Conformational Effects on Gas-Phase Acidities of Isomeric C and C Alkanols.

The competitive threshold collision-induced dissociation technique is used to examine conformational effects on the relative gas-phase acidities of selected alcohols. By use of HF and HO as reference acids in a local thermochemical network to obtain absolute acidities, the measured 0 K gas-phase acidities for the propanol and pentanol isomers are Δ H(CHCHCHO-H) = 1563.9 ± 2.

Radical Thermometers, Thermochemistry, and Photoelectron Spectra: A Photoelectron Photoion Coincidence Spectroscopy Study of the Methyl Peroxy Radical.

We investigated the simplest alkylperoxy radical, CHOO, formed by reacting photolytically generated CH radicals with O, using the new combustion reactions followed by photoelectron photoion coincidence (CRF-PEPICO) apparatus at the Swiss Light Source. Modeling the experimental photoion mass-selected threshold photoelectron spectrum using Franck-Condon simulations including transitions to triplet and singlet cationic states yielded the adiabatic ionization energy of 10.265 ± 0.

Anchoring the Gas-Phase Acidity Scale from Hydrogen Sulfide to Pyrrole. Experimental Bond Dissociation Energies of Nitromethane, Ethanethiol, and Cyclopentadiene.

A meta-analysis of experimental information from a variety of sources is combined with statistical thermodynamics calculations to refine the gas-phase acidity scale from hydrogen sulfide to pyrrole. The absolute acidities of hydrogen sulfide, methanethiol, and pyrrole are evaluated from literature R-H bond energies and radical electron affinities to anchor the scale. Relative acidities from proton-transfer equilibrium experiments are used in a local thermochemical network optimized by least-squares analysis to obtain absolute acidities of 14 additional acids in the region.

Energy-resolved collision-induced dissociation of peroxyformate anion: enthalpies of formation of peroxyformic acid and peroxyformyl radical.

We measure the oxygen-oxygen bond dissociation energy of the peroxyformate anion (HCO(3)(-)) using energy-resolved collision-induced dissociation with a guided ion beam tandem mass spectrometer. The analysis of the dissociation process from HCO(3)(-) ((1)A') to HCO(2)(-) ((1)A(2)) + O((3)P) requires consideration of the singlet-triplet crossing along the reaction path and of the competing OH(-) and O(2)H(-) product channels. The measured oxygen-oxygen bond dissociation energy is D(0)(HCO(2)(-)-O) = 1.

Optimization of a quadrupole ion storage trap as a source for time-of-flight mass spectrometry.

Designs of a quadrupole ion trap (QIT) as a source for time-of-flight (TOF) mass spectrometry are evaluated for mass resolution, ion trapping, and laser activation of trapped ions. Comparisons are made with the standard hyperbolic electrode ion trap geometry for TOF mass analysis in both linear and reflectron modes. A parallel-plate design for the QIT is found to give significantly improved TOF mass spectrometer performance.

Photoelectron spectra of dihalomethyl anions: testing the limits of normal mode analysis.

We report the 364-nm negative ion photoelectron spectra of CHX(2)(-) and CDX(2)(-), where X = Cl, Br, and I. The pyramidal dihalomethyl anions undergo a large geometry change upon electron photodetachment to become nearly planar, resulting in multiple extended vibrational progressions in the photoelectron spectra. The normal mode analysis that successfully models photoelectron spectra when geometry changes are modest is unable to reproduce qualitatively the experimental data using physically reasonable parameters.

Pulsed ion extraction diagnostics in a quadrupole ion trap linear time-of-flight mass spectrometer.

Pulsed extraction techniques are investigated for a quadrupole ion trap (QIT) interfaced to a linear time-of-flight (TOF) mass analyzer. A nonfocusing short-pulse mode of operation is developed and characterized. The short-pulse mode creates a near-monoenergetic ion packet, which is useful for reaction kinetics experiments and for making diagnostic measurements of the ion cloud size in the trap.

The photoelectron spectrum of CCl2-: the convergence of theory and experiment after a decade of debate.

We report new 351 nm negative ion photoelectron spectra of CCl(2)(-), CBr(2)(-), and CI(2)(-). This study was undertaken in an attempt to understand the major discrepancy between dihalocarbene (CX(2), X = Cl, Br, I) singlet-triplet splittings reported by our laboratory (R. L.

Low-energy photoelectron imaging spectroscopy of nitromethane anions: Electron affinity, vibrational features, anisotropies, and the dipole-bound state.

We present low-energy velocity map photoelectron imaging results for nitromethane anions. The photoelectron spectrum is interpreted with the aid of ab initio theory and Franck-Condon factor calculations. We obtain a new value for the adiabatic electron affinity of nitromethane of (172+/-6) meV and observe the dipole-bound state of nitromethane.

Fluorescence and photodissociation of rhodamine 575 cations in a quadrupole ion trap.

The fluorescence and photodissociation of rhodamine 575 cations confined to a quadrupole ion trap are observed during laser irradiation at 488 nm. The kinetics of photodissociation is measured by time-dependent mass spectra and time-dependent fluorescence. The rhodamine ion signal and fluorescence decay are studied as functions of buffer gas pressure, laser fluence, and irradiation time.

Statistical rate theory and kinetic energy-resolved ion chemistry: theory and applications.

Ion chemistry, first discovered 100 years ago, has profitably been coupled with statistical rate theories, developed about 80 years ago and refined since. In this overview, the application of statistical rate theory to the analysis of kinetic-energy-dependent collision-induced dissociation (CID) reactions is reviewed. This procedure accounts for and quantifies the kinetic shifts that are observed as systems increase in size.

Photodissociation and collisional cooling of rhodamine 575 cations in a quadrupole ion trap.

The photodissociation of rhodamine 575 cations held in a quadrupole ion trap is studied using 514 nm light as a function of buffer gas pressure, irradiation time, and laser fluence. The laser-induced photodissociation decays of rhodamine ions have lifetimes on the order of seconds for the range of pressures and powers investigated and exhibit strong nonlinear pressure dependence. Dissociation mechanisms are considered that involve the sequential absorption of multiple photons and several collisional deactivation steps.

Threshold collision-induced dissociation of hydrogen-bonded dimers of carboxylic acids.

Energy-resolved competitive collision-induced dissociation is used to investigate the proton-bound heterodimer anions of a series of carboxylic acids (formic, acetic, and benzoic acid) and nitrous acid with their conjugate bases. The dissociation reactions of the complexes [CH3COO.H.

Hydrogen atom transfer reactions of C2-, C4-, and C6-: bond dissociation energies of linear H-C2n- and H-C2n (n = 1, 2, 3).

The reactions of C2-, C4-, and C6- with D2O and ND3 and of C4- with CH3OH, CH4, and C2H6 have been investigated using guided ion beam tandem mass spectrometry. Hydrogen (or deuterium) atom transfer is the major product channel for each of the reactions. The reaction threshold energies for collisional activation are reported.

Gas-phase acidities and O-H bond dissociation enthalpies of phenol, 3-methylphenol, 2,4,6-trimethylphenol, and ethanoic acid.

Energy-resolved, competitive threshold collision-induced dissociation (TCID) methods are used to measure the gas-phase acidities of phenol, 3-methylphenol, 2,4,6-trimethylphenol, and ethanoic acid relative to hydrogen cyanide, hydrogen sulfide, and the hydroperoxyl radical using guided ion beam tandem mass spectrometry. The gas-phase acidities of Delta(acid)H298(C6H5OH) = 1456 +/- 4 kJ/mol, Delta(acid)H298(3-CH3C6H4OH) = 1457 +/- 5 kJ/mol, Delta(acid)H298(2,4,6-(CH3)3C6H2OH) = 1456 +/- 4 kJ/mol, and Delta(acid)H298(CH3COOH) = 1457 +/- 6 kJ/mol are determined. The O-H bond dissociation enthalpy of D298(C6H5O-H) = 361 +/- 4 kJ/mol is derived using the previously published experimental electron affinity for C6H5O, and thermochemical values for the other species are reported.

Collision-induced dissociation of HS-(HCN): unsymmetrical hydrogen bonding in a proton-bound dimer anion.

The energy-resolved competitive collision-induced dissociation of the proton-bound complex [HS.H.CN](-) is studied in a guided ion beam tandem mass spectrometer.

Photoelectron spectroscopy of phosphorus hydride anions.

Negative-ion photoelectron spectroscopy is applied to the PH-, PH2-, P2H-, P2H2-, and P2H3-molecular anions. Franck-Condon simulations of the photoelectron spectra are used to analyze the spectra and to identify various P2H(n)- species. The simulations employ density-functional theory calculations of molecular geometries and vibrational frequencies and normal modes, and coupled-cluster theory calculations of electron affinities.

Threshold collision-induced dissociation of diatomic molecules: a case study of the energetics and dynamics of O2- collisions with Ar and Xe.

The energetics and dynamics of collision-induced dissociation of O2- with Ar and Xe targets are studied experimentally using guided ion-beam tandem mass spectrometry. The cross sections and the collision dynamics are modeled theoretically by classical trajectory calculations. Experimental apparent threshold energies are 2.

Systematic and random errors in ion affinities and activation entropies from the extended kinetic method.

An evaluation of the extended kinetic method with full entropy analysis was conducted using RRKM theory to simulate data for collision-induced dissociation under single-collision conditions. A rigorous method for analyzing kinetic method data, orthogonal distance regression, is introduced and compared with previous methods in the literature. The results demonstrate that the use of the extended kinetic method is definitely superior to the standard kinetic method, but final ion affinities and activation entropies differ intrinsically from the correct values.

Gas-phase SN2 and bromine abstraction reactions of chloride ion with bromomethane: reaction cross sections and energy disposal into products.

Reaction cross sections and product velocity distributions are presented for the bimolecular gas-phase nucleophilic substitution (S(N)2) reaction Cl(-) + CH(3)Br --> CH(3)Cl + Br(-) as a function of collision energy, 0.06-24 eV. The exothermic S(N)2 reaction is inefficient compared with phase space theory (PST) and ion-dipole capture models.

Microcanonical analysis of the kinetic method. the meaning of the "apparent entropy".

A rigorous analysis of the kinetic method is carried out using Rice-Ramsperger-Kassel-Marcus (RRKM) theory of microcanonical statistical unimolecular dissociation rates. The model employs a kinetics treatment appropriate for metastable ion dissociation. Proton-bound alkoxide dimer anions are used as model systems, with realistic vibrational and rotational parameters calculated by ab initio methods for the cluster ion and transition states leading to the competitive dissociation channels.

Dynamics of the gas-phase reactions of chloride ion with fluoromethane: high excess translational activation energy for an endothermic S(N)2 reaction.

Guided ion beam tandem mass spectrometry techniques are used to examine the competing product channels in the reaction of Cl(-) with CH(3)F in the center-of-mass collision energy range 0.05-27 eV. Four anionic reaction products are detected: F(-), CH(2)Cl(-), FCl(-), and CHCl(-).