mol.     

Kinetic energy release and position of transition state during the intramolecular substitution of ionized 2-benzoyl pyridines

The loss of substituents X from molecular ions of ortho substituted 2-benzoyl pyridines has been investigated as a function of the dissociation energy of the C? X bond. Comparison of unimolecular and collisional induced decompositions of the resulting [M ? X]⁺ ions and reference ions arising from 3-hydroxypyrido[1,2-α]indole shows that cyclic fragment ions are formed in every case by an intramolecular substitution reaction with the exception of the parent compound (X = H), which gives rise to a mixture of [M ? H]⁺ ions with different structures. The heat of formation of the cyclic ion has been estimated experimentally and by calculation using thermochemical data, and from this value and the appearance energies, the activation energies of the reverse reactions have been evaluated for the different reaction systems. Measurement of the kinetic energy release during the substitution reactions shows that only part of the reverse activation energy is released as kinetic energy. The energy partitioning quotient varies from 0.37 to 0.08 depending on the dissociation energy of the C? X bond or the reaction enthalpy. A sudden change in the energy partitioning quotient is observed with increasing exothermicity of the reaction, paralleling the behaviour of similar reaction systems. These results are interpreted as a demonstration of the influence of the variation of transition state position on the energy partitioning quotient.     

Sequence-specific fragmentation of benzyloxycarbonyl dipeptides by resonance-enhanced multiphoton ionization

The mechanism of fragment ion formation in resonance-enhanced multiphoton ionization (REMPI) of benzyloxycarbonyl (CBZ)-derivitized dipeptides is presented. At 266 nm, the entire multiphoton process can be thought of as a two-part scheme where ionization occurs by resonant two-photon ionization followed by photodissociation of the created ions. When the energy of two photons exceeds the molecular ionization energy by a significant amount, REMPI has the advantage of producing both parent ions and low appearance energy fragments in large amounts. For CBZ dipeptides, resonant two-photon ionization at 266 nm produces parent ions as well as A type sequence ions with high abundance. On the other hand, a three-photon process (resonant two-photon ionization followed by parent ion photodissociation) forms sequence-related ions which also involve complex fragmentations of the CBZ chromophore. These results are compared to mass spectra obtained by other ionization/dissociation methods and to REMPI mass spectra of related compounds. Factors related to molecular structure elucidation based upon REMPI mass spectra are discussed. Enhanced isomer distinction is demonstrated for CBZ-leu-ala-OCH₃ and CBZ-ile-ala-OCH₃ based upon REMPI fragmentation.     

Electron attachment to POCl3: measurement and theoretical analysis of rate constants and branching ratios as a function of gas pressure and temperature, electron temperature, and electron energy

Two experimental techniques, electron swarm and electron beam, have been applied to the problem of electron attachment to POCl3, with results indicating that there is a competition between dissociation of the resonant POCl3-* state and collisional stabilization of the parent anion. In the electron beam experiment at zero electron energy, the fragment ion POCl2- is the dominant ion product of attachment (96%), under single-collision conditions. Small amounts (approximately 2% each) of POCl3- and Cl- were observed. POCl3- and POCl2- ion products were observed only at zero electron energy, but higher-energy resonances were recorded for POCl-, Cl-, and Cl2- ion products. In the electron swarm experiment, which was carried out in 0.4-7 Torr of He buffer gas, the parent anion branching ratio increased significantly with pressure and decreased with temperature. The electron attachment rate constant at 297 K was measured to be (2.5+/-0.6)x10(-7) cm3 s(-1), with ion products POCl2- (71%) and POCl3- (29%) in 1 Torr of He gas. The rate constant decreased as the electron temperature was increased above 1500 K. Theory is developed for (a) the unimolecular dissociation of the nascent POCl3-* and (b) a stepladder collisional stabilization mechanism using the average energy transferred per collision as a parameter. These ideas were then used to model the experimental data. The modeling showed that D0 o(Cl-POCl2-) and EA(POCl3) must be the same within +/-0.03 eV.     

丁酮分子的共振增强多光子电离解离研究

利用可调谐染料激光研究了丁酮分子的共振增强多光子电离解离过程,发现在428～448nm激光波段丁酮分子发生的是经4p和4dRydberg态的(3+1)多光子过程。此外,我们还用“梯开关”模型对丁酮母体离子的解离机理和各碎片来源作了详细的分析,分析认为在丁酮母体离子的解离过程中存在H原子重排与电荷的重新分布现象。     

Analysis of carbohydrates by fast atom bombardment mass spectrometry: 2—Influence of the matrix and the nature of the alkaline cations in the attachment process of an alkaline cation to a disaccharide molecule

The fast atom bombardment (FAB) ionization process of a non-reducing disaccharide by an attachment reaction with an alkaline cation has been investigated according to the nature of both the matrix (glycerol, diethanolamine, triethanolamine) and the alkaline cation (lithium, sodium, potassium, rubidium, caesium). We have established that one way of forming the cationized disaccharide molecular ions, [disaccharide-cat]⁺, is by a desolvation reaction from the cationized solvated disaccharide molecular ions, [disaccharide-cat-matrix]⁺. This process, which has been established by mass-analysed ion kinetic energy (MIKE) spectral analysis of the solvated species, is shown to be drastically affected by the nature of the involved matrix but only slightly by the alkaline cation. The variations in the relative abundances of the disaccharide cationized molecular ions compared to their solvated clusters in the FAB mass spectra, due to the matrix employed, have been explained according to the unimolecular dissociation of the solvated clusters examined by MIKE analysis. However, the variations in the abundance of the disaccharide cationized molecular ions in relation to the alkaline cation used—a higher sensitivity has been observed for lithium, sodium and potassium alkaline cations—have been explained in terms of the cations available at the target surface for the attachment process to the sugar molecule, and by a ligand exchange reaction between the matrix and the disaccharide.     

Kinetics of Surface-Induced Dissociation of N(CH3) 4 + and N(CD3) 4 + Using Silicon Nanoparticle Assisted Laser Desorption/Ionization and Laser Desorption/Ionization

The implementation of surface-induced dissociation (SID) to study the fast dissociation kinetics (sub-microsecond dissociation) of peptides in a MALDI TOF instrument has been reported previously. Silicon nanoparticle assisted laser desorption/ionization (SPALDI) now allows the study of small molecule dissociation kinetics for ions formed with low initial source internal energy and without MALDI matrix interference. The dissociation kinetics of N(CH₃)₄⁺ and N(CD₃)₄⁺ were chosen for investigation because the dissociation mechanisms of N(CH₃)₄⁺ have been studied extensively, providing well-characterized systems to investigate by collision with a surface. With changes in laboratory collision energy, changes in fragmentation timescale and dominant fragment ions were observed, verifying that these ions dissociate via unimolecular decay. At lower collision energies, methyl radical (CH₃) loss with a sub-microsecond dissociation rate is dominant, but consecutive H loss after CH₃ loss becomes dominant at higher collision energies. These observations are consistent with the known dissociation pathways. The dissociation rate of CH₃ loss from N(CH₃)₄⁺ formed by SPALDI and dissociated by an SID lab collision energy of 15 eV corresponds to log k = 8.1, a value achieved by laser desorption ionization (LDI) and SID at 5 eV. The results obtained with SPALDI SID and LDI SID confirm that (1) the dissociation follows unimolecular decay as predicted by RRKM calculations; (2) the SPALDI process deposits less initial energy than LDI, which has advantages for kinetics studies; and (3) fluorinated self-assembled monolayers convert about 18% of laboratory collision energy into internal energy. SID TOF experiments combined with SPALDI and peak shape analysis enable the measurement of dissociation rates for fast dissociation of small molecules.     

Dissociative scattering of hyperthermal energy CF3+ ions from modified surfaces

Dissociative scattering of CF3+ ions in collision with a self-assembled monolayer surface of fluorinated alkyl thiol on a gold 111 crystal has been studied at low ion kinetic energies (from 29 to 159 eV) using a custom built tandem mass spectrometer with a rotatable second stage energy analyzer and mass spectrometer detectors. Energy and intensity distributions of the scattered fragment ions were measured as a function of the fragment ion mass and scattering angle. Inelastically scattered CF3+ ions were not observed even at the lowest energy studied here. All fragment ions, CF2+, CF+, F+, and C+, were observed at all energies studied with the relative intensity of the highest energy pathway, C+, increasing and that of the lowest energy pathway, CF2+, decreasing with collision energy. Also, the dissociation efficiency of CF3+ decreased significantly as the collision energy was increased to 159 eV. Energy distributions of all fragment ions from the alkyl thiol surface showed two distinct components, one corresponding to the loss of nearly all of the kinetic energy and scattered over a broad angular range while the other corresponding to smaller kinetic energy losses and scattered closer to the surface parallel. The latter process is due to delayed dissociation of collisionally excited ions after they have passed the collision region as excited parent ions. A similar study performed at 74 eV using a LiF coated surface on a titanium substrate resulted only in one process for all fragment ions; corresponding to the delayed dissociation process. The intensity maxima for these fragmentation processes were shifted farther away from the surface parallel compared to the thiol surface. A new mechanism is proposed for the delayed dissociation process as proceeding via projectile ions' neutralization to long-lived highly excited Rydberg state(s), reionization by the potential field between the collision region and entrance to the energy analyzer, and subsequent dissociation several microseconds after collisional excitation. A kinematic analysis of experimental data plotted as velocity Newton diagrams demonstrates that the delayed dissociation process results from the collisions of the ion with the bulk surface; i.e., the self-assembled monolayer surface acts as a bulk surface. A similar analysis for the highly inelastic collision processes shows that these are due to stronger collisions with a fraction of the thiol molecular chain, varying in length (mass) with the ion energy.