T.I. Ivanov

QED Effects in Molecules: Test on Rotational Quantum States of H(2)

Quantum electrodynamic effects have been systematically tested in the progression of rotational quantum states in the X 1Σ(g)(+), v=0 vibronic ground state of molecular hydrogen. High-precision Doppler-free spectroscopy of the EF 1Σ(g)(+)-X 1Σ(g)(+) (0,0) band was performed with 0.005  cm(-1) accuracy on rotationally hot H2 (with rotational quantum states J up to 16). QED and relativistic contributions to rotational level energies as high as 0.13  cm(-1) are extracted, and are in perfect agreement with recent calculations of QED and high-order relativistic effects for the H2 ground state.

Synchrotron vacuum ultraviolet radiation studies of the D(1)Pi(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-transform spectroscopy of HD in the vacuum ultraviolet at lambda = 87-112 nm

Absorption spectroscopy in the vacuum ultraviolet (VUV) domain was performed on the hydrogen-deuteride molecule with a novel Fourier-transform spectrometer based upon wavefront division interferometry. This unique instrument, which is a permanent endstation of the undulator-based beamline DESIRS on the synchrotron SOLEIL facility, opens the way to Fourier-transform spectroscopy in the VUV range. The HD spectral lines in the Lyman and Werner bands were recorded in the 87–112 nm range from a quasi-static gas sample in a windowless configuration and with a Doppler-limited resolution. Line positions of some 268 transitions in the Lyman bands and 141 transitions in the Werner bands were deduced with uncertainties of 0.04 cm−1 (1σ) which correspond to Δλ/λ ∼ 4 × 10−7. This extensive laboratory database is of relevance for comparison with astronomical observations of H2 and HD spectra from highly redshifted objects, with the goal of extracting a possible variation of the proton-to-electron mass ratio (μ = m p /m e ) on a cosmological time scale. For this reason also calculations of the so-called sensitivity coefficients K i were performed in order to allow for deducing constraints on Δμ/μ. The K i coefficients, associated with the line shift that each spectral line undergoes as a result of a varying value for μ, were derived from calculations as a function of μ solving the Schrödinger equation using ab initio potentials.

VUV spectroscopic study of the D1Piu state of molecular deuterium

The D 1Π u – absorption system of molecular deuterium has been re-investigated using the VUV Fourier-Transform (FT) spectrometer at the DESIRS beamline of the synchrotron SOLEIL and photon-induced fluorescence spectrometry (PIFS) using the 10 m normal incidence monochromator at the synchrotron BESSY II. Using the FT spectrometer absorption spectra in the range 72–82 nm were recorded in quasi static gas at 100 K and in a free flowing jet at a spectroscopic resolution of 0.50 and 0.20 cm−1 respectively. The narrow Q-branch transitions, probing states of Π− symmetry, were observed up to vibrational level v = 22. The states of Π+ symmetry, known to be broadened due to predissociation and giving rise to asymmetric Beutler–Fano resonances, were studied up to v = 18. The 10 m normal incidence beamline setup at BESSY II was used to simultaneously record absorption, dissociation, ionization and fluorescence decay channels from which information on the line intensities, predissociated widths, and Fano q-parameters were extracted. R-branch transitions were observed up to v = 23 for J = 1–3 as well as several transitions for J = 4 and 5 up to v = 22 and 18 respectively. The Q-branch transitions are found to weakly predissociate and were observed from v = 8 to the final vibrational level of the state v = 23. The spectroscopic study is supported by two theoretical frameworks. Results on the Π− symmetry states are compared to ab initio multi-channel-quantum defect theory (MQDT) calculations, demonstrating that these calculations are accurate to within 0.5 cm−1. Furthermore, the calculated line intensities of Q-lines agree well with measured values. For the states of Π+ symmetry a perturbative model based on a single bound state interacting with a predissociation continuum was explored, yielding good agreement for predissociation widths, Fano q-parameters and line intensities.

Spectroscopic observation and characterization of H(+)H(-) heavy Rydberg states.

A series of discrete resonances was observed in the spectrum of H2, which can be unambiguously assigned to bound quantum states in the 1/R Coulombic potential of the H+H- ion-pair system. Two-step laser excitation was performed, using tunable extreme ultraviolet radiation at lambda = 94-96 nm in the first step, and tunable ultraviolet radiation in the range lambda = 310-350 nm in the second step. The resonances, detected via H+ and H2+ ions produced in the decay process, follow a sequence of principal quantum numbers (n = 140-230) associated with a Rydberg formula in which the Rydberg constant is mass scaled. The series converges upon the ionic H+H- dissociation threshold. This limit can be calculated without further assumptions from known ionization and dissociation energies in the hydrogen system and the electronegativity of the hydrogen atom. A possible excitation mechanism is discussed in terms of a complex resonance. Detailed measurements are performed to unravel and quantify the decay of the heavy Rydberg states into molecular H2+ ions, as well as into atomic fragments, both H(n = 2) and H(n = 3). Lifetimes are found to scale as n3.

Quantum-interference effects in the o(1)Pi(u)(v=1)similar to b(1)Pi(u)(v=9) Rydberg-valence complex of molecular nitrogen

Two distinct high-resolution experimental techniques, 1 UV laser-based ionization spectroscopy and synchrotron-based XUV photoabsorption spectroscopy, have been used to study the o Rydberg–valence complex of 14N2, providing new and detailed information on the perturbed rotational structures, oscillator strengths, and predissociation linewidths. Ionization spectra probing the b state of 14N2, which crosses o1Πu(v=1) between J = 24 and J = 25, and the o1Πu(v=1), b,1Πu(v=9), and b states of 14N15N, have also been recorded. In the case of 14N2, rotational and deperturbation analyses correct previous misassignments for the low-J levels of o(v=1) and b(v=9). In addition, a two-level quantum-mechanical interference effect has been found between the o–X(1, 0) and b–X(9, 0) transition amplitudes which is totally destructive for the lower-energy levels just above the level crossing, making it impossible to observe transitions to b(v=9,J=6). A similar interference effect is found to affect the o(v=1) and b(v=9) predissociation linewidths, but, in this case, a small non-interfering component of the b(v=9) linewidth is indicated, attributed to an additional spin–orbit predissociation by the repulsive state.

Frequency calibration of B (1)Sigma(+)(u)-X (1)Sigma(+)(g) (6,0) Lyman transitions in H-2 for comparison with quasar data

The Lyman and Werner spectroscopic transitions of molecular hydrogen, the most ubiquitous molecular spectral lines observed in the universe, provide a tool to probe a possible variation of the proton-to-electron mass ratio mu on a cosmological time scale. Such procedures require a database of zero-redshift, or laboratory-based wavelengths at the highest possible level of accuracy. Accurate transitions in the B (1)Sigma(+)(u)-X (1)Sigma(+)(g) (6,0) Lyman band of H2 are still missing in the set of laboratory data, due to previously encountered problems in generating the appropriate wavelengths using a narrow-band extreme ultraviolet laser source. Here frequency calibrations of the missing transitions are presented from a laser-based study at a (5 - 8) x 10(-8) accuracy level.

Spectral identification of diffuse resonances in H2 above the n = 2 dissociation limit

The resonance structure in molecular hydrogen above the n = 2 dissociation limit is experimentally investigated in a 1 XUV + 1 VIS coherent two-step laser excitation process, with subsequent ionization of H(n = 2) products. Diffuse spectral features exhibiting widths of several cm(-1) in the excitation range of 118,500-120,500 cm(-1) are probed. Information on angular momentum selection rules for parallel and crossed polarizations, combination differences, the para-ortho distinction, extrapolation from rovibrational structure in the bound region below the n = 2 threshold, and mass-selective detection of H(2)(+) parent and H(+) daughter fragments is used as input. This allows for an assignment of the diffuse resonances observed in terms of (1)Σ(g)(+), (1)Π(g), and (1)Δ(g) states, specified with vibrational and rotational quantum numbers.