Absolute photoionization cross-section of the methyl radical

The absolute photoionization cross-section of the methyl radical has been measured using two completely independent methods. The CH3 photoionization cross-section was determined relative to that of acetone and methyl vinyl ketone at photon energies of 10.2 and 11.0 eV by using a pulsed laser-photolysis/time-resolved synchrotron photoionization mass spectrometry method. The time-resolved depletion of the acetone or methyl vinyl ketone precursor and the production of methyl radicals following 193 nm photolysis are monitored simultaneously by using time-resolved synchrotron photoionization mass spectrometry. Comparison of the initial methyl signal with the decrease in precursor signal, in combination with previously measured absolute photoionization cross-sections of the precursors, yields the absolute photoionization cross-section of the methyl radical; sigma(CH3)(10.2 eV) = (5.7 +/- 0.9) x 10(-18) cm(2) and sigma(CH3)(11.0 eV) = (6.0 +/- 2.0) x 10(-18) cm(2). The photoionization cross-section for vinyl radical determined by photolysis of methyl vinyl ketone is in good agreement with previous measurements. The methyl radical photoionization cross-section was also independently measured relative to that of the iodine atom by comparison of ionization signals from CH3 and I fragments following 266 nm photolysis of methyl iodide in a molecular-beam ion-imaging apparatus. These measurements gave a cross-section of (5.4 +/- 2.0) x 10(-18) cm(2) at 10.460 eV, (5.5 +/- 2.0) x 10(-18) cm(2) at 10.466 eV, and (4.9 +/- 2.0) x 10(-18) cm(2) at 10.471 eV. The measurements allow relative photoionization efficiency spectra of methyl radical to be placed on an absolute scale and will facilitate quantitative measurements of methyl concentrations by photoionization mass spectrometry.     

Thermal vaporization of biological nanoparticles: fragment-free vacuum ultraviolet photoionization mass spectra of tryptophan, phenylalanine-glycine-glycine, and beta-carotene

A simple, new way to introduce fragile biomolecules into the gas phase via thermal vaporization of nanoparticles is described. The general utility of this technique for the study of biomolecules is demonstrated by coupling this source to tunable synchrotron vacuum ultraviolet radiation. Fragment-free photoionization mass spectra of tryptophan, phenylalanine-glycine-glycine, and beta-carotene are detected with signal-to-noise ratios exceeding 100. The 8.0 eV photoionization mass spectrum of tryptophan nanoparticles vaporized at 373 K is dominated by a single parent ion peak that exhibits a 20-fold enhancement over the methylene indole fragment ion. The degree of dissociative photoionization of tryptophan can be precisely controlled either by the thermal energy imparted into the neutral tryptophan molecule or by the energy of the ionizing photon. The results reveal how approximately 0.5 eV changes in internal energy affect both the photoionization mass spectrum of tryptophan and the appearance energy of the daughter ion fragments. This method allows the ionization energies of glycine (9.3 +/- 0.1 eV), tryptophan (7.3 +/- 0.2 eV), phenylalanine (8.6 +/- 0.1 eV), phenylalanine-glycine-glycine (9.1 +/- 0.1 eV), and beta-carotene (<7.0 eV) molecules to be determined directly from the photoionization efficiency spectra.     

Calculation of photoionization cross sections of small metal clusters

In this paper we present photoionization cross sections of the Cu and Al dimers and tetramers. The local spin density method is applied to calculate the electronic structure and the ground state potential. The cross sections are calculated using the continuum multiple scattering method, and a basic analysis of the photoionization process is given within the independent particle picture.     

Determination of dimethylselenide and dimethyldiselenide by gas chromatography-photoionization detection

A simple method for the determination of volatile selenium compounds employing a gas chromatograph equipped with a photoionization detector is described. The method involves the direct injection of dimethylselenide (DMS) or dimethyldiselenide (DMDS) into the gas chromatograph; no derivatization of the sample was required. The photoionization detector was capable of detecting 60 pg (0.55 pmol) of DMS and 150pg (0.80pmol) DMDS. Sensitivity was 10-50 times greater with DMS and 4-20 times greater with DMDS when the photoionization detector was employed than when the flame ionization detector was employed.     

Calculation of photoionization cross sections of Na2–8 and K2–8 clusters

Analysis of free metal clusters studied with photoionization mass spectrometry or photoelectron spectroscopy requires theoretical predictions of the photoionization cross sections to gain a deeper physical understanding. Calculated energy-dependent photoionization cross sections of Na_2–8 and K_2–8 clusters are presented in this study. The ground state electronic structure of the clusters are calculated using the Local Spin Density method (LSD) which is also the starting point for the cross section calculation with the continuum multiple scattering method. A basic analysis of the photoionization process is given within the independent electron picture. Strong resonances are predicted in the UV cross sections (5–10 eV) of K_3–8 but not for Na_3–8, interpreted as shape resonances, i.e. quasibound states in which electrons are trapped by a potential barrier. Unfortunately experimental data are only known close to the ionization threshold and a comparison between our values and experimental data in a broad energy range is not possible.     

Determining the partial photoionization cross-sections of ethyl radicals

Using a crossed laser-molecular beam scattering apparatus, these experiments photodissociate ethyl chloride at 193 nm and detect the Cl and ethyl products, resolved by their center-of-mass recoil velocities, with vacuum ultraviolet photoionization. The data determine the relative partial cross-sections for the photoionization of ethyl radicals to form C2H5+, C2H4+, and C2H3+ at 12.1 and 13.8 eV. The data also determine the internal energy distribution of the ethyl radical prior to photoionization, so we can assess the internal energy dependence of the photoionization cross-sections. The results show that the C2H4++H and C2H3++H2 dissociative photoionization cross-sections strongly depend on the photoionization energy. Calibrating the ethyl radical partial photoionization cross-sections relative to the bandwidth-averaged photoionization cross-section of Cl atoms near 13.8 eV allows us to use these data in conjunction with literature estimates of the Cl atom photoionization cross-sections to put the present bandwidth-averaged cross-sections on an absolute scale. The resulting bandwidth-averaged cross-section for the photoionization of ethyl radicals to C2H5+ near 13.8 eV is 8+/-2 Mb. Comparison of our 12.1 eV data with high-resolution ethyl radical photoionization spectra allows us to roughly put the high-resolution spectrum on the same absolute scale. Thus, one obtains the photoionization cross-section of ethyl radicals to C2H5+ from threshold to 12.1 eV. The data show that the onset of the C2H4++H dissociative photoionization channel is above 12.1 eV; this result offers a simple way to determine whether the signal observed in photoionization experiments on complex mixtures is due to ethyl radicals. We discuss an application of the results for resolving the product branching in the O+allyl bimolecular reaction.     

Near threshold photoionization of the ground and first excited states of C(2)

Calculations using the multichannel Schwinger configuration-interaction method are presented for the photoionization from the ground and the first excited states of the C(2) molecule. Both single channel and multichannel calculations are presented in a photon energy range from the threshold to about 50 eV of photon energy. For the ground state, inclusion of both intrinsic and dynamical correlation effects is seen to strongly alter the picture of the photoionization process inferred from single-channel frozen-core Hartree-Fock calculations. Furthermore, the photoionization study of the first excited state of molecular carbon has revealed the presence of strong interchannel coupling between the 3sigma(g)-->ksigma(u) channel and the photoionization channels leading to the A (4)Pi(g) and f (2)Pi(g) ionic states in the near threshold region.     

Single center method: a computational tool for ionization and electronic excitation studies of molecules

We discuss the recent progress in the development of the single center (SC) method for computation of highly-delocalized discrete and partial photoelectron wave continuous functions of molecules. Basic equations of the SC method are presented, and an efficient scheme for the numerical solution of a system of coupled Hartree-Fock equations for a photoelectron is described. Several illustrative applications of the method to photoionization and electronic excitation processes in diatomic molecules are considered. Thereby, we demonstrate its potential for theoretically studying angularly resolved molecular photoionization processes.     

ON THE SUMMATION OF QUANTA FOR THE PHOTOIONIZATION OF TYROSINE AND TRYPTOPHAN IN ALKALINE SOLUTIONS AT 80°K

Abstract— Some results of a study of the summation of quanta for the photoionization of tyrosine and tryptophan in frozen alkaline solution are presented. By means of a double-beam irradiation method it has been shown that the photoionization of aromatic amino acids in such solutions proceeds via a triplet state intermediate.     

Angular distribution of photoelectrons in small molecules: a molecular quantum defect calculation

The molecular quantum defect orbital (MQDO) method, previously used in the determination of molecular photoionization cross sections, is applied here to calculate the angular distribution of photoelectrons arising from the molecular photoionization. Calculations are performed for the ionization from outer valence orbitals of HF, H(2)O, NH(3), N(2)O, and H(2)CO molecules. The results are compared with previous measurements and with theoretical curves found in the literature. Profiles of the angular distribution parameter as a function of photoelectron energy covering a range from the photoionization threshold to 120 eV are presented for the above molecules. The energy dependence of the angular distributions predicted by the MQDO calculations agrees fairly well with predictions from more sophisticated theories and with observed results.     

ESCA Peak intensities in the dipole and generalized sudden approximations using fourier transforms of GTO's

Analytical expressions for the square of the spherical average of Fourier transforms of Gaussian type orbitals (GTO 's) are given. A direct application of these expressions to the calculation of molecular photoionization cross sections is considered under the generalized sudden (GSA ) and dipole (DA ) Approximations. Numerical calculations were done on the CO molecule using bound orbitals obtained by ab initio LCAO –MO calculations with Gaussian basis sets. The results are in good agreement with experiments. Those obtained by the GSA method however, suggest a limitation in its use: the GSA method is only applicable when comparing photoionization intensities of neighboring ionization energy orbitals. Applications to other molecules are immediate.     

UV Photoionization Study of the Ethyl Radical

Introduction Ashighlyreactivebuildingblocksandfundamen talreactionintermediatesinorganicsynthesis,thealkyl radicalfamilyplaysacentralroleinadiversearrayof importantprocessesrangingfromcombustion[1]toat mosphericchemistry[2].Amongalkylradicals,theeth ylrad…     

Functional group effects in laser-excited multi-photon photoionization of organics in liquid solutions

Of the organic compounds examined for possible two-photon photoionization behavior, 43% were found to yield analytically useful photoionization with excitation at 308 nm. Fifty-five per cent produced greater photoionization responses than aniline, the de facto photoionization standard. Additionally, 16 of the surveyed compounds were more photoionization efficient (i.e., exhibit higher photoionization per unit absorption cross-section) than aniline. It was found that photoionization is relatively easily achieved with primary amines, anilines and diamines. Less readily photoionized were primary and tertiary amides, esters, alkyl ethers, and most halogenated compounds, the main exceptions being the halogenated anilines. Tertiary amines and fluorinated compounds gave poor photoionization results.     

State-dependent photoionization cross-sections of 3d transition metal atoms

Using the saturation method, we measured the absolute photoionization cross-sections of several excited states of titanium, vanadium, chromium, iron, and cobalt. These results are reported for the first time in this paper. The measured values range from 0.4 ± 0.1 Mb to 6.9 ± 2.0 Mb. The results show that the photoionization cross-section depends on the atomic state and not just on the electronic configuration.     

Photoabsorption and S 2p photoionization of the SF6 molecule: resonances in the excitation energy range of 200-280 eV

Photoabsorption and S 2p photoionization of the SF(6) molecule have been studied experimentally and theoretically in the excitation energy range up to 100 eV above the S 2p ionization potentials. In addition to the well-known 2t(2g) and 4e(g) shape resonances, the spin-orbit-resolved S 2p photoionization cross sections display two weak resonances between 200 and 210 eV, a wide resonance around 217 eV, a Fano-type resonance around 240 eV, and a second wide resonance around 260 eV. Calculations based on time-dependent density functional theory allow us to assign the 217-eV and 260-eV features to the shape resonances in S 2p photoionization. The Fano resonance is caused by the interference between the direct S 2p photoionization channel and the resonant channel that results from the participator decay of the S 2s(-1)6t(1u) excited state. The weak resonances below 210-eV photon energy, not predicted by theory, are tentatively suggested to originate from the coupling between S 2p shake-up photoionization and S 2p single-hole photoionization. The experimental and calculated angular anisotropy parameters for S 2p photoionization are in good agreement.     

Electric field effects in the photoionization and photoabsorption of methyl iodide

The effects of relatively high static electric fields (133–6533 V/cm) in the photoionization and photoabsorption of methyl iodide below the first and second ionization limits are reported. As opposed to the minor effect of the field in the photoabsorption, significant changes are observed in the photoionization below the thresholds. The changes induced by the field in the photoionization signal are explained in terms of a simple model based on the absorption spectra and on the photoionization spectrum recorded with the lowest applied field.     

Absolute photoionization cross section of the ethyl radical in the range 8-11.5 eV: synchrotron and vacuum ultraviolet laser measurements

The absolute photoionization cross section of C(2)H(5) has been measured at 10.54 eV using vacuum ultraviolet (VUV) laser photoionization. The C(2)H(5) radical was produced in situ using the rapid C(2)H(6) + F → C(2)H(5) + HF reaction. Its absolute photoionization cross section has been determined in two different ways: first using the C(2)H(5) + NO(2) → C(2)H(5)O + NO reaction in a fast flow reactor, and the known absolute photoionization cross section of NO. In a second experiment, it has been measured relative to the known absolute photoionization cross section of CH(3) as a reference by using the CH(4) + F → CH(3) + HF and C(2)H(6) + F → C(2)H(5) + HF reactions successively. Both methods gave similar results, the second one being more precise and yielding the value: σ(C(2)H(5))(ion) = (5.6 ± 1.4) Mb at 10.54 eV. This value is used to calibrate on an absolute scale the photoionization curve of C(2)H(5) produced in a pyrolytic source from the C(2)H(5)NO(2) precursor, and ionized by the VUV beam of the DESIRS beamline at SOLEIL synchrotron facility. In this latter experiment, a recently developed ion imaging technique is used to discriminate the direct photoionization process from dissociative ionization contributions to the C(2)H(5)(+) signal. The imaging technique applied on the photoelectron signal also allows a slow photoelectron spectrum with a 40 meV resolution to be extracted, indicating that photoionization around the adiabatic ionization threshold involves a complex vibrational overlap between the neutral and cationic ground states, as was previously observed in the literature. Comparison with earlier photoionization studies, in particular with the photoionization yield recorded by Ruscic et al. is also discussed.     

汽油/氧气预混火焰中烯丙基自由基的真空紫外光电离研究

The allyl radical has been observed in a low-pressure premixed gasoline/oxygen/argon flame by using tunable vacuum ultraviolet photoionization mass spectrometry. The ionization potential of the allyl radical is derived to be (8.13 + 0.02) eV from photoionization efficiency curve. In addition, a high level ab initio Gaussian-3(G3) method was used to calculate the energies of the radical and its cation. The calculated adiabatic ionization potential is 8.18 eV, which is in excellent agreement with the experimental value. The result is helpful for identifying the allyl radical formed from other flames and for understanding the mechanism of soot formation.