In the version of this Article originally published, Figures 3 and 4 were erroneously swapped, this has been corrected in all versions of the Article.
View Article and Find Full Text PDFCollision-induced absorption is the phenomenon in which interactions between colliding molecules lead to absorption of light, even for transitions that are forbidden for the isolated molecules. Collision-induced absorption contributes to the atmospheric heat balance and is important for the electronic excitations of O that are used for remote sensing. Here, we present a theoretical study of five vibronic transitions in O-O and O-N, using analytical models and numerical quantum scattering calculations.
View Article and Find Full Text PDFThe ac magnetoconductance of bulk InSb at THz frequencies in high magnetic fields, as measured by the transmission of THz radiation, shows a field-induced transmission, which at high temperatures (≈100 K) is well explained with classical magnetoplasma effects (helicon waves). However, at low temperatures (4 K), the transmitted radiation intensity shows magnetoquantum oscillations that represent the Shubnikov-de Haas effect at THz frequencies. At frequencies above 0.
View Article and Find Full Text PDFWe present far infrared spectra of the conformer A of tryptamine in the 200 to 500 cm wavenumber range along with resonant photoionization spectra of the far-infrared excited conformer A of tryptamine. We show that single-far-infrared photon excited tryptamine has highly structured resonance enhanced multi-photon ionization spectra, revealing the mode composition of the S-state. Upon multiple-far-infrared photon absorption, the resonance enhanced multi-photon ionization spectrum broadens allowing ion gain spectroscopy to be performed.
View Article and Find Full Text PDFThe rotationally resolved magnetic dipole absorption spectrum of the oxygen A-band b(1)Σ(g)(+)(v=0) <- X(3)Σ(g)(-)(v=0) perturbed by collisions with helium was studied theoretically using the impact approximation. To calculate the relaxation matrix, scattering calculations were performed on a newly computed helium-oxygen (b(1)Σ(g)(+)) interaction potential as well as on a helium-oxygen (X(3)Σ(g)(-)) interaction potential from the literature. The calculated integrated line cross sections and broadening coefficients are in good agreement with experimental results from the literature.
View Article and Find Full Text PDFThe conformational preferences of peptides are mainly controlled by the stabilizing effect of intramolecular interactions. In peptides with polar side chains, not only the backbone but also the side chain interactions determine the resulting conformations. In this paper, the conformational preferences of the capped dipeptides Ac-Phe-Ser-NH2 (FS) and Ac-Phe-Cys-NH2 (FC) are resolved under laser-desorbed jet cooling conditions using IR-UV ion dip spectroscopy and density functional theory (DFT) quantum chemistry calculations.
View Article and Find Full Text PDFPhotodissociation of singlet oxygen, O2 a(1)Δg, by ultraviolet radiation in the region from 200 to 240 nm has been investigated using velocity map imaging of the atomic oxygen photofragments. Singlet oxygen molecules are generated in a pulsed discharge and studied by one-laser photodissociation and detection around 226 nm as well as two color photodissociation at various wavelengths in the range from 200 to 240 nm. A simple model of the discharge on and off signal indicates efficient conversion of O2 X(3)Σg(-)(v = 0) in the parent beam to O2 a(1)Δg(v = 0-2).
View Article and Find Full Text PDFPhys Chem Chem Phys
July 2012
Using cavity ring-down spectroscopy we measured the collision induced absorption spectrum associated with the a(1)Δ(v = 2) ←X(3)Σ(g)(-)(v = 0) band of oxygen near 922 nm both in pure oxygen and in mixtures of oxygen and nitrogen. For pure oxygen, we report for this band an integrated absorption of (1.56 - 0.
View Article and Find Full Text PDFWe have determined the collision-induced absorption (CIA) spectrum in the O(2) B-band in pure oxygen. We present absolute extinction coefficients of the minimums in between rotational lines using cavity ring-down spectroscopy. The measured extinction is corrected for the B-band magnetic dipole absorption using a model which includes line-mixing.
View Article and Find Full Text PDFWe have designed and implemented a large aperture electrostatic Einzel lens that magnifies the images of low energy ions or electrons in a standard velocity map imaging apparatus by up to a factor of 5 while allowing the normal use of the apparatus (without blocking any part of the detector). The field strength in the interaction region remains reasonably constant with or without magnification, and the lens can be used in the normal "crush" mode or with any of the different variants of the "slicing" mode. We have characterized the performance of the lens by imaging ion recoil due to two-photon resonant three-photon ionization [(2+1) REMPI] of O((3)P(2)) atoms and by imaging slow NO molecules from the near-threshold photodissociation of the NO-Ar van der Waals complex.
View Article and Find Full Text PDFLarmor precession of a quantum mechanical angular momentum vector about an applied magnetic field forms the basis for a range of magnetic resonance techniques, including nuclear magnetic resonance spectroscopy and magnetic resonance imaging. We have used a polarized laser pump-probe scheme with velocity-map imaging detection to visualize, for the first time, the precessional motion of a quantum mechanical angular momentum vector. Photodissociation of O(2) at 157 nm provides a clean source of fast-moving O((1)D(2)) atoms, with their electronic angular momentum vector strongly aligned perpendicular to the recoil direction.
View Article and Find Full Text PDFSliced velocity-map imaging has been used to measure photofragment scattering distributions for the O((3)P(2)) and O((3)P(1)) products of O(2) photolysis following laser excitation into the Herzberg continuum between 205 and 241 nm. The images were analysed to extract the photofragment spatial anisotropy parameter, β, together with the alignment parameters a(∥), a(⊥), a(⊥), and Re[a(∥, ⊥)]. Our alignment measurements bridge the gap between the recent 193 nm measurement of Brouard et al.
View Article and Find Full Text PDFThis paper reports on the absorption of molecular oxygen in the region of the A-band near 760 nm under atmospheric conditions relevant for satellite retrieval studies. We use pulsed laser cavity ring-down spectroscopy with a narrow bandwidth laser and use pressure scans to increase the accuracy of the measured oxygen extinction coefficients. Absolute binary absorption coefficients in minima between absorption lines of the A-band spectrum have been measured and tabulated.
View Article and Find Full Text PDFWe show experimentally and theoretically that a polarization-shaped femtosecond laser pulse with a zero net angular momentum creates a net angular momentum in atomic rubidium during resonant two-photon excitation. The necessary conditions for the creation of a nonzero angular momentum as well as the excitation efficiencies are analyzed in the framework of second-order time-dependent perturbation theory.
View Article and Find Full Text PDFDissociative recombination of the Zundel cation D(5)O(2)(+) almost exclusively produces D + 2 D(2)O with a maximum kinetic energy release of 5.1 eV. An imaging technique is used to investigate the distribution of the available reaction energy among these products.
View Article and Find Full Text PDFThe determination of the dissociative recombination rate coefficient of H(3) (+) has had a turbulent history, but both experiment and theory have recently converged to a common value. Despite this convergence, it has not been clear if there should be a difference between the rate coefficients for ortho-H(3) (+) and para-H(3) (+). A difference has been predicted theoretically and could conceivably impact the ortho:para ratio of H(3) (+) in the diffuse interstellar medium, where H(3) (+) has been widely observed.
View Article and Find Full Text PDFWe have studied the dissociative recombination (DR) of molecular hydrogen ions with slow electrons over a range of collision energies from 0 to 400 meV. By employing a pulsed expansion source for rotational cooling and by exploiting super elastic collisions with near-0-eV electrons in a heavy ion storage ring for vibrational cooling, we observe a highly structured DR cross section, comparable to that reported for HD+. Using para-hydrogen-enriched ion beams, we identify for the first time features in the DR cross sections attributed to nu=0, J=even molecules (para-H2) and nu=0, J=odd (ortho-H2) molecules, separately.
View Article and Find Full Text PDFThe size distribution of semitransparent irregularly shaped mineral dust aerosol samples is determined using a commonly used laser particle-sizing technique. The size distribution is derived from intensity measurements of singly scattered light at various scattering angles close to the forward-scattering direction at a wavelength of 632.8 nm.
View Article and Find Full Text PDFDissociative recombination (DR) of the dimer ion (NO)(2) (+) has been studied at the heavy-ion storage ring CRYRING at the Manne Siegbahn Laboratory, Stockholm. The experiments were aimed at determining details on the strongly enhanced thermal rate coefficient for the dimer, interpreting the dissociation dynamics of the dimer ion, and studying the degree of similarity to the behavior in the monomer. The DR rate reveals that the very large efficiency of the dimer rate with respect to the monomer is limited to electron energies below 0.
View Article and Find Full Text PDFWe present product state distributions and quantum yields from the dissociative recombination reaction of O2+ in its electronic and vibrational ground states as a function of electron collision energy between 0 and 300 meV. The experiments have been performed in the heavy-ion storage ring, CRYRING, and use a cold hollow-cathode discharge source for the production of cold molecular oxygen ions. The branching fractions over the different dissociation limits show distinct oscillations while the resulting product quantum yields are largely independent of electron collision energy above 40 meV.
View Article and Find Full Text PDFWe have studied the dissociative recombination of the first three vibrational levels of O(2) (+) in its electronic ground X (2)Pi(g) state. Absolute rate coefficients, cross sections, quantum yields and branching fractions have been determined in a merged-beam experiment in the heavy-ion storage ring, CRYRING, employing fragment imaging for the reaction dynamics. We present the absolute total rate coefficients as function of collision energies up to 0.
View Article and Find Full Text PDFWe demonstrate an intricate combination of strong and weak interactions of a broadband half-cycle pulse with Rydberg atoms. A transition, which is resonant with a frequency that was taken out of the frequency spectrum, can be enhanced. In the experiment, the broadband ultrashort terahertz half-cycle pulse propagates through water vapor, which absorbs on discrete lines in the spectrum, thus removing frequencies from the spectrum.
View Article and Find Full Text PDFWe report time-resolved electron emission in experiments on ionization of rubidium Rydberg atoms (n=90) by few-cycle radio-frequency (RF) (1-10 MHz) pulses. The electron emission occurs in multiple bursts and strongly depends on the carrier-envelope phase as well as the duration and amplitude of the RF pulses. Remarkably, ionization is observed during a series of cycles with the same amplitude.
View Article and Find Full Text PDFWe present measurements of the electron ejection direction in the ionization of high (n=90) Rydberg states of rubidium subjected to few-cycle radio-frequency (RF) pulses. For weak pulses we find a strong asymmetry for even (cosine) pulses and no asymmetry for odd (sine) pulses. This asymmetry disappears for pulses longer than four RF cycles.
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