The Lehmann Lab is located in on the ground floor of the UVa Chemistry Building, Rm 119. Lehmann's office, Rm 124, is down the hall.
There are many problems of both fundamental and of practical importance that require measurement of extremely low concentrations of certain impurities. Molecular Spectroscopy provides one approach that excels in the high specificity provided by the detailed structure in the spectrum, particularly for molecules in the gas phase. Lehmann’s group has been working on the development of new trace sensors, largely based upon the method of cavity ring-down spectroscopy (CRDS). In CRDS, one forms a stable optical cavity using mirrors with reflectivity > 99.99% and observes absorption of a sample contained inside the cavity by an increase in the rate of decay of light that is trapped between the mirrors. Sample absorption as low as 1 part in 109 per pass of the cell can be measured in this way. The Lehmann group pioneered the use of low cost and rugged diode lasers developed for the telecom industry in CRDS and has demonstrated detection of a number of small molecules, such as H2O, NH3, and CH4 at levels below one part per billion in a sample gas. Tiger Optics, Inc. is now selling instruments based upon this work to several industries. We have developed a new, fiber optic version of CRDS and have demonstrated that this could be used to detect a single cell that sticks to the surface of an optical fiber. We are presently developing an ultrabroad bandwidth version of CRDS that will allow multiple chemical species to be monitored simultaneously, such as with an FTIR, but with much higher sensitivity. The key enabling tchnologies are prism retrorefletors and a supercontinuum lightsource. Breath analysis for medical diagnosis is an important potential application of CRDS that we beginning to work in this area. In collaboration with Dr. Ben Gaston of the UVa Medical School, we are developing a mid-IR based nitric oxide detector. NO in breath detector can serve as a diagnoistic marker for both asthma and infection. We are also developing technology to use near IR CRDS to determine the 13C/12C and D/H isotope ratios of methane in atmospheric air. These give informaton on the sources and sinks of methane in the environment.
Spectroscopy in super fluid Helium
Research in the Lehmann group has long used laser spectroscopy and theoretical modeling to study molecular dynamics – studying chemical reactions at their most fundamental level. In recent years, this line of work has focused on the spectroscopy of atoms and molecules dissolved in nanodroplets of superfluid helium. Helium Nanodroplet Isolation (HENDI) combines many of the most attractive features of both high resolution, molecular beam spectroscopy and more traditional rare gas matrix spectroscopy. The droplets cool any solvated molecule down to a temperature of only 0.38 K but remain liquid, which allows molecules to move and rotate nearly freely with relaxation times three to four orders of magnitude longer than in traditional liquids. This allows for the study of the interaction of molecules with a unique solvent of very low entropy and where quantum effects are dominant. Fundamental questions are yet unresolved, such as how the molecules come into equilibrium with the superfluid and why quantized vortices (which are common in build liquid helium) have not been observed in the droplets. The droplets allow the production of new chemical species and new isomers of known compounds.
We are working on the spectroscopy of free radicals in helium. Traditional wisdom is that the reaction of two free radicals can occur without a barrier, but high level ab initio calculations suggest that in many such reactions (such as O2 + O -> O3), small entrance channel barriers exist and these are believed to play an important role in the rates of three body recombination; a process that produces O3 in the atmosphere. It should be possible to quench entrance channel complexes and study their properties using HENDI. We have a "hydrogen cracker" that will produce an effusive beam of atomic hydrogen, which we will dope into the droplets. The plan is to study hydrogen addition reactions, such as H + CO -> HCO, which are believed to proceed at low temperatures (posibly due to tunneling) and are important reactions in interstellar space. We are finishing construction of a new beam machine to study ions in helium droplet. Doped droplets (which have a very low velocity spead) will be mass selected using a hemispherical energy analyzer. This will allow several novel measurements. We plan to study the translational motion of the ions inside the droples and determine the rate of translational cooling as a function of droplet size and the chemical nature of the ion. By exciting the ions with circularly polarized microwaves, we hope to create vortices in the droplets. The binding energies of atomic and molecular cluster ions will be determined from the number of helium atoms evaporated from the droplet after cluster formation.
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