Ion Internal Energy Research Articles

Extension of Improved Particle and Energy Confinement Regime in the Core of LHD Plasma

Recent two major topics of Large Helical Device (LHD) towards fusion relevant conditions, high-density operation and high-ion-temperature operation, are reported. Super dense core plasma was obtained by the combination of repetitive hydrogen ice pellet injection and high power neutral beam injection (NBI) heating. A very peaked density profile with the highest central density of 1.1 × 1021 m-3 was produced showing that the particle transport was suppressed very well in the plasma core. The spatial density profile varies as the position of magnetic axis (Rax), and the steepest profile is obtained at Rax = 3.95 m. The highest central ion temperature of 5.6 keV was obtained in hydrogen plasma at electron density of 1.6 × 1019 m-3 by NBI, where a peaked ion-temperature profile with internal ion energy transport barrier was observed. The profile of electron temperature did not change much and was broad even when the ion temperature had a peaked profile. The central ion temperature is higher than the electron temperature, which is a new operation regime of LHD. High central ion temperature accompanied strong toroidal rotation and an extreme hollow profile of carbon ions (impurity hole). These steep temperature profiles were obtained so far at around Rax = 3.6 m. The compatibility between particle and energy confinement is a new issue of LHD to explore a new operation regime for attractive fusion reactor.

Electron Capture and Transfer Dissociation: Peptide Structure Analysis at Different Ion Internal Energy Levels

We decoupled electron-transfer dissociation (ETD) and collision-induced dissociation of charge-reduced species (CRCID) events to probe the lifetimes of intermediate radical species in ETD-based ion trap tandem mass spectrometry of peptides. Short-lived intermediates formed upon electron transfer require less energy for product ion formation and appear in regular ETD mass spectra, whereas long-lived intermediates require additional vibrational energy and yield product ions as a function of CRCID amplitude. The observed dependencies complement the results obtained by double-resonance electron-capture dissociation (ECD) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and ECD in a cryogenic ICR trap. Compared with ECD FT-ICR MS, ion trap MS offers lower precursor ion internal energy conditions, leading to more abundant charge-reduced radical intermediates and larger variation of product ion abundance as a function of vibrational post-activation amplitude. In many cases decoupled CRCID after ETD exhibits abundant radical c-type and even-electron z-type ions, in striking contrast to predominantly even-electron c-type and radical z-type ions in ECD FT-ICR MS and especially activated ion-ECD, thus providing a new insight into the fundamentals of ECD/ETD.

The dissociation dynamics of energy-selected neopentylamine ions: Heats of formation of neopentylamine and neopentyl alcohol

The dissociation dynamics of energy-selected neopentylamine cations, (CH 3) 3CCH 2NH 2 +, were studied using threshold photoelectron photoion coincidence (TPEPICO) spectroscopy in which ion time-of-flight (TOF) distributions are recorded as a function of the ion internal energy. The lowest energy pathway, producing the CH 3NH 3 + ion, involves a rearrangement of the molecular ion. The 0 K dissociation onsets for the production of the CH 3NH 3 +, CH 2NH 2 +, and (CH 3) 2CCH 2NH 2 + ions have been determined to be 9.54 ± 0.05, 9.647 ± 0.025 and 9.90 ± 0.1 eV, respectively. Because the heat of formation of the CH 2NH 2 + + t-C 4H 9 products are established, we can use the measured onset of 9.647 eV for this reaction to establish the neopentylamine Δ f H 298 ° = − 130.3 ± 3.3 kJ / mol . This result is used in a group additivity scheme to estimate the neopentyl alcohol heat of formation as Δ f H 298 ° = − 315.5 ± 4 kJ mo l − 1 . Both of these results are strongly supported by a series of isodesmic reactions calculated at the G3B3 and CBS-APNO levels. This is the first reported experimental heat of formation of the neopentylamine and the first reported heat of formation of the neopentyl alcohol.

Ion internal energy distributions validate the charge residue model for small molecule ion formation by spray methods

This paper reports a detailed study of the internal energy distribution of ions formed by four electrospray ionization (ESI)-related ionization methods, with particular emphasis on electrosonic spray ionization (ESSI). Substituted benzylpyridinium ions were used as thermometer ions to probe the internal energy distribution. The influence of different instrumental parameters was studied. Cone and skimmer voltages as well as the collision energy were found to strongly affect the ion internal energy distribution, whereas the distance between the emitter and the inlet of the mass spectrometer, the nebulizing gas pressure or the flow rate showed no influence. The internal energy distribution obtained with an ESSI source was compared with those obtained for electrospray (ESI), nanoelectrospray (nanoESI) and sonic spray ionization (SSI) on the same mass spectrometer with the same instrumental parameters. No clear differences were observed. As the charge residue model is the only ion formation mechanism possible for SSI, we conclude that benzylpyridinium ions are formed by the pathway suggested by this model.

Internal energy distribution of peptides in electrospray ionization : ESI and collision‐induced dissociation spectra calculation

The internal energy of ions and the timescale play fundamental roles in mass spectrometry. The main objective of this study is to estimate and compare the internal energy distributions of different ions (different nature, degree of freedom 'DOF' and fragmentations) produced in an electrospray source (ESI) of a triple-quadrupole instrument (Quattro I Micromass). These measurements were performed using both the Survival Yield method (as proposed by De Pauw) and the MassKinetics software (kinetic model introduced by Vékey). The internal energy calibration is the preliminary step for ESI and collision-induced dissociation (CID) spectra calculation. meta-Methyl-benzylpyridinium ion and four protonated peptides (YGGFL, LDIFSDF, LDIFSDFR and RLDIFSDF) were produced using an electrospray source. These ions were used as thermometer probe compounds. Cone voltages (V(c)) were linearly correlated with the mean internal energy values (<E(int) >) carried by desolvated ions. These mean internal energy values seem to be slightly dependent on the size of the studied ion. ESI mass spectra and CID spectra were then simulated using the MassKinetics software to propose an empirical equation for the mean internal energy (<E(int) >) versus cone voltage (V(c)) for different source temperatures (T): < E(int) > = [405 x 10(-6) - 480 x 10(-9) (DOF)] V(c)T + E(therm)(T). In this equation, the E(therm)(T) parameter is the mean internal energy due to the source temperature at 0 V(c).

Ion Activation in Electron Capture Dissociation To Distinguish between N-Terminal and C-Terminal Product Ions

We present a method to distinguish N-terminal from C-terminal product ions in electron capture dissociation (ECD) MS/MS due to the change in relative abundances of even-electron (prime) and odd-electron (radical) product ions produced in consecutive ECD and activated ion-ECD mass spectra. The method is based on the rate and direction of hydrogen atom transfer between N-terminal and C-terminal ECD products and its dependence on ion internal energy. We demonstrate that increasing ion internal energy by vibrational activation prior to ECD results in decreased ratio of radical/prime N-terminal product ions (c*/c' ratio), but increased ratio of radical/prime C-terminal product ions (z*/z' ratio) in many cases. The combination of AI-ECD and ECD promises to increase the confidence of mass spectrometry-based peptide sequencing and protein identification.

A thermal extrapolation method for the effective temperatures and internal energies of activated ions

The internal energies of dissociating ions, activated chemically or collisionally, can be estimated using the kinetics of thermal dissociation. The thermal Arrhenius parameters can be combined with the observed dissociation rate of the activated ions using k diss = A thermalexp(− E a,thermal/ RT eff). This Arrhenius-type relation yields the effective temperature, T eff, at which the ions would dissociate thermally at the same rate, or yield the same product distributions, as the activated ions. In turn, T eff is used to calculate the internal energy of the ions and the energy deposited by the activation process. The method yields an energy deposition efficiency of 10% for a chemical ionization proton transfer reaction and 8–26% for the surface collisions of various peptide ions. Internal energies of ions activated by chemical ionization or by gas phase collisions, and of ions produced by desorption methods such as fast atom bombardment, can be also evaluated. Thermal extrapolation is especially useful for ion–molecule reaction products and for biological ions, where other methods to evaluate internal energies are laborious or unavailable.

Collision induced dissociation study of 10 monoterpenes for identification in trace gas measurements using the newly developed proton-transfer reaction ion trap mass spectrometer

We present the study of fragmentation patterns of different monoterpene species after dissociative proton-transfer and after collision induced dissociation (CID) in a newly developed proton-transfer reaction ion trap mass spectrometer (PIT-MS). For the monoterpene measurements the proton-transfer reaction chamber was set at an E/ N-value of 90–100 Td; at this value the monoterpenes can be found at m/ z values of 137 and 81. CID patterns of all 10 monoterpenes studied are found to be distinguishable, making it possible to positively identify a monoterpene solely on the basis of its CID pattern. However, identification of compounds in a mixture of several monoterpenes will still be difficult. Additionally, we find that the outcome of a CID experiment, expressed in the ratio between different fragments, depends on the kinetic energy of the ions as they exit the drift tube. This behavior is attributed to differences in ion internal energy at different drift tube voltages. The effect of ion internal energy change on the CID pattern is shown when the cooling time between isolation and dissociation of the parent ions is changed, and the CID fragmentation ratio of fragments 95 and 81 amu of α-terpinene is affected.

Collisional cooling in a quadrupole ion trap at sub-ambient temperatures

Quadrupole ion traps have been used successfully as ion storage devices for infrared multiphoton dissociation (IRMPD) experiments. Recently there has been interest in doing low temperature action spectroscopy experiments using ion traps as detectors for IRMPD spectroscopy. Cooling the trapping electrodes has the effect of cooling the trapped ions to the same internal temperature, because quadrupole ion traps operate at He bath gas pressures high enough to produce equilibrium ion internal energy distributions. It has previously been shown that collisions of the ions with the bath gas cool the ions’ internal vibrational modes at a rate that competes with IRMPD excitation at ambient temperatures. To investigate the implications of doing IRMPD in a quadrupole ion trap at lower trapping temperatures, the present study measures the collisional cooling rate constants at sub-ambient temperatures down to 25 K. The change in collisional cooling rate constant with trap temperature is correlated to the increased energy needed to dissociate the ions at these lower trap temperatures. It is found that both the energy needed to effect dissociation and the collisional cooling rate increase exponentially as trap temperature drops.

Constraining supernova models using the hot gas in clusters of galaxies

The hot Intra-Cluster Medium (ICM) in clusters of galaxies is a very large repository of metals produced by supernovae. We aim to accurately measure the abundances in the ICM of many clusters and compare these data with metal yields produced by supernovae. Using the data archive of the XMM-Newton X-ray observatory, we compile a sample of 22 clusters. We fit spectra extracted from the core regions and determine the abundances of silicon, sulfur, argon, alcium, iron, and nickel. The abundances from the spectral fits are subsequently fitted to supernova yields determined from several supernova type Ia and core-collapse supernova models. We find that the argon and calcium abundances cannot be fitted with currently favoured supernova type Ia models. We obtain a major improvement of the fit, when we use an empirically modified delayed-detonation model that is calibrated on the Tycho supernova remnant. The two modified parameters are the density where the sound wave in the supernova turns into a shock and the ratio of the specific internal energies of ions and electrons at the shock. Our fits also suggest that the core-collapse supernovae that contributed to the enrichment of the ICM had progenitors which were already enriched. The Ar/Ca ratio in clusters is a good touchstone for determining the quality of type Ia models. The core-collapse contribution, which is about 50% and not strongly dependent on the IMF or progenitor metallicity, does not have a significant impact on the Ar/Ca ratio. The number ratio between supernova type Ia and core-collapse supernovae suggests that binary systems in the appropriate mass range are very efficient (~ 5-16%) in eventually forming supernova type Ia explosions.

Liquid chromatography/electrospray ionization mass spectrometric characterization of Harpagophytum in equine urine and plasma

A method has been developed for the analysis and characterization in equine urine and plasma of iridoid glycosides: harpagide, harpagoside and 8-para-coumaroyl harpagide, which are the main active principles of Harpagophytum, a plant with antiinflammatory properties. The method involves liquid chromatography coupled with positive electrospray ionization mass spectrometry. The addition of sodium or lithium chloride instead of formic acid in the eluting solvent has been studied in order to enhance the signal and to modify the ion's internal energy. Fragmentation pathways and associated patterns are proposed for each analyte. A comparison of three types of mass spectrometer: a 3D ion trap, a triple quadrupole and a linear ion trap, has been conducted. The 3D ion trap was selected for drug screening analysis whereas the linear ion trap was retained for identification and quantitation analysis.

Thermochemistry and Dissociative Photoionization of Si(CH3)4, BrSi(CH3)3, ISi(CH3)3, and Si2(CH3)6Studied by Threshold Photoelectron−Photoion Coincidence Spectroscopy

Threshold photoelectron-photoion coincidence spectroscopy (TPEPICO) has been used to study the dissociation kinetics and thermochemistry of Me(4)Si, Me(6)Si(2), and Me(3)SiX, (X = Br, I) molecules. Accurate 0 K dissociative photoionization onsets for these species have been measured from the breakdown diagram and the ion time-of-flight distribution, both of them analyzed and simulated in terms of the statistical RRKM theory and DFT calculations. The average enthalpy of formation of trimethylsilyl ion, Delta fH(o)298K(Me(3)Si(+)) = 617.3 +/- 2.3 kJ/mol, has been determined from the measured onsets for methyl loss (10.243 +/- 0.010 eV) from Me(4)Si, and Br and I loss from Me(3)SiBr (10.624 +/- 0.010 eV) and Me(3)SiI (9.773 +/- 0.015 eV), respectively. The methyl loss onsets for the trimethyl halo silanes lead to Delta fH(o)298K(Me(2)SiBr(+)) = 590.3 +/- 4.4 kJ/mol and Delta fH(o)298K(Me(5)Si(2)(+)) = 487.6 +/- 6.2 kJ/mol. The dissociative photoionization of Me(3)SiSiMe(3) proceeds by a very slow Si-Si bond breaking step, whose rate constants were measured as a function of the ion internal energy. Extrapolation of this rate constant to the dissociation limit leads to the 0 K dissociation onset (9.670 +/- 0.030 eV). This onset, along with the previously determined trimethylsilyl ion energy, leads to an enthalpy of formation of the trimethylsilyl radical, Delta fH(o)298K(Me(3)Si(*)) = 14.0 +/- 6.6 kJ/mol. In combination with other experimental values, we propose a more accurate average value for Delta fH(o)298K(Me(3)Si(*)) of 14.8 +/- 2.0 kJ/mol. Finally, the bond dissociation enthalpies (DeltaH(298K)) Si-H, Si-C, Si-X (X=Cl, Br, I) and Si-Si are derived and discussed in this study.

Ground and Excited State Dissociation Dynamics of Ionized 1,1-Difluoroethene

The kinetic energy release distributions (KERDs) for the fluorine atom loss from the 1,1-difluoroethene cation have been recorded with two spectrometers in two different energy ranges. A first experiment uses dissociative photoionization with the He(I) and Ne(I) resonance lines, providing the ions with a broad internal energy range, up to 7 eV above the dissociation threshold. The second experiment samples the metastable range, and the average ion internal energy is limited to about 0.2 eV above the threshold. In both energy domains, KERDs are found to be bimodal. Each component has been analyzed by the maximum entropy method. The narrow, low kinetic energy components display for both experiments the characteristics of a statistical, simple bond cleavage reaction: constraint equal to the square root of the fragment kinetic energy and ergodicity index higher than 90%. Furthermore, this component is satisfactorily accounted for in the metastable time scale by the orbiting transition state theory. Potential energy surfaces corresponding to the five lowest electronic states of the dissociating 1,1-C2H2F2+ ion have been investigated by ab initio calculations at various levels. The equilibrium geometry of these states, their dissociation energies, and their vibrational wavenumbers have been calculated, and a few conical intersections between these surfaces have been identified. It comes out that the ionic ground state X2B1 is adiabatically correlated with the lowest dissociation asymptote. Its potential energy curve increases in a monotonic way along the reaction coordinate, giving rise to the narrow KERD component. Two states embedded in the third photoelectron band (B2A1 at 15.95 eV and C2B2 at 16.17 eV) also correlate with the lowest asymptote at 14.24 eV. We suggest that their repulsive behavior along the reaction coordinate be responsible for the KERD high kinetic energy contribution.

Comparison of the Effects of Ionization Mechanism, Analyte Concentration, and Ion “Cool-Times” on the Internal Energies of Peptide Ions Produced by Electrospray and Atmospheric Pressure Matrix-Assisted Laser Desorption Ionization

The propensities of a series of peptide ions produced by both electrospray and atmospheric pressure matrix assisted laser desorption ionization (AP-MALDI) to fragment in an ion trap mass spectrometer under various conditions were studied in detail by measuring the extent of fragmentation of precursor ions by collision induced dissociation (CID) as a function of applied resonance excitation RF voltage. For the most basic peptides, the energy required to fragment MH+ ions generated by electrospray exceeded that required to fragment equivalent AP-MALDI ions under identical instrumental conditions; the reverse was observed for a peptide incorporating no basic residues, while peptides of intermediate basicity showed little difference between the ionization methods. This correlation between peptide basicity and the difference in the energy required to induce fragmentation of MH+ ions generated by AP-MALDI and electrospray is attributed primarily to a trend in the internal energies of the ions generated by AP-MALDI (the greater the difference in gas-phase basicities between the matrix and the analyte the greater the internal energy of the analyte ions produced). Furthermore the internal energies of ions produced by AP-MALDI, but not the equivalent ions formed by electrospray, were observed to decrease with decreasing analyte concentration. We attribute this finding to the cooling effect of endothermic dissociation of analyte ion/matrix molecule clusters following the matrix assisted laser desorption step. Time-resolved analyses (measurement of extent of fragmentation of precursor ions by CID as a function of pre-CID "cool times") revealed that cooling periods in excess of 250 ms were required to achieve internal energy equilibrium through cooling collisions with the helium buffer gas. Furthermore, these analyses demonstrated that, even after these extended cooling times, equivalent ions formed by the two ionization techniques showed different propensities to fragment. We conclude that the two different ionization techniques produce ion populations that may differ in their three-dimensional structure.

Heats of Formation of the Propionyl Ion and Radical and 2,3-Pentanedione by Threshold Photoelectron Photoion Coincidence Spectroscopy

The dissociative photoionization onsets for the formation of the propionyl ion (C(2)H(5)CO(+)) and the acetyl ion (CH(3)CO(+)) were measured from energy selected butanone and 2,3-pentanedione ions using the technique of threshold photoelectron photoion coincidence (TPEPICO) spectroscopy. Ion time-of-flight (TOF) mass spectra recorded as a function of the ion internal energy permitted the construction of breakdown diagrams, which are the fractional abundances of ions as a function of the photon energy. The fitting of these diagrams with the statistical theory of unimolecular decay permitted the extraction of the 0 K dissociation limits of the first and second dissociation channels. This procedure was tested using the known energetics of the higher energy dissociation channel in butanone that produced the acetyl ion and the ethyl radical. By combining the measured dissociative photoionization onsets with the well-established heats of formation of CH(3)(*), CH(3)CO(+), CH(3)CO(*), and butanone, the 298 K heats of formation, Delta(f)H degrees (298K), of the propionyl ion and radical were determined to be 618.6 +/- 1.4 and -31.7 +/- 3.4 kJ/mol, respectively, and Delta(f)H degrees (298K)[2,3-pentanedione] was determined to be -343.7 +/- 2.5 kJ/mol. This is the first experimentally determined value for the heat of formation for 2,3-pentanedione. Ab initio calculations at the Weizmann-1 (W1) level of theory predict Delta(f)H degrees (298K) values for the propionyl ion and radical of 617.9 and -33.3 kJ/mol, respectively, in excellent agreement with the measured values.

Internal energy and fragmentation of ions produced in electrospray sources.

This review addresses the determination of the internal energy of ions produced by electrospray ionization (ESI) sources, and the influence of the internal energy on analyte fragmentation. A control of the analyte internal energy is crucial for several applications of electrospray mass spectrometry, like structural studies, construction of reproducible and exportable spectral libraries, analysis of non-covalent complexes. Sections II and III summarize the Electrospray mechanisms and source design considerations which are relevant to the problem of internal energy, and Section IV gives an overview of the inter-relationships between ion internal energy, reaction time scale, and analyte fragmentation. In these three sections we tried to make the most important theoretical elements understandable by all ESI users, and their understanding requires a minimal background in physical chemistry. We then present the different approaches used to experimentally determine the ion internal energy, as well as various attempts in modeling the internal energy uptake in electrospray sources. Finally, a tentative comparison between electrospray and other ionization sources is made. As the reader will see, although many reports appeared on the subject, the knowledge in the field of internal energy of ions produced by soft ionization sources is still scarce, because of the complexity of the system, and this is what makes this area of research so interesting. The last section presents some perspectives for future research.

Internal energy build-up in matrix-assisted laser desorption/ionization.

This paper reports detailed studies on the internal energy of ions formed in matrix-assisted laser desorption/ionization (MALDI) using delayed extraction MALDI-time-of-flight (TOF) and atmospheric pressure (AP) MALDI mass spectrometric (MS) methods. We use benzylpyridinium cations as internal energy probes. Our study reveals three distinct contributions to internal energy build-up in vacuum-MALDI (classical MALDI-TOF), each having different effects on ion fragmentation. Some fragments are formed before ion extraction (i.e. no more than 100 ns after the laser impact), and they are therefore well resolved and recorded as sharp signals in the MALDI-TOFMS scan. This prompt fragmentation can have two origins: (i) in-plume thermal activation, presumably always present, and (ii) in-plume chemical activation, in the course of reactions with hydrogen radicals. In addition to early internal energy build-up associated with these well-resolved promptly formed fragments, a broad peak slightly offset to higher masses could be detected corresponding to fragments formed after the extraction has started. This second signal corresponds to a third source of internal energy in MALDI ions, (iii) the extraction-induced collisional activation of the ions with the neutral components of the plume. These three contributions are difficult to quantify in vacuum-MALDI, because of the combined influence of several parameters (nature of the matrix, spot-to-spot variability, total laser exposure, delay time, acceleration voltage) on extraction-induced fragmentation. AP-MALDI, on the other hand, has two advantages for comparative studies of analyte fragmentation. First, extraction-induced fragmentation is absent, and only the contributions of early plume activation remain. Second, the reproducibility is far better than in vacuum-MALDI. AP-MALDI is therefore expected to shed new light on the early steps of the MALDI process.

Heats of Formation of the Acetyl Radical and Ion Obtained by Threshold Photoelectron Photoion Coincidence

The dissociative photoionization onsets for the production of CH 3 CO + + CH 3 _from acetone and CH 3 CO + + CH 3 CO_from butanedione have been measured by threshold photoelectron photoion coincidence (TPEPICO) in which time-of-flight (TOF) mass spectra are obtained as a function of the ion internal energy. The use of velocity focusing for threshold electrons and the subtraction of hot electron coincidences from the TPEPICO spectra allow the 0 K dissociation onset to be measured with a precision of I kJ/mol. The experimental onset for CH 3 _loss from CH 3 COCH 3 was measured to be 10.563 ′ 0.010 eV and the onset for CH 3 CO_ loss from CH 3 COCOCH 3 was found to be 10.090 ′ 0.006 eV. A 298 K heat of formation of the CH 3 CO + of 659.4 ′ 1.1 kJ/mol is obtained by combining the measured dissociation onset with the well-established heats of formation of acetone and the methyl radical. A 298 K heat of formation of the CH 3 CO_ radical of -9.8 ′ 1.8 kJ/mol is obtained by combining the measured dissociation onset with the well-known heat of formation of butanedione and the measured heat of formation of CH 3 CO + . The acetone and butanedione ionization energies were measured to be 9.708 ′ 0.004 and 9.21 ′ 0.05 eV, respectively.

Atmospheric pressure chemical ionization mass spectrometry and in‐source fragmentation of lutein esters

Negative-ion atmospheric pressure chemical ionization (APCI) mass spectrometry and in-source collisionally induced dissociation (CID) were employed to obtain structural information of lutein esters from marigold extract. Both molecular ions and structurally significant fragments corresponding to the loss of fatty acids were observed in high abundance in the current study. Six lutein diesters including lauroylmyristoyl-lutein (LML), dimyristoyl-lutein (dML), myristoylpalmitoyl-lutein (MPL), dipalmitoyl-lutein (dPL), palmitoylstearoyl-lutein (PSL) and distearoyl-lutein (dSL) were characterized in a marigold flower extract. Breakdown curves (plots of relative ion abundance vs. internal energy) of three lutein diesters were established by monitoring the relative ion abundance of molecular and fragment ions at different cone voltages during negative-ion APCI-LC/MS analysis.

The use of kinetic isotope effects for the determination of internal energy distributions in isolated transient species in the gas phase

Isotope effects on the loss of H and D are used to estimate the internal energy distribution in transient radicals produced by collisional electron transfer in the gas phase, as studied by neutralization–reionization mass spectrometry (NRMS). Experimental intermolecular and intramolecular isotope effects are compared to those calculated by RRKM theory on ab initio potential energy surfaces and convoluted with energy distribution curves. Fitting parameters in trial energy distribution curves provides widths and maxima that are compared with the energetics of ion and neutral formation. For collisional neutralization of 2-hydroxypyridinium, 3-hydroxypyridinium, and C(OH) 3 + cations by electron transfer from polarizable molecular targets, the most probable internal energy of the resulting transient radical is expressed as a simple sum of the precursor ion internal energy and the Franck–Condon energy acquired by vertical electron capture. This simple formula allows one to predict internal energies in transient neutral systems where a complete kinetic analysis of isotope effects is difficult or impractical.