Reducing the first-order Doppler shift in a Sagnac interferometer

We demonstrate a technique to reduce first-order Doppler shifts in crossed atomic/molecular and laser beam setups by aligning two counterpropagating laser beams as part of a Sagnac interferometer. Interference fringes on the exit port of the interferometer reveal minute deviations from perfect antiparallelism. Residual Doppler shifts of this method scale with the ratio v/(4d) of the typical atomic/molecular velocity v and the laser beam diameter d. The method is implemented for precision frequency calibration studies at deep-UV wavelengths, both in one- and two-photon excitation schemes: the 6s(2) --> 6s30p(3/2)J=1 line in Yb at 199 nm and the 4p(6) --> 4p(5)p[1/2](0) transition in Kr at lambda=212 nm. The achieved precision of 6 x 10(-10) is limited by the characteristics of the laser system.     

Primary reactions of bacteriophytochrome observed with ultrafast mid-infrared spectroscopy

Phytochromes are red-light photoreceptor proteins that regulate a variety of responses and cellular processes in plants, bacteria, and fungi. The phytochrome light activation mechanism involves isomerization around the C(15)═C(16) double bond of an open-chain tetrapyrrole chromophore, resulting in a flip of its D-ring. In an important recent development, bacteriophytochrome (Bph) has been engineered for use as a fluorescent marker in mammalian tissues. Bphs covalently bind a biliverdin (BV) chromophore, naturally abundant in mammalian cells. Here, we report an ultrafast time-resolved mid-infrared spectroscopic study on the Pr state of two highly related Bphs from Rps. palustris , RpBphP2 (P2) and RpBphP3 (P3) with distinct photoconversion and fluorescence properties. We observed that the BV excited state of P2 decays in 58 ps, while the BV excited state of P3 decays in 362 ps. By combining ultrafast mid-IR spectroscopy with FTIR spectroscopy on P2 and P3 wild type and mutant proteins, we demonstrate that the hydrogen bond strength at the ring D carbonyl of the BV chromophore is significantly stronger in P3 as compared to P2. This result is consistent with the X-ray structures of Bph, which indicate one hydrogen bond from a conserved histidine to the BV ring D carbonyl for classical bacteriophytochromes such as P2, and one or two additional hydrogen bonds from a serine and a lysine side chain to the BV ring D carbonyl for P3. We conclude that the hydrogen-bond strength at BV ring D is a key determinant of excited-state lifetime and fluorescence quantum yield. Excited-state decay is followed by the formation of a primary intermediate that does not decay on the nanosecond time scale of the experiment, which shows a narrow absorption band at ～1540 cm(-1). Possible origins of this product band are discussed. This work may aid in rational structure- and mechanism-based conversion of BPh into an efficient near-IR fluorescent marker.     

High-resolution Fourier-transform extreme ultraviolet photoabsorption spectroscopy of 14N15N

The first comprehensive high-resolution photoabsorption spectrum of (14)N(15)N has been recorded using the Fourier-transform spectrometer attached to the Desirs beamline at the Soleil synchrotron. Observations are made in the extreme ultraviolet and span 100 000-109 000 cm(-1) (100-91.7 nm). The observed absorption lines have been assigned to 25 bands and reduced to a set of transition energies, f values, and linewidths. This analysis has verified the predictions of a theoretical model of N(2) that simulates its photoabsorption and photodissociation cross section by solution of an isotopomer independent formulation of the coupled-channel Schro?dinger equation. The mass dependence of predissociation linewidths and oscillator strengths is clearly evident and many local perturbations of transition energies, strengths, and widths within individual rotational series have been observed.     

QED effects in molecules: test on rotational quantum states of H2

Quantum electrodynamic effects have been systematically tested in the progression of rotational quantum states in the X?1Σ(g)(+), v=0 vibronic ground state of molecular hydrogen. High-precision Doppler-free spectroscopy of the EF?1Σ(g)(+)-X?1Σ(g)(+) (0,0) band was performed with 0.005 cm(-1) accuracy on rotationally hot H2 (with rotational quantum states J up to 16). QED and relativistic contributions to rotational level energies as high as 0.13 cm(-1) are extracted, and are in perfect agreement with recent calculations of QED and high-order relativistic effects for the H2 ground state.