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.

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.

Evolutionary algorithms to solve complicated NMR spectra.

The complexity of (1)H NMR spectra of solutes in partially ordered solvents such as liquid crystals increases rapidly with the number of spins. Spectra of simple solutes with sufficient symmetry and containing not too many spins (typically

Observation of a Rydberg series in H+H-: a heavy Bohr atom.

We report on the realization of a heavy "Bohr atom," through the spectroscopic observation of a Rydberg series of bound quantum states at principal quantum numbers n=140 to 230. The system is made heavy by replacing an electron inside a hydrogen atom by a composite H- particle, thus forming a H+H- Coulombically bound system obeying the physical laws of a generalized atom with appropriate mass scaling.

Interactions of the 3ppi u c1Pi u(v=2) Rydberg-complex member in isotopic N2.

The 3ppi u c1Pi u-X 1Sigmag+(2,0) Rydberg and b' 1Sigmau+-X 1Sigmag+(7,0) valence transitions of 14N2, 14N15N, and 15N2 are studied using laser-based 1 extreme ultraviolet (XUV)+1' UV two-photon-ionization spectroscopy, supplemented by synchrotron-based hotoabsorption measurements in the case of 14N2. For each isotopomer, effective rotational interactions between the c(v=2) and b'(v=7) levels are found to cause strong Lambda-doubling in c(v=2) and dramatic P/R-branch intensity anomalies in the b'-X(7,0) band due to the effects of quantum interference. Local perturbations in energy and predissociation line width for the c(v=2) Rydberg level are observed and attributed to a spin-orbit interaction with the crossing, short-lived C 3Pi u(v=17) valence level.

HD as a probe for detecting mass variation on a cosmological time scale.

The strong electronic absorption systems of the B1 Sigma u+-X1 Sigma g+ Lyman and the C1Pi u-X1 Sigma g+ Werner bands can be used to probe possible mass-variation effects on a cosmological time scale from spectra observed at high redshift, not only in H2 but also in the second most abundant hydrogen isotopomer HD. High resolution laboratory determination of the most prominent HD lines at extreme ultraviolet wavelengths is performed at an accuracy of delta lambda/lambda approximately 5 x 10(-8), forming a database for comparison with astrophysical data. Sensitivity coefficients Ki = d ln lambda i/d ln mu are determined for HD from quantum ab initio calculations as a function of the proton-electron mass ratio mu. Strategies to deduce possible effects beyond first-order baryon/lepton mass ratio deviations are discussed.

Molecules with large-amplitude torsional motion partially oriented in a nematic liquid crystal: ethane and isotopomers.

An NMR study on ethane and five isotopomers dissolved in the nematic liquid crystal Merck ZLI 1132 is performed. A consistent set of dipolar and quadrupolar couplings is obtained. The dipolar couplings are corrected for harmonic vibrational effects, while the contribution from the torsional motion is incorporated classically. The corrected dipolar couplings cannot be understood in terms of a reasonable molecular structure unless effects of the reorientation-vibration interaction are taken into account. Assuming that the reorientation-vibration contributions that are known for the methyl group in methyl fluoride are transferable to ethane, excellent agreement between observed and calculated dipolar couplings is obtained on the basis of the ethane gas-phase structure. The observed and calculated deuterium quadrupolar couplings show discrepancies supporting the notion that average electric field gradients are important in liquid-crystal solvents. An important consequence of the transferability of the reorientation-vibration correlation is that in other molecules with a methyl group the same procedure as for ethane can be followed. Inclusion of this effect generally removes the need to interpret changes in observed dipolar couplings in terms of elusive chemical effects.

NMR as a tool in the investigation of fundamental problems in ordered liquids.

An overview is presented of modern NMR techniques and a variety of experimental and theoretical tools employed in the study of solutes dissolved in liquid crystals. The NMR techniques involve multiple quantum and spectral subtraction methods. In addition, various experimental and theoretical tools are discussed, including: the theoretical background of observed order parameters; the use of 'magic mixtures' to separate orientational contributions; the reorientation-vibration interaction; the use of model calculations based on size and shape of the various solutes; and the use of computer simulations. Applications to the benchmark probe molecules hydrogen, methane, ethane, and butane and their isotopomers are treated.

Dynamic polarization in the strong-field ionization of small metal clusters.

We report on the strong field ionization of small transition metal clusters (nickel, Ni(n) n=1-36) within the quasistatic regime at an infrared wavelength of 1.5 microm and at intensities up to 2 x 10(14) W/cm(2). From ion yields in a constant axial intensity beam, we obtained saturation intensities for the individual Ni(n) clusters. As compared to quasistatic, single active electron calculations, a dramatic suppression of ionization was observed. Dynamic polarization in the laser field likely leads to strong multielectron screening of the "active" electron. Representing the metal clusters as classical conducting spheres, we obtained, via a barrier suppression calculation, the classical ionization rates. Agreement was obtained for larger clusters with n>10 when the dynamic polarization was taken into account, emphasizing the multielectron nature of the ionization suppression.

Absolute ionization rates of multielectron transition metal atoms in strong infrared laser fields.

We report on nonresonant strong field ionization of the multielectron transition metal atoms V, Nb, Ta, Ni, and Pd. Operating in the adiabatic regime (lambda = 1.5 microm), we quantitatively determined both (i) the first charge state saturation intensities and (ii) the absolute ionization rates for intensities ranging from threshold up to 3 x 10(14) W/cm2. We observed a dramatic suppression of ionization relative to single active electron approximation expectations. We suggest that this derives from dynamic polarization or screening effects within the multielectron atom, stressing a need for many-body theories of strong field ionization.