Absolute fluorescence and absorption measurements over a dynamic range of 106 with cavity-enhanced laser-induced fluorescence.

We present a novel spectroscopic technique that exhibits high sensitivity and a large dynamic range for the measurement of absolute absorption coefficients. We perform a simultaneous and correlated laser-induced fluorescence and cavity ring-down measurement of the same sample in a single pulsed laser beam. The combined measurement offers a large dynamic range and a lower limit of detection than either technique on its own. The methodology, dubbed cavity-enhanced laser-induced fluorescence, is developed and rigorously tested against the electronic spectroscopy of 1,4-bis(phenylethynyl)benzene in a molecular beam and density measurements in a cell. We outline how the method can be used to determine absolute quantities, such as sample densities, absorption cross sections, and fluorescence quantum yields, particularly in spatially confined samples.

Vibrational excitation through tug-of-war inelastic collisions.

Vibrationally inelastic scattering is a fundamental collision process that converts some of the kinetic energy of the colliding partners into vibrational excitation(,). The conventional wisdom is that collisions with high impact parameters (where the partners only 'graze' each other) are forward scattered and essentially elastic, whereas collisions with low impact parameters transfer a large amount of energy into vibrations and are mainly back scattered. Here we report experimental observations of exactly the opposite behaviour for the simplest and most studied of all neutral-neutral collisions: we find that the inelastic scattering process H + D(2)(v = 0, j = 0, 2) --> H + D(2)(v' = 3, j' = 0, 2, 4, 6, 8) leads dominantly to forward scattering (v and j respectively refer to the vibrational and rotational quantum numbers of the D(2) molecule). Quasi-classical trajectory calculations show that the vibrational excitation is caused by extension, not compression, of the D-D bond through interaction with the passing H atom. However, the H-D interaction never becomes strong enough for capture of the H atom before it departs with diminished kinetic energy; that is, the inelastic scattering process is essentially a frustrated reaction in which the collision typically excites the outward-going half of the H-D-D symmetric stretch before the H-D(2) complex dissociates. We suggest that this 'tug of war' between H and D(2) is a new mechanism for vibrational excitation that should play a role in all neutral-neutral collisions where strong attraction can develop between the collision partners.

Absolute density measurement of SD radicals in a supersonic jet at the quantum-noise-limit.

The absolute density of SD radicals in a supersonic jet has been measured down to (1.1 ± 0.1) × 10(5) cm(-3) in a modestly specified apparatus that uses a cross-correlated combination of cavity ring-down and laser-induced fluorescence detection. Such a density corresponds to 215 ± 21 molecules in the probe volume at any given time. The minimum detectable absorption coefficient was quantum-noise-limited and measured to be (7.9 ± 0.6) × 10(-11) cm(-1), in 200 s of acquisition time, corresponding to a noise-equivalent absorption sensitivity for the apparatus of (1.6 ± 0.1) × 10(-9) cm(-1) Hz(-1/2).

A quasiclassical trajectory study of the time-delayed forward scattering in the hydrogen exchange reaction.

The time-delayed forward scattering mechanism recently identified by Althorpe et al. [Nature (London) 416, 67 (2002)] for the H+D(2)(v=0,j=0)-->HD(v(')=3,j(')=0)+D reaction was analyzed by using quasiclassical trajectory (QCT) methodology. The QCT results were found to match the quantum wavepacket snapshots of Althorpe et al., albeit without the quantum scattering effects. Trajectories were analyzed on the fly to investigate the dynamics of the atoms during the reaction. The dominant reaction mechanism progresses from hard collinear impacts, leading to direct recoil, toward glancing impacts. The increased time required for forward scattered trajectories is due to the rotation of the transient HDD complex. Forward scattered trajectories display symmetric stretch vibrations of the transient HDD complex, a signature of the presence of a resonance, or a quantum bottleneck state.

New, unexpected, and dominant mechanisms in the hydrogen exchange reaction.

A quasiclassical trajectory study of the state specific H+D(2)(upsilon = 0,j = 0) --> HD(upsilon' = 0,j' = 0) + D reaction at a collision energy of 1.85 eV (total energy of 2.04 eV) found that the scattering is governed by two unexpected and dominant new mechanisms, and not by direct recoil as is generally assumed. The new mechanisms involve strong interaction with the sloping potential around the conical intersection, an area of the potential energy surface not previously considered to have much effect upon reactive scattering. Initial investigations indicate that more than 50% of reactive scattering could be the result of these new mechanisms at this collision energy. Features in the corresponding quantum mechanical results can be attributed to these new (classical) reaction mechanisms.

On the dynamics of the H+ +D2(v=0,j=0)-->HD+D + reaction: a comparison between theory and experiment.

The H+ +D2(v=0,j=0)-->HD+D + reaction has been theoretically investigated by means of a time independent exact quantum mechanical approach, a quantum wave packet calculation within an adiabatic centrifugal sudden approximation, a statistical quantum model, and a quasiclassical trajectory calculation. Besides reaction probabilities as a function of collision energy at different values of the total angular momentum, J, special emphasis has been made at two specific collision energies, 0.1 and 0.524 eV. The occurrence of distinctive dynamical behavior at these two energies is analyzed in some detail. An extensive comparison with previous experimental measurements on the Rydberg H atom with D2 molecules has been carried out at the higher collision energy. In particular, the present theoretical results have been employed to perform simulations of the experimental kinetic energy spectra.

Facile photoinduced charge separation through a cyanoacetylide bridge in a heterobimetallic Fe(II)-Re(I) complex.

Photoinduced Fe-to-bpy charge transfer in [{Cp(dppe)Fe}(mu-C[triple bond]CC[triple bond]N){Re(CO)(3)(bpy)}]PF(6) has been observed by ps-TRIR spectroscopy, supported by UV-Vis/IR spectroelectrochemistry and DFT calculations.

Effect of the geometric phase on the dynamics of the hydrogen-exchange reaction.

A recent puzzle in nonadiabatic quantum dynamics is that geometric phase (GP) effects are present in the state-to-state opacity functions of the hydrogen-exchange reaction, but cancel out in the state-to-state integral cross sections (ICSs). Here the authors explain this result by using topology to separate the scattering amplitudes into contributions from Feynman paths that loop in opposite senses around the conical intersection. The clockwise-looping paths pass over one transition state (1-TS) and scatter into positive deflection angles; the counterclockwise-looping paths pass over two transition states (2-TS) and scatter into negative deflection angles. The interference between the 1-TS and 2-TS paths thus integrates to a very small value, which cancels the GP effects in the ICS. Quasiclassical trajectory (QCT) calculations reproduce the scattering of the 1-TS and 2-TS paths into positive and negative deflection angles and show that the 2-TS paths describe a direct insertion mechanism. The inserting atom follows a highly constrained "S-bend" path, which allows it to avoid both the other atoms and the conical intersection and forces the product diatom to scatter into high rotational states. By contrast, the quantum 2-TS paths scatter into a mainly statistical distribution of rotational states, so that the quantum 2-TS total ICS is roughly twice the QCT ICS at 2.3 eV total energy. This suggests that the S-bend constraint is relaxed by tunneling in the quantum system. These findings on H+H(2) suggest that similar cancellations or reductions in GP effects are likely in many other reactions.

Cavity ring-down spectroscopy of the torsional motions of 1,4-bis(phenylethynyl)benzene.

The torsional motions of jet-cooled 1,4-bis(phenylethynyl)benzene (BPEB), a prototype molecular wire, were studied using cavity ring-down spectroscopy in the first UV absorption band (316-321 nm). The torsional spectrum of 1,4-bis(phenylethynyl)-2,3,5,6-tetradeuteriobenzene was also recorded in the gas phase. Both spectra were successfully simulated using simple cosine potentials to describe the torsional motions. The ground-state barrier to rotation was estimated to be 220-235 cm(-1), which is similar to that of diphenylacetylene (tolane). Complementary DFT calculations were found to overestimate the torsional barrier.

Theoretical study of geometric phase effects in the hydrogen-exchange reaction.

The crossing of two electronic potential surfaces (a conical intersection) should result in geometric phase effects even for molecular processes confined to the lower surface. However, recent quantum simulations of the hydrogen exchange reaction (H + H2 --> H2 + H) have predicted a cancellation in such effects when product distributions are integrated over all scattering angles. We used a simple topological argument to extract reaction paths with different senses from a nuclear wave function that encircles a conical intersection. In the hydrogen-exchange reaction, these senses correspond to paths that cross one or two transition states. These two sets of paths scatter their products into different regions of space, which causes the cancellation in geometric phase effects. The analysis should generalize to other direct reactions.

Reactive scattering of rydberg atoms: H* + D2 --> HD + D*.

The scattering of highly excited hydrogen Rydberg atoms, H* (n = 36), with deuterium molecules in their rovibrational ground state, D2(v = 0, j = 0), has been investigated at a relative collision energy of 0.53 eV. Time-of-flight distributions of elastically/inelastically scattered H* Rydberg atoms and reactively scattered D* Rydberg atoms have been measured at different laboratory angles. The extracted rovibrationally resolved state distributions of the HD product molecules from reactive collisions resemble closely those reported for the corresponding ion-molecule reaction, H+ + D2 --> HD + D+. This similarity is rationalised using the free electron model which predicts that the Rydberg electron acts as a spectator while the ionic reaction takes place.

Observation and interpretation of a time-delayed mechanism in the hydrogen exchange reaction.

Extensive theoretical and experimental studies have shown the hydrogen exchange reaction H+H2 --> H2+H to occur predominantly through a 'direct recoil' mechanism: the H--H bonds break and form concertedly while the system passes straight over a collinear transition state, with recoil from the collision causing the H2 product molecules to scatter backward. Theoretical predictions agree well with experimental observations of this scattering process. Indirect exchange mechanisms involving H3 intermediates have been suggested to occur as well, but these are difficult to test because bimolecular reactions cannot be studied by the femtosecond spectroscopies used to monitor unimolecular reactions. Moreover, full quantum simulations of the time evolution of bimolecular reactions have not been performed. For the isotopic variant of the hydrogen exchange reaction, H+D2 --> HD+D, forward scattering features observed in the product angular distribution have been attributed to possible scattering resonances associated with a quasibound collision complex. Here we extend these measurements to a wide range of collision energies and interpret the results using a full time-dependent quantum simulation of the reaction, thus showing that two different reaction mechanisms modulate the measured product angular distribution features. One of the mechanisms is direct and leads to backward scattering, the other is indirect and leads to forward scattering after a delay of about 25 femtoseconds.