Resonantly enhanced vacuum-ultraviolet generation and multiphoton ionization in carbon monoxide gas

Competition between three-photon resonantly enhanced vacuum ultraviolet third-harmonic generation and six-photon multiphoton ionization using the A state in gaseous carbon monoxide is observed. Excitation spectra of the third-harmonic emission exhibit increasing blue shifts and broadening with increasing pressure due to the phase matching requirements. Estimates for the efficiency and tunability show that third-harmonic generation in carbon monoxide molecules is a promising source for coherent vacuum ultraviolet light

Desorption of NO/Pd(111) induced by subpicosecond laser pulses: internal energy distributions

Results are presented on the desorption of nitric oxide (NO) from a Pd(111) surface under exposure to visible laser radiation in a 200-fs pulse. The desorption process for this prototype system of a diatomic molecule chemisorbed on a nonreactive metal surface has been investigated by measuring the yield and energy distribution of the desorbed molecules. The salient features of the experiment are described, with emphasis on the internal energy distributions of the desorbed NO molecules. A rotational energy distribution for desorbed NO molecules in the ground vibrational and electronic states is shown and discussed

The Photoactive Excited State of the B12-Based Photoreceptor CarH

7 pags., 5 figs.We have used transient absorption spectroscopy in the UV-visible and X-ray regions to characterize the excited state of CarH, a protein photoreceptor that uses a form of B12, adenosylcobalamin (AdoCbl), to sense light. With visible excitation, a nanosecond-lifetime photoactive excited state is formed with unit quantum yield. The time-resolved X-ray absorption near edge structure difference spectrum of this state demonstrates that the excited state of AdoCbl in CarH undergoes only modest structural expansion around the central cobalt, a behavior similar to that observed for methylcobalamin rather than for AdoCbl free in solution. We propose a new mechanism for CarH photoreactivity involving formation of a triplet excited state. This allows the sensor to operate with high quantum efficiency and without formation of potentially dangerous side products. By stabilizing the excited electronic state, CarH controls reactivity of AdoCbl and enables slow reactions that yield nonreactive products and bypass bond homolysis and reactive radical species formation.This work was supported by grants from the National Science Foundation NSF-CHE 1464584 and NSFCHE 1836435 to R.J.S., NSF-CHE 1565795 to K.J.K., NSFCHE 1608553 and NSF-CHE-1904759 to E.N.G.M., and NSF-CHE 1945174 to M.K.; from the Agencia Estatal de Investigación (AEI)-Spain and the European Regional Development Fund (FEDER) grants PGC2018-094635-BC21 (to M.E.-A.) and PGC2018-094635-B-C22 (to S.P.); and from the Fundacion Seneca (Murcia)-Spain grant 20992/PI/ ́ 18 (to M.E.-A.). Portions of this work were carried out in the Laboratory for Ultrafast Multidimensional Optical Spectroscopy (LUMOS) supported by NSF-CHE 1428479. Use of the Linac Coherent Light Source (LCLS), SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under contract no. DE-AC02-76SF00515