Fourier transform ion cyclotron resonance detection of multiphoton ionization spectroscopy

Fourier transform ion cyclotron resonance (FT-ICR) detection was tested for resonanceenhanced multiphoton ionization (REMPI) spectroscopy. The (2+1) REMPI spectra of acetaldehyde were obtained in the wavelength range 364–354 nm via a two-photon resonant 3s ← n Rydberg transition. The space-charge effects on the REMPI spectra were examined in the vicinity of the 0 ₀ ⁰ transition. The trapping efficiency measurement shows that all the ions produced from REMPI dissociation processes are arrested in the ion cyclotron resonance cell even in the presence of space-charge interactions. Axial kinetic energy release distributions of ions were extracted from the trapping efficiency data obtained under a new space-charge-free condition. FT-ICR peak heights were measured as a function of pressure at different laser powers, magnetic field strengths, and ion excitation methods to test for the detection linearity. The FT-ICR detection responds linearly to the number of ions in a low pressure limit. The product branching ratio was measured by using various ion excitation methods and was compared with the previous quadrupole mass spectrometric study. FT-ICR detection yields the mass-selected REMPI spectra and the product branching ratio in the absence of kinetic shifts.     

Saturation and fragmentation in non resonant laser postionization of sputtered atoms and molecules

Summary Using non resonant two photon ionization at =248 nm, the emission of neutral atoms and dimers was investigated during ion beam sputtering of polycrystalline silver and copper with 5 keV Ar⁺. Saturation effects were examined by measuring the ion intensities as a function of the photon flux density. It is found that with the maximum available laser power density (1·10⁹ W/cm²) the ionization of Ag atoms can be easily saturated, whereas no complete saturation was achieved for Cu atoms. At the same time the saturation curve measured for Ag differs significantly both from that measured for Cu and from the theoretically expected behaviour for non resonant two photon ionization. For Ag₂ and Cu₂ the ionization is shown to be strongly resonance enhanced already being saturated in the region of 10⁷ W/cm². From the data taken at low laser power densities (<10⁶ W/cm²), the role of fragmentation processes either by dissociative ionization or by neutral dissociation is discussed. As an example, the results using laser postionization are employed to quantitatively determine the abundance of Ag₂ molecules in the flux of neutral particles sputtered from the silver sample.     

Formation of gold cluster cations by direct laser vaporization

Gold cluster cations, Au⁺_n, with n= 1 to 6 have been produced by direct laser vaporization of gold metal in a Fourier transform ion cyclotron resonance mass spectrometer. Wavelength studies at λ = 532, 355, and 266 nm show similar results. However, the intensities and intensity ratios of the cluster ions strongly depended on laser power at the two longer wavelengths. Ionization energies of Au⁺ , Au⁺₂, and Au⁺₃ have also been estimated.     

Multiphoton dissociation of molecules with low power cw infrared lasers: collisional enhancement of dissociation probabilities

Multiphoton dissociation of C₃F⁺₆ is observed using low intensity cw CO₂ laser radiation. Ion cyclotron resonance (ICR) techniques are used to store ions for irradiation. Ion storage times up to 2 s are used. Multiphoton dissociation is observed at laser intensities below 100 W cm^?2 and at pressures below 10^?5 Torr. Only the lowest energy decomposition of C₃F⁺₆, to give C₂⁺₄ and CF₂, is observed. Multiphoton dissociation probabilities show a sharp wavelength dependence in contrast to typical pulsed laser multiphoton dissociation experiments. The photodissociation spectrum of C₃F⁺₆ is similar to the infrared absorption spectrum of neutral C₃F₆ at both low and high resolution. Collisions between C₃F⁺₆ and unreactive buffer gases (Ar, N₂, SF₆) are seen to enhance multiphoton dissociation, while collisions with C₃F₆ deactive the laser excited species. The results are discussed in terms of mechanisms for slow multiphoton dissociation.     

Electron spectra of WO molecule. New electron state <Superscript>3</Superscript>Π

The electron spectrum of the tungsten monooxide molecule is observed in the 550–800 nm region using intracavity laser absorption spectroscopy. The WO molecules are produced in a pulsed electric discharge through the mixture of tungsten hexacarbonyl vapors. The spectrum is recorded using a diffraction spectrometer (resolving power of 240000). The bands in the 16400–15500 cm^–1 region are assigned to the ³Π₀–X³Σ⁺ component of the ³Π₀–X³Σ⁺–³XΣ⁺ electron transition. The rotational analysis of the 0-0 and 1-0 bands is carried out and the rotational constants for the ground X″³Σ and the exited ³Π₀ states are computed: В′ = 0.385738 cm^–1, B″ = 0.415538 cm^–1.     

Fourier transform ion cyclotron resonance spectroscopy

An ion cyclotron resonance (ICR) absorption spectrum has been obtained by exciting an ICR spectral segment with a fixed-frequency electric field pulse, followed by broad-band detection, digitization of the (time-domain) transient response, and digital Fourier transformation to produce the (frequency-domain) absorption spectrum. For a given signal-to-noise ratio and resolution, the FT-ICR method generates a spectrum in a time which is two orders of magnitude shorter than that required in conventional slow-sweep ICR detection. In the present example, a signal-to-noise ratio of 8:1 and a mass resolution of about 0.005 amu for CH₄⁺ (from CH₄ at a pressure of 8 X 10^?7 torr) have been achieved, using a single data acquisition period of 25.6 msec.     

Observation of photodissociation of S2Cl2 and resonance Raman and fluorescence spectra of S2Cl under 514.5 nm radiation

The laser Raman spectrum of S₂Cl₂ varies with the sample temperature and/or the laser power. The Raman signals of S₂Cl₂ decreases as the sample molecules within the laser beam are dissociated by absorbing 514.5 nm photons. Above 540 K and 2 W of laser power, new resonance Raman and fluorescence bands appear. These bands were all assigned to S₂Cl. The fluorescence bands could be classified into two transition systems. Only one of them had the ground electronic state X̃ as its lower state. For the other, the low lying first excited state à was suspected. The fundamental frequencies suggested for the three vibrational modes were 664, 196 and 450 cm⁻¹ for the X̃ state and 630, 249 and 554 cm⁻¹ for the à state respectively.     

Tuning the Reactivities of the Heteronuclear [AlnV3−nO7−n]+ (n=1, 2) Cluster Oxides towards Methane by Varying the Composition of the Metal Centers

The thermal gas-phase reactions of [Al₂VO₅]⁺ and [AlV₂O₆]⁺ with methane have been explored by using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry complemented by high-level quantum chemical calculations. Both cluster ions chemisorbed methane as the major reaction channels at room temperature. [Al₂VO₅]⁺ could break only one C−H bond to liberate CH₃, whereas [AlV₂O₆]⁺ exhibited higher oxidizing ability such that it brings about the selective generation of formaldehyde. Mechanistic aspects are revealed and the crucial roles of the metal centers are discussed.     

Use of CF3,Br/Al,discharges for reactive ion etching of III-V semiconductors

The reactive ion etching of GaAs, InP, InGaAs, and InAlAs in CF₃Br/Ar discharges was investigated as a function of both plasma power density (0.56-1.3 W - cm^–2) and total pressure (10-40 mTorr) The etch rate of GaAs in 19CF₃Br:1Ar discharges at 10 m Torr increases linearly with power density, from 600 Å min^–1 at 0.56 W · cm^–2, to 1550 Å · min at 1.3 W · cm^–2. The in-based materials show linear increases in etch rates only for power densities above – 1.0 W · cm^–2. These etch rates are comparable to those obtained with CCI₂F₂:O₂ mixtures under the same conditions. Smooth surface morphologies and vertical sidewalls are obtained over a wide range of plasma parameters. Reductions in the near-surface carrier concentration in n-type GaAs are evident for etching with power densities of >0.8 W cm^–2, due to the introduction of deep level trapping centers. At 1.3 W· cm^–2, the Schottky barrier height of TiPtAu contacts on GaAs is reduced from 0.74 to 0.53 eV as a result of this damage, and the photoluminescent intensity from the material is degraded. Alter RIE, we detect the presence of both F and Br on the surface of all of the semiconductors. This contamination is worse than with CCl₂F₂-based mixtures. High-power etching with CF₃Br/Ar together with Al-containing electrodes can lead to the presence of a substantial layer of aluminum oxide on the samples if the moisture content in the reactor is appreciable.     

Gas-Phase studies of valinomycin-alkali metal cation complexes: attachment rates and cation affinities

Reactions of laser-desorbed Na⁺, K⁺, Rb⁺, and Cs⁺ with thermally vaporized valinomycin generate metal-ligand complexes in a Fourier transform ion cyclotron resonance trapping cell, proving that complexes can form via gas-phase ion-molecule reactions. Although desorption of intact pre-formed complexes cannot be ruled out, this route appears minor. Relative rate constants for the complexation reactions show strong dependence on the charge densities of the cations. Competition experiments between valinomycin and the synthetic ionophores 18-crown-6 (18C6) and [2.2.2]-cryptand ([2.2.2]) show that valinomycin has a higher intrinsic alkali metal cation affinity than either 18C6 or [2.2.2], in contrast to the complex formation constants observed in methanol, where K+ affinities are in the order [2.2.2] > 18C6 > valinomycin.     

Untersuchungen an 1,2-Komplexen der Nickel(II)-halogenide mit N-substituierten Aminoäthylpyridinen-(2)

In the solid state complexes of the type MiL₂X₂ (L = N-substituted β-aminoethyl-pyridine; X = Cl, Br, J) have a cis-octahedral (X = Cl, Br) or a distorted trigonal bipyramidal structure (X = J). In solutions in acetone a partial dissociation occurs with the formation of NiLX₂, L, NiL₂X⁺, and X^?. Using a spectrophotometric method stability constants K_2S of the complexes NiL₂X₂ are determined. A correlation exists between log K_2s and the pK- values of the quarternary ammonium ions derived from the ligands L. Sterical factors cause the exeptional position of the chelates of β-methylaminoethylpyridine-(2).     

Gas-phase protonation and methyl cation transfer from methyl halide ions

The ion-molecule reactions between [CH₃X]⁺˙ [CH₃XH] ⁺, [CH₃XCH₃]⁺ ions (X = F, Cl, Br, I) and a number of nucleophiles have been studied by ion cyclotron resonance techniques. Protonation of the nucleophiles is observed to occur from both the molecular ions [CH₃]X⁺˙ and protonated species [CH₃XH]⁺ whereas dimethylhalonium ions [CH₃XCH₃]⁺ react principally by methyl cation transfer. A notable exception occurs in methyl iodide where the molecular ions [CH₃I]⁺˙ act both as proton and methyl cation donors, whereas dimethyliodonium ions are found unreactive. The results are discussed with reference to the use of alkyl halides as reagent gases in chemical ionization experiments.     

Adducts of coordination compounds-XIII. Nitrates,hydrogen and silver dinitrates,and polysilver nitrates of trans-dihalotetrakispyridinerhodium(III) and iridium(III) ions

The synthesis and characterization, chiefly as salts of the anions [X(ONO₂)₂]⁻ (X = H⁺ or Ag⁺) (by analysis, X-ray powder photography, vibrational spectra and thermogravimetry) of adducts of the nitrates trans-[M(L)₄X₂](NO₃) (M =Rh or Ir; L = pyridine, perdeuteriopyridine or 4-methylpyridine; X = Cl or Br) with hydrogen nitrate and silver nitrate are described.     

Substituent Effects in P- and As-centered Radical Cations

The first vertical ionization potentials of isostructural P(III) and As(III) compounds EX₃ (E = P, As) whose highest occupied molecular orbital is preferentially localized on the lone electron pairs of atom E depend on the inductive, resonance, and polarization effects of substituents X. Hyperconjugation in fragments like As^{+ ·}-C-H is the only resonance effect in radical cations As^{+ ·}X₃. The same effect in similar P-centered radical cations is weaker.     

A new semiempirical kinetic method for the determination of ion exchange constants for counterions of cationic micelles: Study of the rate of pH‐independent hydrolysis of phthalimide as the kinetic probe

Pseudo‐first‐order rate constants (k_obs) for pH‐independent hydrolysis of phthalimide ( 1 ), obtained at a constant total concentration of cetyltrimethylammonium bromide and hydroxide ([CTABr]_T), 2.0 × 10^?4 M 1 , 0.02 M MOH (M⁺ = Li⁺, Na⁺ and K⁺) and various concentrations of inert salt MX (= LiCl, LiBr, NaCl, NaBr, KCl and KBr), follow a relationship derived from the pseudophase micellar (PM) model coupled with an empirical equation. This relationship gives empirical constants, F_X/S and K_{X /S}, with S representing anionic 1 . The magnitude of F_X/S is the measure of the fraction of micellized anionic 1 (S^?_M) transferred to the aqueous phase by the limiting concentration of X^?. The value of K_X/S is the measure of the ability of the counterions (X^?) to expel the reactive counterions (S^?) from the cationic micellar surface to the aqueous phase. The values of F_{X/ S} are ～ 1 for MBr (M⁺ = Li⁺, Na⁺ and K⁺) and in the range ? 0.7 to ? 0.5 for MCl (M⁺ = Na⁺ and K⁺) at 0.006, 0.010 and 0.016 M CTABr. For LiCl, the values of F_X/S become ～1 at 0.006 and 0.010 M CTABr and 0.8 at 0.016 M CTABr. The values of the empirical constants, F_X/S and K_X/S, have been used to determine the usual ion exchange constant (K^Cl_Br). The mean values of K^Cl_Br are 3.9 ± 0.5, 2.7 ± 0.1, and 2.6 ± 0.3 for LiX, NaX, and KX, respectively. These values of K^Cl_Br are comparable with those obtained directly by other physicochemical techniques. Thus, this new method for the determination of ion exchange constants for various counterions of cationic micelles may be considered as a reliable one. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 43: 9–20, 2011     

Exploring the Anion–Cation Interaction in m‐Terphenyltetrafluorosilicates by Using Multinuclear NMR Spectroscopy,X‐ray Diffraction,and ICR‐FT‐MS

The synthesis of a series of m‐terphenyl‐substituted tetrafluorosilicates with different cations (Na⁺, K⁺, Rb⁺, Cs⁺, Ag⁺, Tl⁺) is described and the interactions between the anion and cation are investigated in the solid, solution, and gas states by using multinuclear NMR spectroscopy, X‐ray diffraction, and ion cyclotron resonance Fourier‐transform mass spectrometry (ICR‐FT‐MS). In solution, heteronuclear NMR spectroscopy parameters show only limited sensitivity to the nature of the cation, which furthermore can be affected by solvent effects. More pronounced effects are observed in the structural data obtained from X‐ray diffraction studies, which are in good agreement with experimental gas‐phase data from ESIMS. ESIMS also reveals the existence of dimeric species of the type [M(DmpSiF₄)₂]^? (Dmp=2,6‐dimesitylphenyl), the stability of which was determined by normalized collision energy experiments.     

Cluster isobars for high-precision mass spectrometry

Doublet mass measurements of the isobars²⁸Si₃ and¹²C₇ are performed by use of a Penning trap mass spectrometer and the Fourier transform ion cyclotron resonance (FT-ICR). The carbon and silicon cluster ions are produced by laser ablation. Results of these preliminary measurements are presented.     

Radiative lifetime for v = 1 and v = 2 ground state NO+ ions

Radiative lifetimes of vibrationally excited ions in their electronic ground state have been measured for the first time. A nonoptical technique has been developed, involving ion cyclotron resonance trapping in conjunction with chemical monitoring of the energy content of the ions. For NO⁺(X ¹Σ⁺) ions, the measured lifetimes of 95 ± 15 ms for v = 1 and 46 ± 10 ms for v = 2 are in excellent agreement with the values obtained from the ab initio calculations of Werner and Rosmus.     

Electrochemical studies on ion-selective polymer membrane electrodes

The selectivity and response of neutral carrier based polymer membrane electrodes are investigated via exchange current measurements for systems containing valinomycin, dibenzo-18-crown-6, and plasticizer alone in a polyvinyl chloride matrix. Using a transient galvanostatic step method, apparent exchange current densities of 1.3 X 10^?3 A/cm², 5.4 X 10^?6 A/cm², and 2.2 X 10^?9 A/cm² were obtained with K⁺ as the primary ion for the three types of membranes, respectively. Preliminary results indicate that the exchange current data obtained with this technique are complementary to the potentiometric response observed for the membranes studied.     

b1Σ+ and a1Δ emissions from group VI-VI diatomic molecules: b0+ → X10+, x21 emissions of TeO and TeS

Near infrared emissions of the b0⁺→X₁0⁺, X₂1 band systems of TeO and TeS have been observed by chemiluminescence studies in a fast flow system. In both cases the b → X₁ and b → X₂ subtransitions were found to occur with similar intensities. Analysis of the spectra yielded values of the b0⁺ energies T_e of 9966 ^± 10 cm^?1 and 8457 ^± 10 cm^?1 for TeO and TeS, respectively, and vibrational separations ω_e in these states of 726 ^± 10 cm^?1 and 436 ^± 5 cm^?1. The energy splittings of the X₁0⁺ and X₂1 ground state levels were determined to be 789 ^± 10 cm^?1 and 829 ^± 5 cm^?1.