Optical absorption of lithium metal vapor at high temperatures

Experimental results are reported for a unique spectroscopic device called the Plasma Spectroscopy Cell. Optical absorption of lithium metal vapor was observed at high density and temperature. Absorption spectra are analyzed using theoretical calculations of absorption cross sections for lithium-helium interactions, and singlet and triplet state transitions of diatomic lithium in the visible spectral range. This is believed to be the most complex example yet calculated in which absolute bound-bound, bound-free, free-bound, and free-free contributions for all possible optically allowed transitions are all included, in quite respectable agreement with experiment.     

Photoassociative spectroscopy of pure long-range molecules

We have experimentally studied the “pure long-range” state, 0 _g ^? , of³⁹K₂ for the first time by high resolution photoassociative spectroscopy of ultracold potassium atoms. Well-resolved vibrational levels have yielded molecular constants for this state. Analytical expressions for the potential energy curves of the two pure long-range states, 0 _g ^? and 1 _u , are obtained. All the available theoretical and experimental molecular constants of the three special long-range potentials with extrema for all the alkali metals are summarized.     

The A 1Σ+ → X 1Σ+ bands of the isotopic lithium hydrides

In order to obtain a better understanding of the X¹Σ⁺ ground state and the A¹Σ⁺ state potential energy curves of lithium hydride and to examine in detail the concept of “mass-reduced quantum numbers” for both an ordinary (X¹Σ⁺) and an anomalous (A¹Σ⁺) electronic state, the emission spectra of the A¹Σ⁺ → X¹Σ⁺ bands of the isotopic lithium hydrides and deuterides were photographed in the 3000–5000-Å region with a 3.4-m Ebert Spectrograph. The bands found involved v″ = 0 to 7 to various v′ = 0 to 17 for ⁶LiH, and v″ = 0 to 7 to various v′ = 1 to 16 for ⁶LiD. Additional bands involving v″ = 4 and 5 were also found for ⁷LiH. The vibrational-rotational spectroscopic analysis of ⁷LiH, ⁶LiH, and ⁶LiD are reported here, as are the reanalyses of the ⁷LiH and ⁷LiD data reported by Crawford and Jorgensen. New Rydberg-Klein-Rees (RKR) A¹Σ⁺ and X¹Σ⁺ potential curves have been constructed for each individual molecule and are reported, but detailed isotopic comparisons will be reported in subsequent publications.     

Structure, energetics, and reactions of alkali tetramers

Electronic structure calculations have been carried out for all possible alkali tetramers that can be formed from X(2) + X(2) → X(2)X(2), X(2) + Y(2) → X(2)Y(2), and XY + XY → X(2)Y(2) alkali dimer association reactions. Vibrationally stable rhombic (D(2h)) and planar (C(s)) structures are found for all possible tetramers formed from the alkali metals, Li to Cs. All tetramer formation reactions (from ground state singlet homonuclear or heteronuclear dimers) are found to be exothermic with binding energies ranging from 6282 cm(-1) for Li(2)Li(2) to 1985 cm(-1) for Cs(2)Cs(2). Extensive calculations, carried out at long-range for several reactant pairs, indicate that there are barrier-less pathways for the formation of tetramers from dimer association reactions. At low temperatures, direct formation of tetramers is unlikely, owing to the large exothermicity associated with these association reactions, but atom exchange reactions (X(2) + Y(2) ? XY + XY) are possible for some species.     

Airborne-mercury detection by resonant UV laser pumping

Optical pumping of the Hg(0) (6s (1)S(0) --> 6p (3)P(1)) transition at 253.7 nm (in air) leads to extremely fast energy transfer and strong laser-induced-fluorescence (LIF) from the Hg(0) (7s(3)S(1) --> 6p (3)P(2)) green transition at 546.2 nm, which is not directly populated by the laser. Ionization occurs simultaneously and becomes particularly strong at reduced background pressures. These observations are consistent with the existence of a multiphoton process followed by electron collisional excitation. Preliminary studies are made to evaluate these phenomena for detecting elemental airborne mercury by LIF and point monitoring with an ionization detector. Measured sensitivities of 2 and 10 parts in 10(9) (ppb), respectively, at 0.1-Torr air pressure are projected to increase to 1 x 10(-4) and 1 x 10(-5) ppb after relevant system optimization.     

Photoassociation spectroscopy of ultracold Cs below the 6P1/2 limit

We have performed high precision photoassociation spectroscopy of ultracold cesium gas. Using trap-loss fluorescence detection and controlling the background cesium pressure we were able to photoassociate atoms into excited states of ultracold molecules with large detunings up to 56 cm(-1) below the Cs(6S(1/2)) + Cs(6P(1/2)) atomic asymptote. Vibrational progressions are assigned to 0(g)(-), 0(u)(+), and 1(g) long-range states. By fitting the spectral data to the LeRoy-Bernstein expression, the effective coefficients of the leading long-range interactions and the vibrational quantum number at dissociation are obtained. In addition we have observed spectral perturbations between states of the same symmetry belonging to different asymptotes (6P(1/2) and 6P(3/2)). The perturbations are manifested through irregular vibrational level spacings and are especially pronounced in the 0(u)(+) symmetry. Many observed rotational levels indicate d- and higher partial wave contributions to the photoassociation cross section in the presence of trapping laser light, while spectral regions with only weak features suggest nodes in the lower state wave functions corresponding to the two ground state atoms asymptote.