Showing papers on "Ionization published in 2004"

The dynamics of small molecules in intense laser fields

Abstract: In the past decade, the understanding of the dynamics of small molecules in intense laser fields has advanced enormously. At the same time, the technology of ultra-short pulsed lasers has equally progressed to such an extent that femtosecond lasers are now widely available. This review is written from an experimentalist's point of view and begins by discussing the value of this research and defining the meaning of the word 'intense'. It continues with describing the Ti: sapphire laser, including topics such as pulse compression, chirped pulse amplification, optical parametric amplification, laser-pulse diagnostics and the absolute phase. Further aspects include focusing, the focal volume effect and space charge. The discussion of physics begins with the Keldysh parameter and the three regimes of ionization, i.e. multi-photon, tunnelling and over-the-barrier. Direct-double ionization (non-sequential ionization), high-harmonic generation, above-threshold ionization and attosecond pulses are briefly mentioned. Subsequently, a theoretical calculation, which solves the time-dependent Schrodinger equation, is compared with an experimental result. The dynamics of H-2(+) in an intense laser field is interpreted in terms of bond-softening, vibrational trapping (bond-hardening), below-threshold dissociation and laser-induced alignment of the molecular axis. The final section discusses the modified Franck-Condon principle, enhanced ionization at critical distances and Coulomb explosion of diatomic and triatomic molecules.

Tunnel and multiphoton ionization of atoms and ions in a strong laser field (Keldysh theory)

Abstract: The theoretical description of the nonlinear photoionization of atoms and ions exposed to high-intensity laser radiation is underlain by the Keldysh theory proposed in 1964. The paper reviews this theory and its further development. The discussion is concerned with the energy and angular photoelectron distributions for the cases of linearly, circularly, and elliptically polarized laser radiation, with the ionization rate of atomic states exposed to a monochromatic electromagnetic wave and to ultrashort laser pulses of various shape, and with momentum and angular photoelectron spectra in these cases. The limiting cases of tunnel (γ 1) and multiphoton (γ 1) ionization are discussed, where c is the adiabaticity parameter, or the Keldysh parameter. The probability of above-barrier ionization is calculated for hydrogen atoms in a low-frequency laser field. The effect of a strong magnetic field on the ionization probability is discussed. The process of Lorentz ionization occurring in the motion of atoms and ions in a constant magnetic field is considered. The properties of an exactly solvable model—the ionization of an s-level bound by zero-range forces in the field of a circularly polarized electromagnetic wave—are described. In connection with this example, the Zel'dovich regularization method in the theory of quasistationary states is discussed. Results of the Keldysh theory are compared with experiment. A brief discussion is made of the relativistic ionization theory applicable when the binding energy of the atomic level is comparable with the electron rest mass (multiply charged ions) and the sub-barrier electron motion can no longer be considered to be nonrelativistic. A similar process of electron-positron pair production from a vacuum by the field of high-power optical or X-ray lasers (the Schwinger effect) is considered. The calculations invoke the method of imaginary time, which provides a convenient and physically clear way of calculating the probability of particle tunneling through time-varying barriers. Discussed in the Appendices are the properties of the asymptotic coefficients of the atomic wave function, the expansions for the Keldysh function, and the so-called 'ADK theory'.

Atmospheric pressure ion source

Abstract: A non-radioactive atmospheric pressure device for ionization of analytes comprises an atmospheric pressure chamber having an inlet for carrier gas, a first electrode (31) at one end, and a counter-electrode (32) at the other end of the chamber for creating an electrical discharge in the carrier gas thus creating metastable neutral excited-state species. Optionally, a grid (14) is provided to generate electrons or ions by contact with the excited-state species. The carrier gas containing the excited-state species or the electrons generated therefrom is directed at an analyte at atmospheric pressure near ground potential to form analyte ions.

Optics at critical intensity: Applications to nanomorphing

Abstract: Laser-induced optical breakdown by femtosecond pulses is extraordinarily precise when the energy is near threshold. Despite numerous applications, the basis for this deterministic nature has not been determined. We present experiments that shed light on the basic mechanisms of light-matter interactions in this regime, which we term "optics at critical intensity." We find that the remarkably sharp threshold for laser-induced material damage enables the structure or properties of materials to be modified with nanometer precision. Through detailed study of the minimum ablation size and the effects of polarization, we propose a fundamental framework for describing light-matter interactions in this regime. In surprising contrast to accepted damage theory, multiphoton ionization does not play a significant role. Our results also reject the use of the Keldysh parameter in predicting the role of multiphoton effects. We find that the dominant mechanism is Zener ionization followed by a combination of Zener and Zener-seeded avalanche ionization. We predict that the minimum feature size ultimately depends on the valence electron density, which is sufficiently high and uniform, to confer deterministic behavior on the damage threshold even at the nanoscale. This behavior enables nanomachining with high precision, which we demonstrate by machining highly reproducible nanometer-sized holes and grooves in dielectrics.

Quantum Control by Ultrafast Polarization Shaping

Abstract: We demonstrate that the use of time-dependent light polarization opens a new level of control over quantum systems. With potassium dimer molecules from a supersonic molecular beam, we show that a polarization-shaped laser pulse increases the ionization yield beyond that obtained with an optimally shaped linearly polarized laser pulse. This is due to the different multiphoton ionization pathways in K2 involving dipole transitions which favor different polarization directions of the exciting laser field. This experiment is a qualitative extension of quantum control mechanisms which opens up new directions giving access to the three-dimensional temporal response of molecular systems. DOI: 10.1103/PhysRevLett.92.208301

Complete depletion in prestellar cores

Abstract: We have carried out calculations of ionization equilibrium and deuterium fractionation for conditions appropriate to a completely depleted, low mass pre-protostellar core, where heavy elements such as C, N, and O have vanished from the gas phase and are incorporated in ice mantles frozen on dust grain surfaces. We put particular emphasis on the interpretation of recent observations of H 2 D + towards the centre of the prestellar core L 1544 (Caselli et al. 2003) and also compute the ambipolar diffusion timescale. We consider explicitly the ortho and para forms of H 2 , H + 3, and H 2 D + . Our results show that the ionization degree under such conditions depends sensitively on the grain size distribution or, more precisely, on the mean grain surface area per hydrogen nucleus. Depending upon this parameter and upon density, the major ion may be H + , H + 3, or D + 3. We show that the abundance of ortho-H 2 D + observed towards L 1544 can be explained satisfactorily in terms of a complete depletion model and that this species is, as a consequence, an important tracer of the kinematics of prestellar cores.

The Structure and Evolution of Early Cosmological HII Regions

Abstract: We study the formation and evolution of HII regions around the first stars formed at z=10-30. We use a one-dimensional Lagrangian hydrodynamics code which self-consistently incorporates radiative transfer and non-equilibrium primordial gas chemistry. The star-forming region is defined as a spherical gas cloud with a Population III star embedded at the center. We explore a large parameter space of host halo mass, gas density profile, and stellar luminosity. The formation of the HII region is characterized by initial slow expansion of a weak D-type ionization front near the center, followed by rapid propagation of an R-type front throughout the outer gas envelope. We find that the transition between the two front types is indeed a critical condition for the complete ionization of halos of cosmological interest. In small mass ( 80%) of both ionizing and photodissociating photons. In larger mass (> 10^7 M_sun) halos, the ionization front remains to be of D-type over the lifetime of the massive star, the HII region is confined well inside the virial radius, and the escape fractions are essentially zero. We derive an analytic formula that reproduces well the results of our simulations. We discuss immediate implications of the present results for the star formation history and early reionization of the Universe.

Study of stationary plasma thrusters using two-dimensional fully kinetic simulations

Abstract: Stationary plasma thrusters are devices that use crossed electric and magnetic fields to accelerate ions to high velocities. Ions are created by collisional ionization of a propellant gas with electrons injected from a hollow cathode external to the thruster. A major issue is the electron transport through the magnetic field. It is known to exceed considerably the values predicted by the classical theory. Various 2D models have shown that wall collisions, which have often been invoked as the origin of this anomalous transport, are in fact insufficient. Anomalous turbulent transport has to be added to the model to recover an adequate conductivity. In the present paper the first 2D kinetic model that shows that, indeed, plasma turbulence can explain the observed conductivity is presented. Without any free parameter the model is able to reproduce numerous experimental features. At the end of the paper a preliminary theoretical analysis of the observed instability is provided.

Electrosonic Spray Ionization. A Gentle Technique for Generating Folded Proteins and Protein Complexes in the Gas Phase and for Studying Ion−Molecule Reactions at Atmospheric Pressure

Abstract: Electrosonic spray ionization (ESSI), a variant on electrospray ionization (ESI), employs a traditional micro ESI source with supersonic nebulizing gas. The high linear velocity of the nebulizing gas provides efficient pneumatic spraying of the charged liquid sample. The variable electrostatic potential can be tuned to allow efficient and gentle ionization. This ionization method is successfully applied to aqueous solutions of various proteins at neutral pH, and its performance is compared to that of the nanospray and micro ESI techniques. Evidence for efficient desolvation during ESSI is provided by the fact that the peak widths for various multiply charged protein ions are an order of magnitude narrower than those for nanospray. Narrow charge-state distributions compared to other ESI techniques are observed also; for most of the proteins studied, more than 90% of the protein ions can be accumulated in one charge state using ESSI when optimizing conditions. The fact that the abundant charge state is norm...

ISO spectroscopy of disks around Herbig Ae/Be stars

Abstract: We have investigated the infrared spectra of all 46 Herbig Ae/Be stars for which spectroscopic data is available in the ISO data archive. Our quantitative analysis of these spectra focusses on the emission bands linked to polycyclic aromatic hydrocarbons (PAHs), the amorphous 10 micron silicate band and the crystalline silicate band at 11.3 micron. We have detected PAH emission in 57% of the Herbig stars in our sample. Clear examples of differences in the PAH spectra are present within our sample, indicating differences in PAH size, chemistry and/or ionization. Amorphous silicate emission was detected in the spectra of 52% of the sample stars, amorphous silicate absorption in 13%. We have detected crystalline silicate emission in 11 stars (24% of our sample), of which four (9%) also display strong PAH emission. We have classified the sample sources according to the strength of their mid-IR energy distribution. The systems with stronger mid-infared (20-100 um) excesses relative to their near-infrared (1-5 um) excess display significantly more PAH emission than those with weaker mid-infrared excesses. This provides strong observational support for the disk models by Dullemond (2002), in which systems with a flaring disk geometry display a strong mid-infrared excess, whereas those with disks that are strongly shadowed by the puffed-up inner rim of the disk only display modest amounts of mid-infrared emission. The PAH emission is expected to be produced mainly in the part of the disk atmosphere that is directly exposed to radiation from the central star. In this model, self-shadowed disks should display weaker PAH emission than flared disks, consistent with our observations.

Ion implantation ion source, system and method

Abstract: An ion source (1) for ion implantation system includes a vaporizer (2) for producing process gas; an electron source (12) for directing an electron beam (32) to ionize the process gas within an ionization volume (16); a beam dump (11); an ionization chamber (5); and an extraction aperture (37) for extracting an ion beam.

Kinetic modeling of low-pressure nitrogen discharges and post-discharges

Abstract: The kinetic modeling of low-pressure (p ∼ 1−10 torr) stationary nitrogen discharges and the corresponding afterglows is reviewed. It is shown that a good description of the overall behavior of nitrogen plasmas requires a deep understanding of the coupling between different kinetics. The central role is played by ground-state vibrationally excited molecules, N2(X 1 Σ + g ,v ), which have a strong influence on the shape of the electron energy distribution function, on the creation and destruction of electronically excited states, on the gas heating, dissociation and on afterglow emissions. N2(X 1 Σ + ,v ) molecules are actually the hinge ensuring a strong link between the various kinetics. The noticeable task done by electronically excited metastable molecules, in particular N2(A 3 Σ + u )a nd N2(a � 1 Σ − u ), is also pointed out. Besides contributing to the same phenomena as vibrationally excited molecules, these electronic metastable states play also a categorical role in ionization. Furthermore, vibrationally excited molecules in high v levels are in the origin of the peaks observed in the flowing afterglow for the concentrations of several species, such as N2(A 3 Σ + ), N2(B 3 Πg), N + 2 (B 2 Σ + u ) and electrons, which occur downstream from the discharge after a dark zone as a consequence of the V-V up-pumping mechanism.

Synopsis of the interstellar He parameters from combined neutral gas, pickup ion and UV scattering observations and related consequences

Abstract: A coordinated effort to combine all three methods that are used to determine the physical parameters of interstellar gas in the heliosphere has been undertaken. In order to arrive at a consistent parameter set that agrees with the observations of neutral gas, pickup ions and UV backscattering we have combined data sets from coordinated observation campaigns over three years from 1998 through 2000. The key observations include pickup ions with ACE and Ulysses SWICS, neutral atoms with Ulysses GAS, as well as UV backscattering at the He focusing cone close to the Sun with SOHO UVCS and at I AU with EUVE. For the first time also the solar EUV irradiance that is responsible for photo ionization was monitored with SOHO CELIAS SEM, and the He I 58.4 nm line that illuminates He was observed simultaneously with SOHO SUMER. The solar wind conditions were monitored with SOHO, ACE, and WIND. Based on these data the modeling of the interstellar gas and its secondary products in the heliosphere has resulted in a consistent set of interstellar He parameters with much reduced uncertainties, which satisfy all observations, even extended to earlier data sets. It was also established that a substantial ionization in addition to photo ionization, most likely electron impact, is required, with increasing relative importance closer to the Sun. Furthermore, the total combined ionization rate varies significantly with solar latitude, requiring a fully three dimensional and time dependent treatment of the problem.

Statistical Probes of Reionization with 21 Centimeter Tomography

Abstract: We consider the degree to which 21 cm tomography of the high-redshift universe can distinguish different ionization histories. Using a new analytic model for the size distribution of H II regions that associates these ionized bubbles with large-scale galaxy overdensities, we compute the angular power spectrum and other statistical properties of the 21 cm brightness temperature during reionization. We show that the H II regions imprint features on the power spectrum that allow us to separate histories with discrete bubbles from those with partial uniform ionization (by, for example, X-rays). We also show that double reionization scenarios will modify the morphology of the bubbles in ways that depend on the mechanism through which the first generation of sources shuts off. If, for example, the transition occurs globally at a fixed redshift, the first generation imprints a persistent feature on the 21 cm power spectrum. Finally, we compare our model to one in which voids are ionized first. While the power spectra of these two models are qualitatively similar, we show that the underlying distributions of neutral hydrogen differ dramatically and suggest that other statistical tests can distinguish them. The next generation of low-frequency radio telescopes will have the sensitivity to distinguish all of these models and strongly constrain the history and morphology of reionization.

A Unified Picture of the First Ionization Potential and Inverse First Ionization Potential Effects

Abstract: We discuss models for coronal abundance anomalies observed in the coronae of the sun and other late-type stars following a scenario first introduced by Schwadron, Fisk, & Zurbuchen of the interaction of waves at loop footpoints with the partially neutral gas. Instead of considering wave heating of ions in this location, we explore the effects on the upper chromospheric plasma of the wave pondermotive forces. These can arise when upward-propagating waves from the chromosphere transmit or reflect upon reaching the chromosphere-corona boundary, and are in large part determined by the properties of the coronal loop above. Our scenario has the advantage that for realistic wave energy densities both positive and negative changes in the abundance of ionized species compared to neutrals can result, allowing both first ionization potential (FIP) and inverse FIP effects to come out of the model. We discuss how variations in model parameters can account for essentially all of the abundance anomalies observed in solar spectra. Expected variations with stellar spectral type are also qualitatively consistent with observations of the FIP effect in stellar coronae.

Long-range self-channeling of infrared laser pulses in air: a new propagation regime without ionization

Abstract: We report long-range self-channeling in air of multiterawatt femtosecond laser pulses with large negative initial chirps. The peak intensity in the light channels is at least one order of magnitude lower than required for multiphoton ionization of air molecules. A detailed comparison is made between experiments and realistic 3+1-dimensional numerical simulations. It reveals that the mechanism limiting the growth of intensity by filamentation is connected with broken revolution symmetry in the transverse diffraction plane.

Photoionization Modeling and the K Lines of Iron

Abstract: We calculate the efficiency of iron K line emission and iron K absorption in photoionized models using a new set of atomic data. These data are more comprehensive than those previously applied to the modeling of iron K lines from photoionized gases, and allow us to systematically examine the behavior of the properties of line emission and absorption as a function of the ionization parameter, density and column density of model constant density clouds. We show that, for example, the net fluorescence yield for the highly charged ions is sensitive to the level population distribution produced by photoionization, and these yields are generally smaller than those predicted assuming the population is according to statistical weight. We demonstrate that the effects of the many strongly damped resonances below the K ionization thresholds conspire to smear the edge, thereby potentially affecting the astrophysical interpretation of absorption features in the 7-9 keV energy band. We show that the centroid of the ensemble of K(alpha) lines, the K(beta) energy, and the ratio of the K(alpha(sub 1)) to K(alpha(sub 2)) components are all diagnostics of the ionization parameter of our model slabs.

Photoconductivity studies of treated CdSe quantum dot films exhibiting increased exciton ionization efficiency

Abstract: We present measurements of photoconductivity in CdSe quantum dot films treated with a variety of reagents. While the photocurrent of untreated samples is highly voltage dependent at all voltages, after treatment the photocurrent is much larger, depends strongly on voltage at low voltage, displays a linear region above a voltage threshold, and finally saturates at high voltage. All regions of the current-voltage curves after treatment can be reproduced with a model that requires noninjecting contacts and a field dependent exciton ionization efficiency that saturates to unity. This model is shown to be consistent with the trends observed with different treatments. The changes in photocurrent with treatment are shown to be largely a consequence of increased quantum dot surface passivation and decreased quantum dot spacing, regardless of whether the molecules used for treatment are conjugated or able to cross-link the quantum dots.

Energy Levels and Observed Spectral Lines of Xenon, Xe I through Xe LIV

Abstract: The energy levels and observed spectral lines of the xenon atom, in all stages of ionization for which experimental data are available, have been compiled. Sufficient data were found to generate level and line tables for Xe I–Xe XI, Xe XIX, Xe XXV–Xe XXIX, Xe XLIII–Xe XLV, and Xe LI–Xe LIV. For Xe LIII and Xe LIV theoretical values are compiled for the energy levels. In 15 of the other stages a few lines are reported. Experimental g factors are included for Xe I, Xe II, and Xe III. A value, either experimental, semiempirical, or theoretical, is included for the ionization energy of each ion.

Inelastic electron interaction (attachment/ionization) with deoxyribose.

Abstract: We have investigated experimentally the formation of anions and cations of deoxyribose sugar (C5H10O4) via inelastic electron interaction (attachment/ionization) using a monochromatic electron beam in combination with a quadrupole mass spectrometer. The ion yields were measured as a function of the incident electron energy between about 0 and 20 eV. As in the case of other biomolecules (nucleobases and amino acids), low energy electron attachment leads to destruction of the molecule via dissociative electron attachment reactions. In contrast to the previously investigated biomolecules dehydrogenation is not the predominant reaction channel for deoxyribose; the anion with the highest dissociative electron attachment (DEA) cross section of deoxyribose is formed by the release of neutral particles equal to two water molecules. Moreover, several of the DEA reactions proceed already with “zero energy” incident electrons. In addition, the fragmentation pattern of positively charged ions of deoxyribose also indi...

The electron runaway mechanism in dense gases and the production of high-power subnanosecond electron beams

Abstract: New insight is provided into how runaway electrons are generated in gases. It is shown that the Townsend mechanism of electron multiplication works even for strong fields, when the ionization friction of electrons can be neglected. The non-local electron runaway criterion proposed in the work determines the critical voltage–pd relationship as a two-valued function universal for a given gas (p being the gas pressure, and d the electrode spacing). This relationship exhibits an additional upper branch as contrasted to the familiar Paschen's curves and divides the discharge gap into two regions: one where electrons multiply effectively, and the other which they leave without having enough time to multiply. Experiments on the production of electron beams with subnanosecond pulse duration and an amplitude of tens to hundreds of amperes at atmospheric pressure in various gases are addressed, and the creation of a nanosecond volume discharge with the high density of excitation power and without preionization of the gap by a supplementary source is discussed.

Dynamics of biological molecules irradiated by short x-ray pulses.

Abstract: Very short and intense x-ray pulses can be used for diffraction imaging of single biological molecules. Inevitably, x-ray absorption initiates damage that degrades the molecule's image. This paper presents a continuum model of the physics that leads to damage when a small particle absorbs a large x-ray dose. The main processes are found to be ionization and Coulomb-force driven atomic motion. Trapping of electrons, Debye shielding, and nonuniform collisional ionization all have a significant effect on the overall damage kinetics.

Production and state-selective detection of ultracold RbCs molecules.

Abstract: Using resonance-enhanced two-photon ionization, we detect ultracold, metastable RbCs molecules formed in their lowest triplet state $a\text{ }^{3}\ensuremath{\Sigma}^{+}$ via photoassociation in a laser-cooled mixture of $^{85}\mathrm{Rb}$ and $^{133}\mathrm{Cs}$ atoms. We obtain extensive bound-bound excitation spectra of these molecules, which provide detailed information about their vibrational distribution, as well as spectroscopic data on several RbCs molecular states including $a\text{ }^{3}\ensuremath{\Sigma}^{+}$, $(2)\text{ }^{3}\ensuremath{\Sigma}^{+}$, and $(1)\text{ }^{1}\ensuremath{\Pi}$. Analysis of this data allows us to predict strong transitions from observed levels to the absolute vibronic ground state of RbCs, potentially allowing the production of stable, ultracold polar molecules at rates in excess of ${10}^{6}\text{ }{\mathrm{s}}^{\ensuremath{-}1}$.

Secondary electrospray ionization-ion mobility spectrometry for explosive vapor detection.

Abstract: The unique capability of secondary electrospray ionization (SESI) as a nonradioactive ionization source to detect analytes in both liquid and gaseous samples was evaluated using aqueous solutions of three common military explosives: cyclo-1,3,5-trimethylene-2,4,6-trinitramine (RDX), nitroglycerin (NG) and pentaerythritol tetranitrate (PETN). The adducts formed between the compounds and their respective dissociation product, RDX·NO2-, NG·NO3-, and PETN·NO3-, gave the most intense signal for the individual compound but were more sensitive to temperature than other species. These autoadducts were identified as RDX·NO2-, NG·NO3-, and PETN·NO3- and had maximum signal intensity at 137, 100, and 125 °C, respectively. The reduced mobility values of the three compounds were constant over the temperature range from 75 to 225 °C. The signal-to-noise ratios for RDX, NG, and PETN at 50 mg L-1 in methanol−water were 340, 270, and 170, respectively, with a nominal noise of 8 ± 2 pA. In addition to the investigation of ...

HST STIS Ultraviolet Spectral Evidence of Outflow in Extreme Narrow-line Seyfert 1 Galaxies: II. Modeling and Interpretation

Abstract: We present modeling to explore the conditions of the broad-line emitting gas in two extreme Narrow-line Seyfert 1 galaxies, using the observational results described in the first paper of this series. Photoionization modeling using Cloudy was conducted for the broad, blueshifted wind lines and the narrow, symmetric, rest-wavelength-centered disk lines separately. A broad range of physical conditions were explored for the wind component, and a figure of merit was used to quantitatively evaluate the simulation results. Of the three minima in the figure-of-merit parameter space, we favor the solution characterized by an X-ray weak continuum, elevated abundances, a small column density (log(N_H)\approx 21.4), relatively high ionization parameter (log(U)\approx -1.2 - -0.2), a wide range of densities (log(n)\approx 7 - 11), and a covering fraction of ~0.15. The presence of low-ionization emission lines implies the disk component is optically thick to the continuum, and the SiIII]/CIII] ratio implies a density of 10^10 - 10^10.25 cm^-3. A low ionization parameter (log(U)=-3) is inferred for the intermediate-ionization lines, unless the continuum is ``filtered'' through the wind before illuminating the intermediate-line emitting gas, in which case log(U)=-2.1. The location of the emission regions was inferred from the photoionization modeling and a simple ``toy'' dynamical model. A large black hole mass (1.3 x 10^8 M_\odot) radiating at 11% of the Eddington luminosity is consistent with the kinematics of both the disk and wind lines, and an emission radius of ~10^4 R_S is inferred for both. We compare these results with previous work and discuss implications.

A multimode analysis of the gas-phase photoelectron spectra in oligoacenes

Abstract: We present a multimode vibrational analysis of the gas-phase ultraviolet photoelectron spectra of the first ionization in anthracene, tetracene, and pentacene, using electron-vibration constants computed at the density functional theory level. The first ionization of each molecule exhibits a high-frequency vibronic structure; it is shown that this regularly spaced feature is actually the consequence of the collective action of several vibrational modes rather than the result of the interaction with a single mode. We interpret this feature in terms of the missing mode effect. We also discuss the vibronic coupling constants and relaxation energies obtained from the fit of the photoelectron spectra with the linear vibronic model.