+ + Chem. Rev. 1997, 97, 25−51 25 Cavity Ringdown Laser Absorption Spectroscopy: History, Development, and Application to Pulsed Molecular Beams J. J. Scherer,† J. B. Paul, A. O’Keefe,‡ and R. J. Saykally* Department of Chemistry, University of California, Berkeley, California 94720, and Los Gatos Research, 1685 Plymouth Way, Mountain View, California 94043 Received December 2, 1993 (Revised Manuscript Received September 13, 1996) Contents again, dynamic effects complicate the interpretation of spectra. The same considerations apply to other I. Introduction 25 types of “action” spectroscopy. II. CRLAS History and Development 26 It would often be preferable to measure the elec- CRLAS Applications 29 tronic spectra of molecules and clusters in direct III. CRLAS Sensitivity and Fundamentals 31 absorption, as this approach is the most straightfor- First-Order Considerations 32 ward and accurate means of determining absolute Data Acquisition 32 vibronic band intensities and for accessing states that Shot Noise 33 are invisible to LIF or REMPI. The problem, of Laser Bandwidth and Multiexponential 33 course, is that direct absorption methods are gener- Decays ally orders of magnitude less sensitive than the Interference Effects in CRLAS 34 “action” techniques and are, therefore, difficult to Laser Transverse Mode Considerations 38 apply to transient species, such as clusters or radi- Cavity Mirrors 39 cals. IV. CRLAS of Pulsed Supersonic Jets 39 In this review, we describe a relatively new direct Applications to Metal Cluster Systems 40 absorption technique that we have developed for Copper Dimer 41 measuring the electronic spectra of jet-cooled mol- ecules and clusters with both high sensitivity and Aluminum Dimer 42 high spectral resolution. The method is based on Copper Trimer 42 measurement of the time rate of decay of a pulse of Metal Silicides 44 light trapped in a high reflectance optical cavity; we Copper Silicide 45 call it cavity ringdown laser absorption spectroscopy Silver Silicide 46 (CRLAS). In practice, pulsed laser light is injected Gold Silicide 48 into an optical cavity that is formed by a pair of V. Summary 50 highly reflective (R > 99.9%) mirrors. The small VI. Acknowledgments 50 amount of light that is now trapped inside the cavity VII. References 50 reflects back and forth between the two mirrors, with a small fraction ( 1 - R) transmitting through each mirror with each∼ pass. The resultant transmission I. Introduction of the circulating light is monitored at the output mirror as a function of time and allows the decay time The measurement of electronic spectra of super- of the cavity to be determined. A simple picture of sonically cooled molecules and clusters is a widely the cavity decay event for the case where the laser used approach for addressing many problems in pulse is temporally shorter than the cavity round trip chemistry. The most established techniques for transit time is presented in Figure 1. In this case, making such measurements are laser-induced fluo- the intensity envelope of these discrete transmitted rescence (LIF) and resonance-enhanced multiphoton pulses exhibits a simple exponential decay. The time ionization (REMPI), and both have been employed required for the cavity to decay to 1/e of the initial very successfully in a large number of studies. output pulse is called the “cavity ringdown” time. However, both methods often fail for systems con- Determination of the ringdown time allows the taining more than a few atoms, due to rapid internal absolute single pass transmission coefficient of the conversion, predissociation, or other dynamical pro- cavity to be determined with high accuracy, given the cesses. Even for small systems, the vibronic band mirror spacing. The apparatus is converted to a intensities are often contaminated by intramolecular sensitive absorption spectrometer simply by placing relaxation dynamics; in such cases, these techniques an absorbing medium between the two mirrors and cannot be used for reliable intensity measurements. recording the frequency dependent ringdown time of For clusters that exhibit rapid photofragmentation, the cavity. Ideally, the ringdown time is a function depletion spectroscopy can be employed quite ef- of only the mirror reflectivities, cavity dimensions, fectively to measure their vibronic structure, but and sample absorption. Absolute absorption intensi- ties are obtained by subtracting the base-line trans- mission of the cavity, which is determined when the † IBM Predoctoral Fellow. Current address: Sandia National Laboratories, M/S 9055, Livermore, CA 94551-0969. laser wavelength is off-resonance with all molecular ‡ Los Gatos Research. transitions. S0009-2665(93)00048-2 CCC: $28 00 © 1997 American Chemical Society + + 26 Chemical Reviews, 1997, Vol. 97, No. 1 Scherer et al. James J. Scherer was born and raised in Berkeley, CA. He received his Anthony O’Keefe is President of Los Gatos Research, a small R&D Bachelors degrees in art and physics at the University of California at company located in the San Francisco area that is involved in government- Berkeley, followed by a Doctoral degree in chemistry also at Berkeley. funded laser research for aerospace applications. Prior to this position His research interests include spectroscopic studies of metal cluster he was a partner and co-owner of Deacon Research, where he developed species and free radicals. the Cavity Ringdown Absorption technique that forms the basis of the present work. He has worked to develop this technique from a laboratory curiosity to a widely recognized method of making ultra-high sensitivity spectroscopic measurements. Dr. O’Keefe received his B.S. degree in Chemistry from Beloit College in 1977 and his M.S. and Ph.D. degrees in physical chemistry from the University of California, Berkeley, in 1979 and 1981, respectively. Joshua B. Paul received his Bachelor’s degree in Physics in 1991 from the University of California at Berkeley. As an undergraduate, he worked in Professor Saykally’s laboratories helping to build the current cavity ringdown apparatus. When given the opportunity to join the Chemistry Graduate program at Berkeley, he gladly accepted, electing to continue his work on the ringdown project. Recently, he has switched from UV− visible studies to the mid-infrared, where he has employed ringdown toward Richard Saykally was born in 1947 in Rhinelander, WI. He graduated the study of the O−H stretch fundamentals of water clusters and the − from the University of WisconsinsEau Claire in 1970 and received his N H stretches of nucleotide base clusters. At 28 years of age, Josh will Ph.D. from UWsMadison in 1977 under the direction of R. C. Woods. soon face the realities of life after Graduate School. After spending two years at NIST in Boulder as a NRC postdoctoral fellow with K. M. Evenson, he was appointed Assistant Professor at UC Berkeley in 1979. He has served as Vice-Chair of Chemistry from 1988 to 1991 Because the cavity decay time is independent of and has been the thesis advisor for 30 Ph.Ds. He has received numerous − the initial intensity that exits the cavity, CRLAS honors and awards, including the Harrison Howe Award, the Lippincott Prize for Vibrational Spectroscopy, the Bomem Michelson Award in sensitivity is not seriously degraded by the large shot Spectroscopy, the E. K. Plyler Prize for Molecular Spectroscopy, the Bourke to shot intensity fluctuations common to pulsed Lectureship of the Royal Society of Chemistry, and a Humboldt Senior lasers. With state-of-the-art data collection methods, Scientist Award. He has been a Presidential Young Investigator and a -7 Dreyfus Scholar and is a Fellow of the American Physical Society, the a fractional absorption (1 - I/Io)of3 10 per pass × Optical Society of America, the Royal Society of Chemistry, and the can be measured with a single laser pulse; signal American Academy of Arts and Sciences. He serves on the editorial averaging can be employed to improve this figure. boards of The Journal of Chemical Physics, Molecular Physics, Chemical While currently implemented from the ultraviolet to Physics Letters, The Review of Scientific Instruments, The Journal of the mid-infrared regions, CRLAS is primarily limited Molecular Spectroscopy, and Spectroscopy. Also recognized as an to spectral regions by both the availability of outstanding teacher, Professor Saykally has received the Berkeley Distinguished Teaching Award and was the co-director of Science for highly reflective mirrors and suitable pulsed laser Science Teachers, a national program for secondary school teacher sources. enhancement. He has published nearly 200 papers on subjects ranging from intermolecular forces and molecular ions to astrophysics and laser In this paper, we present an account of the theory, spectroscopy. development, and applications of the CRLAS method, with emphasis on the specific application of pulsed II. CRLAS History and Development molecular beam spectroscopy. In addition to a gen- The history and development of the CRLAS tech- eral review of CRLAS, experimental data are pre- nique dates back to the invention of the cw-based sented that demonstrate the simplicity, sensitivity, cavity attenuated phase shift (CAPS) method by J. and generality of this powerful new spectroscopic tool. M. Herbelin et al. in the early 1980’s.1 Although the + + Cavity Ringdown Laser Absorption Spectroscopy Chemical Reviews, 1997, Vol. 97, No. 1 27 Figure 1. In the short pulse limit, discrete pulses of laser Figure 2. Cavity attenuated phase shift method (CAPS) light leak out of the cavity with each pass. The intensity experimental diagram. Modulated continuous wave laser envelope of the resultant decay is approximated by a light is coupled into a high-finesse optical cavity. Measure- smooth exponential expression. Determination of the decay ment of the resultant phase shift at the exit mirror allows time allows the cavity losses or molecular absorption to be the mirror reflectivities to be determined. In Herbelin’s determined. Typical cavity decays consist of ten thousand original work, a ring resonator was also used.