A Near-Threshold Shape Resonance in the Valence-Shell Photoabsorption of Linear Alkynes.

The room-temperature photoabsorption spectra of a number of linear alkynes with internal triple bonds (e.g., 2-butyne, 2-pentyne, and 2- and 3-hexyne) show similar resonances just above the lowest ionization threshold of the neutral molecules. These features result in a substantial enhancement of the photoabsorption cross sections relative to the cross sections of alkynes with terminal triple bonds (e.g., propyne, 1-butyne, 1-pentyne, ...). Based on earlier work on 2-butyne [ Xu et al., J. Chem. Phys. 2012, 136, 154303 ], these features are assigned to excitation from the neutral highest occupied molecular orbital (HOMO) to a shape resonance with g (l = 4) character and approximate π symmetry. This generic behavior results from the similarity of the HOMOs in all internal alkynes, as well as the similarity of the corresponding gπ virtual orbital in the continuum. Theoretical calculations of the absorption spectrum above the ionization threshold for the 2- and 3-alkynes show the presence of a shape resonance when the coupling between the two degenerate or nearly degenerate π channels is included, with a dominant contribution from l = 4. These calculations thus confirm the qualitative arguments for the importance of the l = 4 continuum near threshold for internal alkynes, which should also apply to other linear internal alkynes and alkynyl radicals. The 1-alkynes do not have such high partial waves present in the shape resonance. The lower l partial waves in these systems are consistent with the broader features observed in the corresponding spectra.

High-resolution vacuum-ultraviolet photoabsorption spectra of 1-butyne and 2-butyne.

The absolute photoabsorption cross sections of 1- and 2-butyne have been recorded at high resolution by using the vacuum-ultraviolet Fourier-Transform spectrometer at the SOLEIL Synchrotron. Both spectra show more resolved structure than previously observed, especially in the case of 2-butyne. In this work, we assess the potential importance of Rydberg states with higher values of orbital angular momentum, l, than are typically observed in photoabsorption experiments from ground state molecules. We show how the character of the highest occupied molecular orbitals in 1- and 2-butyne suggests the potential importance of transitions to such high-l (l = 3 and 4) Rydberg states. Furthermore, we use theoretical calculations of the partial wave composition of the absorption cross section just above the ionization threshold and the principle of continuity of oscillator strength through an ionization threshold to support this conclusion. The new absolute photoabsorption cross sections are discussed in light of these arguments, and the results are consistent with the expectations. This type of argument should be valuable for assessing the potential importance of different Rydberg series when sufficiently accurate direct quantum chemical calculations are difficult, for example, in the n ≥ 5 manifolds of excited states of larger molecules.

Observation of a new electronic state of CO perturbing W ¹Π(v=1).

We observe photoabsorption of the W(1) ← X(0) band in five carbon monoxide isotopologues with a vacuum-ultraviolet Fourier-transform spectrometer and a synchrotron radiation source. We deduce transition energies, integrated cross sections, and natural linewidths of the observed rotational transitions and find a perturbation affecting these. Following a deperturbation analysis of all five isotopologues, the perturbing state is assigned to the v = 0 level of a previously unobserved (1)Π state predicted by ab initio calculations to occur with the correct symmetry and equilibrium internuclear distance. We label this new state E″ (1)Π. Both of the interacting levels W(1) and E″(0) are predissociated, leading to dramatic interference effects in their corresponding linewidths.

High-resolution photoabsorption spectrum of jet-cooled propyne.

The absolute photoabsorption cross section of propyne was recorded between 62,000 and 88,000 cm(-1) by using the vacuum-ultraviolet, Fourier-transform spectrometer at the Synchrotron Soleil. This cross section spans the region including the lowest Rydberg bands and extends above the Franck-Condon envelope for ionization to the ground electronic state of the propyne cation, X̃(+). Room-temperature spectra were recorded in a flowing cell at 0.9 cm(-1) resolution, and jet-cooled spectra were recorded at 1.8 cm(-1) resolution and a rotational temperature of ~100 K. The reduced widths of the rotational band envelopes in the latter spectra reveal new structure and simplify a number of assignments. Although nf Rydberg series have not been assigned previously in the photoabsorption spectrum of propyne, arguments are presented for their potential importance, and the assignment of one nf series is proposed. As expected from previous photoelectron spectra, Rydberg series are also observed above the adiabatic ionization threshold that converge to the v3(+) = 1 and 2 levels of the C≡C stretching vibration.

Excited electronic states of thiophene: high resolution photoabsorption Fourier transform spectroscopy and ab initio calculations.

The recently introduced synchrotron radiation-based Fourier transform spectroscopy has been employed to study the excited electronic states of thiophene. A highly resolved photoabsorption spectrum has been measured between ∼5 and 12.5 eV, providing a wealth of new data. High-level ab initio computations have been performed using the second-order algebraic-diagrammatic construction (ADC(2)) polarization propagator approach, and the equation-of-motion coupled-cluster (EOM-CC) method at the CCSD and CC3 levels, to guide the assignment of the spectrum. The adiabatic energy corrections have been evaluated, thereby extending the theoretical study beyond the vertical excitation picture and leading to a significantly improved understanding of the spectrum. The low-lying π→π* and π→σ* transitions result in prominent broad absorption bands. Two strong Rydberg series converging onto the X(~)(2)A2 state limit have been assigned to the 1a2→npb1(1)B2 and the 1a2→nda2(1)A1 transitions. A second, and much weaker, d-type series has been assigned to the 1a2→ndb1(1)B2 transitions. Excitation into some of the Rydberg states belonging to the two strong series gives rise to vibrational structure, most of which has been interpreted in terms of excitations of the totally symmetric ν4 and ν8 modes. One Rydberg series, assigned to the 3b1→nsa1(1)B1 transitions, has been identified converging onto the Ã(2)B1 state limit, and at higher energies Rydberg states converging onto the B(~)(2)A1 state limit could be identified. The present spectra reveal highly irregular vibrational structure in certain low energy absorption bands, and thus provide a new source of information for the rapidly developing studies of excited state non-adiabatic dynamics and photochemistry.

Temporal coherence and spectral linewidth of an injection-seeded transient collisional soft x-ray laser.

The temporal coherence of an injection-seeded transient 18.9 nm molybdenum soft x-ray laser was measured using a wavefront division interferometer and compared to model simulations. The seeded laser is found to have a coherence time similar to that of the unseeded amplifier, ~1 ps, but a significantly larger degree of temporal coherence. The measured coherence time for the unseeded amplifier is only a small fraction of the pulsewidth, while in the case of the seeded laser it approaches full temporal coherence. The measurements confirm that the bandwidth of the solid target amplifiers is significantly wider than that of soft x-ray lasers that use gaseous targets, an advantage for the development of sub-picosecond soft x-ray lasers.

High-resolution Fourier-transform extreme ultraviolet photoabsorption spectroscopy of 14N15N.

The first comprehensive high-resolution photoabsorption spectrum of (14)N(15)N has been recorded using the Fourier-transform spectrometer attached to the Desirs beamline at the Soleil synchrotron. Observations are made in the extreme ultraviolet and span 100 000-109 000 cm(-1) (100-91.7 nm). The observed absorption lines have been assigned to 25 bands and reduced to a set of transition energies, f values, and linewidths. This analysis has verified the predictions of a theoretical model of N(2) that simulates its photoabsorption and photodissociation cross section by solution of an isotopomer independent formulation of the coupled-channel Schrödinger equation. The mass dependence of predissociation linewidths and oscillator strengths is clearly evident and many local perturbations of transition energies, strengths, and widths within individual rotational series have been observed.

Synchrotron vacuum ultraviolet radiation studies of the D (1)Π(u) state of H(2).

The 3pπD (1)Π(u) state of the H(2) molecule was reinvestigated with different techniques at two synchrotron installations. The Fourier transform spectrometer in the vacuum ultraviolet wavelength range of the DESIRS beamline at the SOLEIL synchrotron was used for recording absorption spectra of the D (1)Π(u) state at high resolution and high absolute accuracy, limited only by the Doppler contribution at 100 K. From these measurements, line positions were extracted, in particular, for the narrow resonances involving (1)Π(u) (-) states, with an accuracy estimated at 0.06 cm(-1). The new data also closely match multichannel quantum defect calculations performed for the Π(-) components observed via the narrow Q-lines. The Λ-doubling in the D (1)Π(u) state was determined up to v=17. The 10 m normal incidence scanning monochromator at the beamline U125/2 of the BESSY II synchrotron, combined with a home-built target chamber and equipped with a variety of detectors, was used to unravel information on ionization, dissociation, and intramolecular fluorescence decay for the D (1)Π(u) vibrational series. The combined results yield accurate information on the characteristic Beutler-Fano profiles associated with the strongly predissociated Π(u) (+) parity components of the D (1)Π(u) levels. Values for the parameters describing the predissociation width as well as the Fano-q line shape parameters for the J=1 and J=2 rotational states were determined for the sequence of vibrational quantum numbers up to v=17.

Fourier-limited seeded soft x-ray laser pulse.

We present what we believe to be the first measurement of the spectral properties of a soft x-ray laser seeded by a high-order harmonic beam. Using an interferometric method, the spectral profile of a seeded Ni-like krypton soft x-ray laser (32.8 nm) generated by optical field ionization has been experimentally determined, and the shortest possible pulse duration has been deduced. The source exhibits a Voigt spectral profile with an FWHM of 3.1+/-0.3 mA, leading to a Fourier-transform pulse duration of 4.7 ps. This value is comparable with the upper limit of the soft x-ray pulse duration determined by experimentally investigating the gain dynamics, from which we conclude that the source has reached the Fourier limit. The measured bandwidth is in good agreement with the predictions of a radiative transfer code, including gain line narrowing and saturation rebroadening.

Internal frequency conversion extreme ultraviolet interferometer using mutual coherence properties of two high-order-harmonic sources.

We report on an innovative two-dimensional imaging extreme ultraviolet (XUV) interferometer operating at 32 nm based on the mutual coherence of two laser high order harmonics (HOH) sources, separately generated in gas. We give the first evidence that the two mutually coherent HOH sources can be produced in two independent spatially separated gas jets, allowing for probing centimeter-sized objects. A magnification factor of 10 leads to a micron resolution associated with a subpicosecond temporal resolution. Single shot interferograms with a fringe visibility better than 30% are routinely produced. As a test of the XUV interferometer, we measure a maximum electronic density of 3x10(20) cm(-3) 1.1 ns after the creation of a plasma on aluminum target.

A Fourier transform spectrometer without a beam splitter for the vacuum ultraviolet range: From the optical design to the first UV spectrum.

We describe a Fourier transform (FT) spectrometer designed to operate down to 60 nm (20 eV) on a synchrotron radiation beamline for high resolution absorption spectrometry. As far as we know, such an instrument is not available below 140 nm mainly because manufacturing accurate and efficient beam splitters remains a major problem at these wavelengths, especially if a wide bandwidth operation is desired. In order to overcome this difficulty, we developed an interferometer based on wave front division instead of amplitude division. It relies on a modified Fresnel bimirror configuration that requires only flat mirrors. The instrument provides path difference scanning through the translation of one reflector. During the scanning, the moving reflector is controlled by an optical system that keeps its direction constant within a tolerable value and provides an accurate interferometric measurement of the path difference variation. Therefore, a regular interferogram sampling is obtained, producing a nominal spectral impulse response and an accurate spectral calibration. The first results presented in this paper show a measured spectral resolution of delta(sigma)=0.33 cm-1 (interval between spectral samples). This was obtained with a sampling interval of 29 nm (path difference) and 512 K samples from a one-sided interferogram using a cosine FT. Such a sampling interval should allow the recording of large bandwidth spectra down to lambda=58 nm with an ultimate resolving power of 500,000 at this wavelength. In order to check the instrument performances, we first recorded an interferogram from a He-Ne stabilized laser. This provided the actual spectral impulse function, which was found to be fully satisfactory. The determination of the impulse response distortion and of the noise on the vacuum ultraviolet (VUV) spectral range provided accurate information in the sampling error profile over a typical scan. Finally, the instrument has been moved to the SU5 undulator-based synchrotron radiation beamline (Super-ACO facility, LURE, Orsay, France). A high resolution spectrum of O2 (the Schumann-Runge absorption bands, 185-200 nm) was computed from recorded interferograms using the beamline monochromator at the zeroth order to feed the instrument with an 11% relative bandwidth "white" beam (2003). These UV measurements are very close to those found in the literature, showing nominal performances of the FT spectrometer that should translate into an unprecedented resolving power at shortest VUV wavelengths. A recent upgrade (2007) and future developments will be discussed in light of the current installation of the upgraded FT spectrometer as a permanent endstation for ultrahigh resolution absorption spectrometry on the VUV beamline DESIRS at SOLEIL, the new French third generation synchrotron facility.

Optimization toward a high-average-brightness soft-x-ray laser pumped at grazing incidence.

We report the near-field imaging characterization of a 10 Hz Ni-like 18.9 nm molybdenum soft-x-ray laser pumped in a grazing incidence pumping (GRIP) geometry with a table-top laser driver. We investigate the effect of varying the GRIP angle on the spatial behavior of the soft-x-ray laser source. After multiparameter optimization, we were able to find conditions to generate routinely a high-repetition-rate soft-x-ray laser with an energy level of up to 3 microJ/pulse and to 6x10(17) photons/s/mm2/mrad2/(0.1% bandwidth) average brightness and 1x10(28) photons/s/mm2/mrad2/(0.1% bandwidth) peak brightness.

Quantitative study of 10 Hz operation of a soft x-ray laser-energy stability and target considerations.

A soft x-ray laser from Ni-like Mo, pumped in grazing incidence (GRIP), is analyzed with regard to high repetition rate operation. Reliable lasing is obtained, but with significant energy fluctuations attributed mainly to beam pointing jitter from the pump laser. Two modes of operation are compared: continuously moving target and stationary target. With a moving target the soft X-ray output is constant on average, whereas the repeated use of the same target position leads to a pulse energy which increases for several tens of shots. This effect might be caused by improved guiding of the pump laser in the formed groove and the removal, through laser ablation, of the oxide layer on the target surface.

Twin-image elimination in in-line holography of finite-support complex objects.

Reconstruction of in-line holograms suffers from the superposition of two twin images having different foci but identical information content. A simple iterative method of twin-image elimination is presented here. It is based on the fact that, if the object has a finite support and the recording distance is not too small, the out-of-focus field is known on a large part of the reconstruction plane and is only superposed by the in-focus one inside a restricted support. An iterative procedure is developed to recover the out-of-focus wave inside the in-focus image support. Inverse diffraction then gives the reconstructed image. This procedure can be easily automated and works for finite-support real or complex objects, recorded in geometries with a Fresnel number of ~1.

High magnification self-imaging.

Strongly magnified images of a periodic object can be obtained by using the Talbot effect. Two particular advantages are simplicity and compactness of the setup even for a high magnification ratio. First we recall the principle of self-imaging and the basic results derived by Rayleigh. These results were obtained from simplifying assumptions, which we show to be particularly unrealistic for high magnification ratios. A possibly more accurate and nevertheless practical approach is proposed.

Optical Fourier transform: what is the optimal setup?

The two basic optical Fourier transform configurations are examined with respect to component complexity, aberrations, and optical noise. It is shown that the converging-beam illumination setup (CB-FT) is much simpler and works better than the classical parallel beam illumination setup within a restricted range of object size and lens aperture. This range corresponds to many practical cases. Therefore, the CB-FT should be preferred in ordinary cases whereas the classical setup with a special purpose Fourier lens should be used only for a large space-bandwidth product. It is probably never a good solution to use the parallel beam configuration with a general purpose lens as the Fourier lens.

Real time measurement of very small transverse displacements of diffuse objects by random moiré. 1: Theory.

Illumination of a random diffuse object by a fringe pattern produced by two symmetrical laser beams leads to phenomena that are usually studied with speckle interferometric techniques. We first show that these phenomena are analogous to moiré. We then propose to apply this method for measuring the transverse vibrations of a diffuse surface in real time with interferometric sensitivity. Further, we show that the discussed system can work as a linear displacement transducer; the theoretical aspects of this so-called random moire transducer are investigated.

Real time measurement of very small transverse displacements of diffuse objects by random moiré, 2: Experiments.

We first briefly describe a realization of the random moiré displacement transducer (Part 1 of this paper). The principal problems arising in practical measurements, namely, stability and noise, are then discussed. Finally, results of several vibration measurements are presented, with various waveforms and amplitudes (2 A to 3 microm peak to peak).