Far-infrared laser-emission spectroscopy on ammonia isotopomers

In this paper we report the investigation of the isotopic ammonia gases¹⁴NH₃,¹⁴NH₂D,¹⁴NHD₂,¹⁵NH₃ and¹⁵ND₃ optically pumped by a continuously tunable 20 atm CO₂-laser. We found 267 far-infrared emission lines, produced by both inversion and Raman processes, in the frequency range from 15 cm^–1 to about 250 cm^–1. 200 of these were observed for the first time. We obtained far-infrared Raman tuning ranges exceeding 3 cm^–1, photon conversion coefficients up to 12% and maximum output energies of 0.9 mJ. Furthermore, the optimum gas pressure, the polarization and the transient behavior of optically pumped ammonia have been investigated.     

Magnetic circular dichroism and absorption spectra of Cs2ZrCl6:Mo4+

Absorption and magnetic circular dichroism (M.C.D.) spectra of Mo⁴⁺ in Cs₂ZrCl₆ have been recorded under high resolution at liquid helium temperature over the range 20 000–38 000 cm^-1. All of the bands can be assigned to parity-allowed, ligand-to-metal charge-transfer transitions in both MoCl₆ ^2-(4d²) and an impurity ion which has been identified as MoOCl₅ ^2-(4d¹). The d¹ and d² systems are easily distinguished by the temperature dependence of their M.C.D. spectra, and detailed assignments are proposed for the latter. The absorption spectrum in the region 23 000–26 000 cm^-1 has recently been attributed to a d→d transition in the ion MoCl₆ ^-(4d¹) [1], but the M.C.D. spectrum proves this assignment to be incorrect, and we find no evidence for the presence of this singly-charged species. From the temperature dependence of the M.C.D. spectrum of MoCl₆ ^2-, we estimate the second-order spin-orbit splitting of the E and T ₂ components of the ³ T _1g ground state to be 27 ± 5 cm^-1 with E lowest. The electrostatic splitting of the ³ T _2u and ⁵ T _2u charge-transfer states arising from the t _1u (π + σ) →t _2g excitation is estimated to be close to 515 cm^-1.     

Atomic beam,optogalvanic and stored ion spectroscopy for radioactive isotopes

Systematic studies of the optical isotope shift and the hyperfine splitting of long chains of stable and radioactive isotopes were performed. The method applied was laser induced resonance absorption; the experimental techniques were the atomic beam method with fluorescence detection and the optogalvanic method. The theory of hyperfine splitting and isotope shift of atoms is reviewed in short with emphasis on the aspects interesting for nuclear physics and on the evaluation problem. The experimental methods are described and their key parameters sensitivity and resolution are discussed. Preliminary results on stored thorium ions are given. Sample results for the nuclear quantity δ<r ²> derived from atomic beam experiments with tin and strontium are presented.     

Collective surface plasmon resonance coupling in silver nanoshell arrays

Collective surface plasmon resonance (SPR) excitations in an ordered array of silver nanoshells have been theoretically studied using generalized Mie theory. Near- and far-field radiative coupling between the nanoshells in the array result in a non-monotonic shift of the collective SPR band. When the distance between the shells in the array approaches that of the collective SPR wavelength, we observe narrowing of the collective SPR band due to constructive interference between the scattered electric field from the particles in the array. Further increase of the distance between the nanoshells in the array leads to destructive interference and broadening of the collective SPR band.     

Magnetic hyperfine fields at 111In probes in submonolayer Cu islands on Co(1 0 0) surfaces

Cu islands in the submonolayer coverage regime deposited on Co(1 0 0) have been studied utilizing the PAC spectroscopy. The ¹¹¹In PAC probes are incorporated into the topmost monolayer, which is corroborated by the presence of a rather unique electric field gradient. In addition, weak magnetic hyperfine fields B_hf between 1.9(2) and 0.37(4) T have been observed depending on the Cu coverage. This is attributed to next neighbours of the PAC probes consisting of mixed Co/Cu configurations. A linear decrease of B_hf as a function of the number of Cu atoms replacing Co is found. This revised version was published online in August 2006 with corrections to the Cover Date.     

Chemisorption of isolated Br atoms on Si(100)-(2 × 1) studied by PAC

Chemisorption and desorption of isolated bromine adatoms on the Si(100)-(2 × 1) surface were investigated with nuclear methods. Br adsorption sites at low coverages of 10⁻³ monolayers (ML) were characterised by measuring the nuclear quadrupole interaction with perturbed γγ-angular correlation (PAC) of ⁷⁷Br→⁷⁷Se probe atoms. Below room temperature, two distinct adsorption sites for Br are revealed by PAC. One of them disappears after isochronal annealing above 300 K. The more stable probe-atom state is associated with single Br atoms saturating a dangling bond of the surface, while the less stable state is attributed to adsorption of Br at a bridge site. The potential barrier between the two adsorption sites is estimated to be 0.9(1) eV. At temperatures above 550 K, the fraction of atoms on distinct sites decreases, presumably due to surface diffusion. By measuring the γ-activity of the sample, complete desorption of the ⁷⁷Br atoms was observed above 620 K.     

The formation of highly excited H in the reaction H2+(v) + H2 → H + H

A quasiclassical trajectory surface hopping method has been used to study H(v) + H₂ → H + H for v = 0, 3, 7, 10, 13, and 17 with an emphasis on determining the H internal energy and angular momentum distributions for high v. For v = 13 and 17, significant cross sections are found for producing H at energies above its dissociation energy. An average metastable H lifetime of 11.5 ps for v = 13 and 4.7 ps for v = 17 is found, but there is also a much longer lived component to the lifetime distributions that is more important for v = 13 than for v = 17. Some of the longer lived metastables correspond to high angular momentum orbiting states of H, but other sources of metastability are also present.     

Microscopic origin of the humidity dependence of the adhesion force in atomic force microscopy

Water condenses between an atomic force microscope (AFM) tip and a surface to form a nanoscale bridge that produces a significant adhesion force on the tip. As humidity increases, the water bridge always becomes wider but the adhesion force sometimes decreases. The authors show that the humidity dependence of the adhesion force is intimately related to the structural properties of the underlying water bridge. A wide bridge whose width does not vary much with tip-surface distance can increase its volume as distance is increased. In this case, the adhesion force decreases as humidity rises. Narrow bridges whose width decreases rapidly with increasing tip-surface distance give the opposite result. This connection between humidity dependence of the adhesion force and the structural susceptibility of the water bridge is illustrated by performing Monte Carlo simulations for AFM tips with various hydrophilicities.