Multiphoton ionization of molecules in selectively excited rovibrational states

Reported are observations of multiphoton ionization of a molecule (NO) due to sequential excitation by a tunable infrared laser and a tunable dye laser. These double-resonance experiments yield multiphoton ionization spectra of specific rotational levels, selectively populated by direct IR absorption. This technique simplifies complex multiphoton ionization spectra and offers a means of sensitively and selectively detecting IR absorption of molecules.     

Influence of clustering and molecular orbital shapes on the ionization enhancement in ammonia

The Coulomb explosion of clusters is known to be an efficient source for producing multiply charged ions through an enhanced ionization process. However, the factors responsible for obtaining these high charge states have not been previously explored in detail and remain poorly understood. By comparing intensity-resolved visible laser excitation experiments with semi-classical theory over a range spanning both multiphoton and tunneling ionization regimes, we reveal the mechanism in which extreme ionization proceeds. Under laser conditions that can only singly ionize individual molecules, ammonia clusters generate ions depleted of all valence electrons. The geometries of the molecular orbitals are revealed to be important in driving the ionization, and can be entirely emptied at the energy requirement for removal of the first electron in the orbital. The results are in accord with non-sequential ionization arising from electrons tunneling from three separate molecular orbitals aided through the ionization ignition mechanism.     

Peptides investigated by laser desorption—multiphoton ionization mass spectrometry

Laser evaporation of intact neutral molecules into a supersonic beam combined with multiphoton ionization (MUPI) is used to study the fragmentation behaviour of peptides. Owing to the separation of desorption and ionization, an optimization of these processes can be applied to the sample. The investigation of mixtures containing hydrophobic and hydrophilic peptides shows equal probabilities for detection of the two molecules, demonstrating that the neutral yield of both classes of compound is equal in the desorption process. A loss of sensitivity is not observed. By employing the feature of tunable fragmentation, it is possible to sequence peptides in the gas phase. At low laser intensities only the molecular ions are formed. By increasing photon intensities, fragmentation reactions are induced. Owing to the nature of the multiphoton ionization, these mass spectra (at moderate laser powers) contain few and only structurally dependent signals. The molecular ion of the sample investigated is detected in every case.     

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.     

Mass resolved MPI spectra of methyl iodide in the 430-490 nm region

The mass resolved multiphoton ionization (MPI) spectra of methyl iodide were obtained in the 430-490 nm region using a time-of-flight (TOF) mass spectrometer. They have the same vibrational structure, which testifies that the fragment species, in the wavelength region under study, are from the photodissociation of multiphoton ionized molecular parent ions. Some features in the spectra are identified as three-photon excitations to 6p and 7s Rydberg states of methyl iodide. Two new vibrational structures of some Rydberg states are observed. The mechanism of ionization and dissociation is also discussed.     

Theory of Multi-Photon Ionization of Atoms and Molecules

In this paper we present a density matrix formalism to treat one-photon ionization and multiphoton ionization of atoms and molecules in the presence of an external field. It is shown that Fano's results for one-photon ionization without an external field can easily be obtained from our formulation. For comparison, the Green's function method applied to multiphoton ionization of molecules is also presented.     

Time‐dependent wave packet approach to Rabi oscillation in strong laser field

The phenomenon of Rabi oscillation is obtained in the investigation of the NO multiphoton ionization (MPI) in femtosecond laser fields. The “split operator‐Fourier transform” method of wave packet propagation is used in the representation of Rabi oscillation of population in each electronic state of NO molecule. The origin of Rabi oscillation and the effect on multiphoton ionization is analyzed. The high‐frequency oscillation riding on the top of Rabi oscillation is attributed to the nonrotating wave component in strong laser fields. Also illustrated is that through adjusting the pump‐probe delay time and the laser intensity appropriately the control of the ionization yield can be realized. This idea may be important for the laser control of chemical reaction. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 95: 30–36, 2003     

Surface analysis by laser desorption of neutral molecules with detection by fourier-transform mass spectrometry

Molecules chemisorbed on a platinum single crystal are desorbed by a pulsed laser, ionized by an electron beam or multiphoton ionization, and detected by Fourier-transform mass spectrometry (F.t.m.s.). Laser desorption of ethylene, methanol, cyanogen, benzene and naphthalene is described. In all cases, molecular ions are the major peaks observed in the mass spectra, and the minor peaks correspond to known electron-impact fragments of the adsorbates. For the systems investigated thus far, the laser-desorption F.t. mass spectra are less complex and esier to interpret than the spectra produced by secondary-ion mass spectrometry, which are complicated by the rapid ion/-molecule reactions that can occur directly above the surface between adsorbates and substrate atoms. In the laser-desorption method, these complications are avoided because the ions are formed after the desorbed molecules have moved away from the surface and have expanded into the vacuum. The sensitivity of the laser-desorption F.t.m.s. method is tested. For carbon monoxide adsorbed on platinum, the detection limit is ca. 5 × 10^?6 monolayer per cm². For naphthalene, a single laser pulse at 248 nm produces abundant molecular ions even when the electron beam is turned off. The ions appear to be produced by resonance-enhanced multiphoton ionization rather than a thermal process. In these experiments, multiphoton ionization of naphthalene at 248 nm is about 35-fold more sensitive than electron ionization.     

Sequential multiphoton ionization spectroscopy: extension of a useful spectroscopic tool

An adaptation of multiphoton ionization spectroscopy is presented in which a single vibrational—rotational level of an excited electronic state is pumped using a dye laser, and a second, independently tunable dye laser beam induces multiphoton ionization from this excited level. Several advantages of this technique are demonstrated using molecular iodine.     

Atmospheric pressure photoionization mechanisms. 2. The case of benzene and toluene

Benzene and toluene have been proposed previously as dopants in atmospheric pressure photoionization (APPI) experiments on compounds exhibiting ionization energies higher than the energy of photons used for irradiation. Their low ionization energies lead to their easy photoionization and the ions so formed lead to the ionization of analytes through charge exchange. However, some measurements have shown that some protonation reactions also take place, and a series of experiments was undertaken to investigate this unexpected behavior. It was shown that, when benzene is irradiated in the APPI source, the odd-electron molecular ions of phenol, diphenyl ether and phenoxyphenol are produced in high yield, together with protonated diphenyl ether and protonated phenoxyphenol. These results have been confirmed by deuterium labelling and MS(n) experiments. A possible mechanism is proposed, based on a radical attack by benzene molecular ions on oxygen molecules present inside the APPI source, analogous to that proposed in the literature for phenyl radicals. Similar results have been obtained with toluene, proving that APPI is able to activate a series of reactions leading to highly reactive species which are highly effective in promoting ionization of molecules with ionization energies higher than the photon energy.     

193 nm Laser photoionization and photodissociation for isomer differentiation in Fourier-transform mass spectrometry

Energetic (6.4 eV) multiphoton ionization (MPI) or photodissociation, effected interchangeably in a Fourier-transform mass spectrometer, can differentiate isomers that yield similar electron ionization spectra. Selectivity is shown for isomers of C₇H₈, C₇H₉N, C₇H₇F, C₈H₁₀, but not of C₆H₃Cl₃ and C₁₄H₁₀. The contrasting MPI fragmentations and ionization efficiencies, as well as high sensitivities, are of substantial analytical utility. The high ionization efficiency makes possible high resolution MPI spectra, such as 470,000 (FWHH) for the molecular ion of anthracene, from a single laser pulse.     

Modification of multiphoton ionization spectra via third harmonic generation in focused laser beams

The modification of multiphoton ionization spectra through third harmonic generation in focused laser beam geometries is reported. A strong enhancement of the ionization peaks corresponding to the decay of thenf' autoionizing series of Kr and the observation of a double resonance in Xe, which is missing in low atomic density spectra, is shown to originate from excitation channels involving absorption of third harmonic photons. This excitation is demonstrated to occur in a significantly extended volume outside the focal region, thus strongly increasing the ionization yield.     

Ultraviolet femtosecond laser ionization mass spectrometry

For this study, multiphoton ionization/mass spectrometry using an ultraviolet (UV) femtosecond laser was employed for the trace analysis of organic compounds. Some of the molecules, such as dioxins, contain several chlorine atoms and have short excited-state lifetimes due to a "heavy atom" effect. A UV femtosecond laser is, then, useful for efficient resonance excitation and subsequent ionization. A technique of multiphoton ionization using an extremely short laser pulse (e.g., <10 fs), referred to as "impulsive ionization," may have a potential for use in fragmentation-free ionization, thus providing information on molecular weight in mass spectrometry.     

在超声分子束条件下Mn2(CO)10的多光子电离解离

近年来，人们对具有金属－金属键的Mn2（CO）10分子的光解离电离动力学的研究十分关注．这一方面是由于其独特的分子结构可以获得丰富的光化学及其化学性质方面的信息；另一方面从其结构和光活性之间的关系，有助于了解双核金属有机化合物在催化反应中所起的作用．Leutwyler和Even[1]曾在超声分子来条件下，用脉冲染料激光实现了Mn2（CO）10的多光子电离解离（MPID）过程，获得Mni＋（i＝1，2，3）金属碎片离子．Lichin等人[2]曾用511nm和483nm激光引起Mn2（CO）10的气相多光子解离和电离，测得产物中除了Mn＋，Mn2＋和MnCO＋离子…     

Laser multiphoton ionization of triethylamine following collision-free IR multiple-photon excitation

The multiphoton ionization mass spectrum of triethylamine can be modified by infrared excitation of the neutral using a pulsed CO₂ laser. The yield of a given ion can be maximized by judiciously controlling the timing, fluence and wavelength of the infrared laser. The results are interpreted in terms of competition between three- and four-photon ionization processes, wherein the former are assisted by favorable Frank—Condon due to vibrational excitation.     

The role of intermediate state polarization in determination of vector properties of the ground state using multiphoton excitation

We present a general theory for calculating the vector and geometrical properties of the multiphoton excitation of an arbitrary atomic or molecular system. The results are applied to study the influence of the polarization of the two-photon excited state, which is usually neglected, on the intensity of (2 + 1) resonant multiphoton ionization in atoms. Two examples of specific atomic systems of practical importance are presented: oxygen and chlorine. For some cases, the effect of the polarization of the pre-ionized state can be significant and must be properly treated.     

Multiphoton ionization photoelectron spectroscopy: xenon and nitric oxide

Photoelectron spectra (≈50 mcV, full width at half maximum) following resonantly enhanced multiphoton ionization of xenon and nitric oxide have been recorded and compared to the previous low-resolution (≈120 mcV) results. Several new features have been resolved and additional experiments, which include iso topic substitution and two-color multiphoton ionization. have been performed.     

吡啶气相分子的共振多光子电离谱

本工作观测了双光子能量在35180-36002cm^-^1范围内吡啶分子的共振多光子电离谱。对电子跃迁S~1(^1B~1)→S~0(^1A~l)的振动带做了归属, 首次在^1B~1态观察到7个新的振动模。讨论了N原子取代对分子结构及振动模的影响。     

State-resolved dynamics of oxygen atom recombination on polycrystalline Ag

Rotationally resolved, velocity distributions for desorbed O2 molecules formed by O-atom recombination on the surface of a polycrystalline Ag surface are reported. Surface O atoms are generated by oxygen permeation through a 0.25-mm-thick Ag foil heated to 1020 K. Desorbing O2 molecules are probed by (2 + 1) resonant multiphoton ionization via the C 3Pig (3ssigma), v' = 2 <-- <-- X 3Sigmag-, v" = 0 transition and time-of-flight mass spectrometry. Measured velocity distributions are near Maxwell-Boltzmann and yield average translational energies which are significantly lower than the surface temperature ([Et]/2kB approximately 515 K) and essentially independent of rotational excitation. Comparison of the observed C-X (2,0) resonantly enhanced multiphoton ionization spectrum with spectral simulations suggests that the v" = 0 rotational state distribution is more consistent with the surface temperature, but spectral congestion and apparent intensity perturbations prevent a more quantitative analysis. The calculated, sticking curves show a small barrier energy barrier (approximately 10 meV) beyond which sticking decreases. These observations are consistent with low energy desorption and adsorption pathways involving a weakly bound molecular O2 precursor.     

A discrete time-dependent method for metastable atoms and molecules in intense fields

The full-dimensional time-dependent Schr?dinger equation for the electronic dynamics of single-electron systems in intense external fields is solved directly using a discrete method. Our approach combines the finite-difference and Lagrange mesh methods. The method is applied to calculate the quasienergies and ionization probabilities of atomic and molecular systems in intense static and dynamic electric fields. The gauge invariance and accuracy of the method is established. Applications to multiphoton ionization of positronium, the hydrogen atom and the hydrogen molecular ion are presented. At very high laser intensity, above the saturation threshold, we extend the method using a scaling technique to estimate the quasienergies of metastable states of the hydrogen molecular ion. The results are in good agreement with recent experiments.