Rotational constants and structure of para-difluorobenzene determined by femtosecond Raman coherence spectroscopy: A new transient type

Femtosecond Raman rotational coherence spectroscopy (RCS) detected by degenerate four-wave mixing is a background-free method that allows to determine accurate gas-phase rotational constants of non-polar molecules. Raman RCS has so far mostly been applied to the regular coherence patterns of symmetric-top molecules, while its application to nonpolar asymmetric tops has been hampered by the large number of RCS transient types, the resulting variability of the RCS patterns, and the 10³–10⁴ times larger computational effort to simulate and fit rotational Raman RCS transients. We present the rotational Raman RCS spectra of the nonpolar asymmetric top 1,4-difluorobenzene (para-difluorobenzene, p-DFB) measured in a pulsed Ar supersonic jet and in a gas cell over delay times up to ~2.5 ns. p-DFB exhibits rotational Raman transitions with ΔJ = 0, 1, 2 and ΔK = 0, 2, leading to the observation of J −, K −, A −, and C–type transients, as well as a novel transient (S–type) that has not been characterized so far. The jet and gas cell RCS measurements were fully analyzed and yield the ground-state (v = 0) rotational constants Aₒ = 5637.68(20) MHz, Bₒ = 1428.23(37) MHz, and Cₒ = 1138.90(48) MHz (1σ uncertainties). Combining the Aₒ, Bₒ, and Cₒ constants with coupled-cluster with single-, double- and perturbatively corrected triple-excitation calculations using large basis sets allows to determine the semi-experimental equilibrium bond lengths rₑ(C₁–C₂) = 1.3849(4) Å, rₑ(C₂–C³) = 1.3917(4) Å, rₑ(C–F) = 1.3422(3) Å, and rₑ(C₂–H₂) = 1.0791(5) Å.

Experiment: summer mortality phenomena in pacific oysters

Mass mortalities of Pacific oysters Crassostrea gigas occur regularly when temperatures are high. Elevated temperatures facilitate the proliferation and spread of pathogens and simultaneously impose physiological stress on the host. Additionally, periods of high temperatures coincide with the oyster spawning season. Spawning is energetically costly and can further compromise oyster immunity. Most studies monitoring the underlying factors of oyster summer mortality in the field, point to the involvement of abiotic and biotic factors including low salinities, high temperatures, pollutants, toxic algae blooms, pathogen exposure and physical stress in conjunction with maturation. However, studies addressing more than two factors experi- mentally are missing thus far. Therefore, we investigated the combination of three main factors including abiotic as well as internal and external biotic stressors by conducting controlled infection experiments on pre-and post-spawning as well as on gravid oysters with opportunistic Vibrio sp. at two different tempera- tures. Based on mortality rates, infection intensity and cellular immune parameters, we provide experimental evidence that all three factors (i.e. reproductive investment, elevated temperatures and infection with oppor- tunistic Vibrio sp.) act additively to the phenomenon of oyster summer mortality, leaving post-spawning oyster more susceptible to SMS than pre-spawning and gravid oysters. While previous studies found that post-spawning oysters have a lower thermal tolerance and a reduced ability to withstand pathogen infec- tions, our study now allows to separate the relative contribution of different causative agents to oyster sum- mer mortality and pinpoint to infection with pathogenic Vibrio sp. being of highest importance. In addition we can add a mechanistic understanding for the higher losses after spawning during which the phagocytic ability of hemocytes was strongly impeded resulting in insufficient clearance of pathogens.

A proposal for multi-tens of GW fully coherent femtosecond soft X-ray lasers

X-ray free-electron lasers1,2 delivering up to 131013 coherent photons in femtosecond pulses are bringing about a revolution in X-ray science3?5. However, some plasma-based soft X-ray lasers6 are attractive because they spontaneously emit an even higher number of photons (131015), but these are emitted in incoherent and long (hundreds of picoseconds) pulses7 as a consequence of the amplification of stochastic incoherent self-emission. Previous experimental attempts to seed such amplifiers with coherent femtosecond soft X-rays resulted in as yet unexplained weak amplification of the seed and strong amplification of incoherent spontaneous emission8. Using a time-dependent Maxwell?Bloch model describing the amplification of both coherent and incoherent soft X-rays in plasma, we explain the observed inefficiency and propose a new amplification scheme based on the seeding of stretched high harmonics using a transposition of chirped pulse amplification to soft X-rays. This scheme is able to deliver 531014 fully coherent soft X-ray photons in 200 fs pulses and with a peak power of 20 GW.

Hysteresis phenomena in transverse galloping of triangular cross-section bodies

Transverse galloping is a type of aeroelastic instability characterised by large amplitude, low frequency oscillation of a structure in the direction normal to the mean wind direction. It normally appears in bodies with small stiffness and structural damping, provided the incident flow velocity is high enough. In the simplest approach transverse galloping can be considered as a one-degree-of-freedom oscillator subjected to aerodynamic forces, which in turn can be described by using a quasi-steady description. In this frame it has been demonstrated that hysteresis phenomena in transverse galloping is related to the existence of inflection points in the curve giving the dependence with the angle of attack of the aerodynamic coefficient normal to the incident flow. Aiming at experimentally checking such a relationship between these inflection points and hysteresis, wind tunnel experiments have been conducted. Experiments have been restricted to isosceles triangular cross-section bodies, whose galloping behaviour is well documented. Experimental results show that, according to theoretical predictions, hysteresis takes place at the angles of attack where there are inflection points in the lift coefficient curve, provided that the body is prone to gallop at these angles of attack.

Modeling of dangerous phenomena and innovative techniques for hazard evaluation and risk mitigation

Society is frequently exposed to and threatened by dangerous phenomena in many parts of the world. Different types of such phenomena require specific actions for proper risk management, from the stages of hazard identification to those of mitigation (including monitoring and early-warning) and/or reduction. The understanding of both predisposing factors and triggering mechanisms of a given danger and the prediction of its evolution from the source to the overall affected zone are relevant issues that must be addressed to properly evaluate a given hazard.

Bridge windshield design to avoid aeroelastic phenomena

Since in 1940 the Tacoma Narrows Bridge was destroyed by the wind, aeroelastic instabilities have been recognized as one of the most challenging aspects of bridge design. They can produce long-term fatigue failure through vortex induced vibrations, or sudden collapse through self-excited flutter. These vibrations may also cause discomfort for the users and temporary closure of the bridge. Wind tunnel studies are a very helpful tool to understand these phenomena. By means of them, the critical wind speed at which vortex induced vibration and flutter appear can be precisely determined and the design of the bridge can be reconsidered in the early steps of the process. In this paper, an optimum design of the bridge section is sought. One of the most relevant parameters that influence the stability of a certain deck is the porosity of the barriers. Section model tests have been carried out to find whether an optimum value of the porosity of the barrier exists. This value or range of values must present neither vortex induced vibration nor flutter.

Femtosecond cluster studies of the solvated 7-azaindole excited state double-proton transfer

Presented here are femtosecond pump-probe studies on the water-solvated 7-azaindole dimer, a model DNA base pair. In particular, studies are presented that further elucidate the nature of the reactive and nonreactive dimers and also provide new insights establishing that the excited state double-proton transfer in the dimer occurs in a stepwise rather than a concerted manner. A major question addressed is whether the incorporation of a water molecule with the dimer results in the formation of species that are unable to undergo excited state double-proton transfer, as suggested by a recent study reported in the literature [Nakajima, A., Hirano, M., Hasumi, R., Kaya, K., Watanabe, H., Carter, C. C., Williamson, J. M. & Miller, T. (1997) J. Phys. Chem. 101, 392–398]. In contrast to this earlier work, our present findings reveal that both reactive and nonreactive dimers can coexist in the molecular beam under the same experimental conditions and definitively show that the clustering of water does not induce the formation of the nonreactive dimer. Rather, when present with a species already determined to be a nonreactive dimer, the addition of water can actually facilitate the occurrence of the proton transfer reaction. Furthermore, on attaining a critical hydration number, the data for the nonreactive dimer suggest a solvation-induced conformational structure change leading to proton transfer on the photoexcited half of the 7-azaindole dimer.

Femtosecond observation of benzyne intermediates in a molecular beam: Bergman rearrangement in the isolated molecule

In this communication, we report our femtosecond real-time observation of the dynamics for the three didehydrobenzene molecules (p-, m-, and o-benzyne) generated from 1,4-, 1,3-, and 1,2-dibromobenzene, respectively, in a molecular beam, by using femtosecond time-resolved mass spectrometry. The time required for the first and the second C-Br bond breakage is less than 100 fs; the benzyne molecules are produced within 100 fs and then decay with a lifetime of 400 ps or more. Density functional theory and high-level ab initio calculations are also reported herein to elucidate the energetics along the reaction path. We discuss the dynamics and possible reaction mechanisms for the disappearance of benzyne intermediates. Our effort focuses on the isolated molecule dynamics of the three isomers on the femtosecond time scale.

Femtosecond resolution of ligand-heme interactions in the high-affinity quinol oxidase bd: A di-heme active site?

Interaction of the two high-spin hemes in the oxygen reduction site of the bd-type quinol oxidase from Escherichia coli has been studied by femtosecond multicolor transient absorption spectroscopy. The previously unidentified Soret band of ferrous heme b595 was determined to be centered around 440 nm by selective excitation of the fully reduced unliganded or CO-bound cytochrome bd in the α-band of heme b595. The redox state of the b-type hemes strongly affects both the line shape and the kinetics of the absorption changes induced by photodissociation of CO from heme d. In the reduced enzyme, CO photodissociation from heme d perturbs the spectrum of ferrous cytochrome b595 within a few ps, pointing to a direct interaction between hemes b595 and d. Whereas in the reduced enzyme no heme d-CO geminate recombination is observed, in the mixed-valence CO-liganded complex with heme b595 initially oxidized, a significant part of photodissociated CO does not leave the protein and recombines with heme d within a few hundred ps. This caging effect may indicate that ferrous heme b595 provides a transient binding site for carbon monoxide within one of the routes by which the dissociated ligand leaves the protein. Taken together, the data indicate physical proximity of the hemes d and b595 and corroborate the possibility of a functional cooperation between the two hemes in the dioxygen-reducing center of cytochrome bd.

Femtosecond dynamics of DNA-mediated electron transfer

Diverse biophysical and biochemical studies have sought to understand electron transfer (ET) in DNA in part because of its importance to DNA damage and its repair. However, the dynamics and mechanisms of the elementary processes of ET in this medium are not fully understood and have been heavily debated. Two fundamental issues are the distance over which charge is transported and the time-scale on which the transport through the π-stack of the DNA base pairs may occur. With femtosecond resolution, we report direct observation in DNA of ultrafast ET, initiated by excitation of tethered ethidium (E), the intercalated electron acceptor (A); the electron donor (D) is 7-deazaguanine (Z), a modified base, placed at different, fixed distances from A. The ultrafast ET between these reactants in DNA has been observed with time constants of 5 ps and 75 ps and was found to be essentially independent of the D–A separation (10–17 Å). However, the ET efficiency does depend on the D–A distance. The 5-ps decay corresponds to direct ET observed from 7-deazaguanine but not guanine to E. From measurements of orientation anisotropies, we conclude that the slower 75-ps process requires the reorientation of E before ET, similar to E/nucleotide complexes in water. These results reveal the nature of ultrafast ET and its mechanism: in DNA, ET cannot be described as in proteins simply by a phenomenological parameter, β. Instead, the involvement of the base pairs controls the time scale and the degree of coherent transport.

Two-dimensional infrared spectroscopy of peptides by phase-controlled femtosecond vibrational photon echoes

Two-dimensional infrared spectra of peptides are introduced that are the direct analogues of two- and three-pulse multiple quantum NMR. Phase matching and heterodyning are used to isolate the phase and amplitudes of the electric fields of vibrational photon echoes as a function of multiple pulse delays. Structural information is made available on the time scale of a few picoseconds. Line narrowed spectra of acyl-proline-NH2 and cross peaks implying the coupling between its amide-I modes are obtained, as are the phases of the various contributions to the signals. Solvent-sensitive structural differences are seen for the dipeptide. The methods show great promise to measure structure changes in biology on a wide range of time scales.

Femtosecond dynamics of the forbidden carotenoid S1 state in light-harvesting complexes of purple bacteria observed after two-photon excitation

Time-resolved excited-state absorption intensities after direct two-photon excitation of the carotenoid S1 state are reported for light-harvesting complexes of purple bacteria. Direct excitation of the carotenoid S1 state enables the measurement of subsequent dynamics on a fs time scale without interference from higher excited states, such as the optically allowed S2 state or the recently discovered dark state situated between S1 and S2. The lifetimes of the carotenoid S1 states in the B800-B850 complex and B800-B820 complex of Rhodopseudomonas acidophila are 7 ± 0.5 ps and 6 ± 0.5 ps, respectively, and in the light-harvesting complex 2 of Rhodobacter sphaeroides ≈1.9 ± 0.5 ps. These results explain the differences in the carotenoid to bacteriochlorophyll energy transfer efficiency after S2 excitation. In Rps. acidophila the carotenoid S1 to bacteriochlorophyll energy transfer is found to be quite inefficient (φET1 <28%) whereas in Rb. sphaeroides this energy transfer is very efficient (φET1 ≈80%). The results are rationalized by calculations of the ensemble averaged time constants. We find that the Car S1 → B800 electronic energy transfer (EET) pathway (≈85%) dominates over Car S1 → B850 EET (≈15%) in Rb. sphaeroides, whereas in Rps. acidophila the Car S1 → B850 EET (≈60%) is more efficient than the Car S1 → B800 EET (≈40%). The individual electronic couplings for the Car S1 → BChl energy transfer are estimated to be approximately 5–26 cm−1. A major contribution to the difference between the energy transfer efficiencies can be explained by different Car S1 energy gaps in the two species.

Femtochemistry

The topic of femtochemistry is surveyed from both theoretical and experimental points of view. A time-dependent wave packet description of the photodissociation of the O—C—S molecule reveals vibrational motion in the transition-state region and suggests targets for direct experimental observation. Theoretical approaches for treating femtosecond chemical phenomena in condensed phases are featured along with prospects for laser-controlled chemical reactions by using tailored ultrashort chirped pulses. An experimental study of the photoisomerization of retinal in the protein bacteriorhodopsin is discussed with an aim to gain insight into the potential energy surfaces on which this remarkably efficient and selective reactions proceeds. Finally, a prospective view of new frontiers in femtochemistry is given.