Two- and three-body photodissociation dynamics of diiodobromide (I2Br-) anion

The photodissociation of gas-phase I(2)Br(-) was investigated using fast beam photofragment translational spectroscopy. Anions were photodissociated from 300 to 270 nm (4.13-4.59 eV) and the recoiling photofragments were detected in coincidence by a time- and position-sensitive detector. Both two- and three-body channels were observed throughout the energy range probed. Analysis of the two-body dissociation showed evidence for four distinct channels: Br(-) + I(2), I(-) + IBr, Br+I(2) (-), and I + IBr(-). In three-body dissociation, Br((2)P(3∕2)) + I((2)P(3∕2)) + I(-) and Br(-) + I((2)P(3∕2)) + I((2)P(3∕2)) were produced primarily from a concerted decay mechanism. A sequential decay mechanism was also observed and attributed to Br(-)((1)S)+I(2)(B(3)Π(0u) (+)) followed by predissociation of I(2)(B).     

Near threshold channel selective photodissociation of NO2

The dynamics of the photodissociation of NO₂ into NO(X ²Π_Ω″, ν″=0,J″)+O(³ P _0,1,2) is investigated near the thermodynamic threshold. Cooling the internal degrees of freedom by a supersonic beam expansion provides a nearly complete quantum state selection prior to the predissociation. Measurements of the wavelength dependent dissociation yield into specific product quantum states are reported. At certain wavelengths Λ″ doublet resolved rotational population distributions of the fragments are obtained. Up to an excess energy ofE _exc=121 cm^?1 about 42% of this energy is partitioned into the rotation of the NO molecules, and correspondingly 58% into the translational degree of freedom. The role of electronic and total parity is discussed.     

The ultraviolet photodissociation of CS2: the S(1D2) channel

The photodissociation of CS(2) has been investigated using velocity-map ion imaging of the S((1)D(2)) atomic photofragments following excitation at 193 nm and at longer wavelengths close to the S((1)D(2)) channel threshold. The experiments probe regions both above and below the energetic barrier to linearity on the (1)Σ(u) (+)((1)B(2)) potential energy surface. The imaging data in both regions indicate that the electronic angular momentum of the S((1)D(2)) atom products is unpolarized, but also reveal different dissociation dynamics in the two regions. Excitation above the barrier to linearity yields an inverted CS((1)Σ(+)) vibrational population distribution, whereas the long-wavelength state-to-state results following excitation below the barrier reveal CS((1)Σ(+))(v, J) coproduct state distributions which are consistent with a statistical partitioning of the energy. Below the barrier, photofragment excitation spectra point to an enhancement of the singlet channel for K = 1, relative to K = 0, where K is the projection of the angular momentum along the principal axis, in agreement with previous work. However, the CS cofragment product state distributions are found to be insensitive to K. It is proposed that dissociation below the barrier to linearity occurs primarily on a surface with a significant potential energy well and without an exit channel barrier, such as that for the ground electronic state. However, oscillatory structure is also observed in the kinetic energy release distributions, which is shown to be consistent with a mapping of parent molecule bending motion. This could indicate the operation of competing direct and indirect dissociation mechanisms below the barrier to linearity.     

Time-resolved imaging of the reaction coordinate

Time-resolved photoelectron imaging of negative ions is employed to study the dynamics along the reaction coordinate in the photodissociation of IBr(-). The results are discussed in a side-by-side comparison with the dissociation of I(2) (-), examined under similar experimental conditions. The I(2) (-) anion, extensively studied in the past, is used as a reference system for interpreting the IBr(-) results. The data provide rigorous dynamical tests of the anion electronic potentials. The evolution of the energetics revealed in the time-resolved (780 nm pump, 390 nm probe) I(2) (-) and IBr(-) photoelectron images is compared to the predictions of classical trajectory calculations, with the time-resolved photoelectron spectra modeled assuming a variety of neutral states accessed in the photodetachment. In light of good overall agreement of the experimental data with the theoretical predictions, the results are used to construct an experimental image of the IBr(-) dissociation potential as a function of the reaction coordinate.     

Photofragment alignment in the photodissociation of I2 from 450 to 510 nm

A combination of velocity map imaging and slicing techniques have been used to measure the product recoil anisotropy and angular momentum polarization for the photodissociation process I2-->I(2P(3/2))+I(2P(3/2)) and I2-->I(2P(3/2)))+I(2P(1/2)) in the 450-510 nm laser wavelength region using linearly polarized photolysis and probe laser light. The former channel is produced predominantly via perpendicular excitation to the 1Piu state, and the latter is predominantly parallel, via the B 3Pi(0u)+ state. In both cases we observe mostly adiabatic dissociation, which produces electronically aligned iodine atoms in the mid /m/=1/2 states with respect to the recoil direction.     

Time-resolved flow-flash FT-IR difference spectroscopy: the kinetics of CO photodissociation from myoglobin revisited

Fourier-transform infrared (FT-IR) difference spectroscopy has been proven to be a significant tool in biospectroscopy. In particular, the step-scan technique monitors structural and electronic changes at time resolutions down to a few nanoseconds retaining the multiplex advantage of FT-IR. For the elucidation of the functional mechanisms of proteins, this technique is currently limited to repetitive systems undergoing a rapid photocycle. To overcome this obstacle, we developed a flow-flash experiment in a miniaturised flow channel which was integrated into a step-scan FT-IR spectroscopic setup. As a proof of principle, we studied the rebinding reaction of CO to myoglobin after photodissociation. The use of microfluidics reduced the sample consumption drastically such that a typical step-scan experiment takes only a few 10 ml of a millimolar sample solution, making this method particularly interesting for the investigation of biological samples that are only available in small quantities. Moreover, the flow cell provides the unique opportunity to assess the reaction mechanism of proteins that cycle slowly or react irreversibly. We infer that this novel approach will help in the elucidation of molecular reactions as complex as those of vectorial ion transfer in membrane proteins. The potential application to the oxygen splitting reaction of cytochrome c oxidase is discussed. An erratum to this article can be found at     

Time-resolved photoion and photoelectron imaging of NO(2)

Time-resolved photoion and photoelectron velocity mapped images from NO(2) excited close to its first dissociation limit [to NO(X(2)Pi) + O((3)P(2))] have been recorded in a two colour pump-probe experiment, using the frequency-doubled and frequency-tripled output of a regeneratively amplified titanium-sapphire laser. At least three processes are responsible for the observed transient signals; a negative pump-probe signal (corresponding to a 266 nm pump), a very short-lived transient close to the cross-correlation of the pump and probe pulses but on the 400 nm pump side, and a longer-lived positive pump-probe signal that exhibits a signature of wavepacket motion (oscillations). These transients have two main origins; multiphoton excitation of the Rydberg states of NO(2) by both 266 and 400 nm light, and electronic relaxation in the 1(2)B(2) state of NO(2), which leads to a quasi-dissociated NO(2) high in the 1(2)A(1) electronic ground state and just below the dissociation threshold. The wavepacket motion that we observe is ascribed to states exhibiting free rotation of the O atom about the NO moiety. These states, which are common for loosely bound systems such as a van der Waals complex but unusual for a chemically-bound molecule, have previously been observed in the frequency domain by optical double resonance spectroscopy but never before in the time domain.     

Velocity-map imaging study of the photodissociation of acetaldehyde

Velocity-map imaging studies are reported for the photodissociation of acetaldehyde over a range of photolysis wavelengths (317.5-282.5 nm). Images are obtained for both the HCO and CH3 fragments. The mean rotational energy of both fragments increases with photodissociation energy, with a lesser degree of excitation in the CH3 fragment. The CH3 images demonstrate that the CH3 fragments are rotationally aligned with respect to the recoil direction and this is interpreted, and well modeled, on the basis of a propensity for forming CH3 fragments with M approximately K, where M is the projection of the rotational angular momentum along the recoil direction. The origin of the CH3 rotation is conserved motion from the torsional and methyl-rocking modes of the parent molecule. Nonstatistical vibrational distributions for the CH3 fragment are obtained at higher energies.     

Slice imaging of nitric acid photodissociation: The O(1D) + HONO channel

We report an imaging study of nitric acid (HNO(3)) photodissociation near 204 nm with detection of O((1)D), one of the major decomposition products in this region. The images show structure reflecting the vibrational distribution of the HONO coproduct and significant angular anisotropy that varies with recoil speed. The images also show substantial alignment of the O((1)D) orbital, which is analyzed using an approximate treatment that reveals that the polarization is dominated by incoherent, high order contributions. The results offer additional insight into the dynamics of the dissociation of nitric acid through the S(3) (2 (1)A(')) excited state, resolving an inconsistency in previously reported angular distributions, and pointing the way to future studies of the angular momentum polarization.     

Femtosecond multichannel photodissociation dynamics of CH3I from the A band by velocity map imaging

The reaction times of several well-defined channels of the C-I bond rupture of methyl iodide from the A band, which involves nonadiabatic dynamics yielding ground state I(2P3/2) and spin-orbit excited I*(2P1/2) and ground and vibrationally excited CH3 fragments, have been measured by a combination of a femtosecond laser pump-probe scheme and velocity map imaging techniques using resonant detection of ground state CH3 fragments. The reaction times found for the different channels studied are directly related with the nonadiabatic nature of this multidimensional photodissociation reaction.     

Time-resolved photoelectron imaging of the chloranil radical anion: ultrafast relaxation of electronically excited electron acceptor states

The spectroscopy and dynamics of near-threshold excited states of the isolated chloranil radical anion are investigated using photoelectron imaging. The photoelectron images taken at 480 nm clearly indicate resonance-enhanced photodetachment via a bound electronic excited state. Time-resolved photoelectron imaging reveals that the excited state rapidly decays on a timescale of 130 fs via internal conversion. The ultrafast relaxation dynamics of excited states near threshold are pertinent to common electron acceptor molecules based on the quinone moiety and may serve as doorway states that enable efficient electron transfer in the highly exergonic inverted regime, despite the presence of large free energy barriers.     

Time-resolved fluorescence microscopy for quantitative Ca2+ imaging in living cells

Calcium (Ca²⁺) is a ubiquitous intracellular second messenger and involved in a plethora of cellular processes. Thus, quantification of the intracellular Ca²⁺ concentration ([Ca²⁺]_i) and of its dynamics is required for a comprehensive understanding of physiological processes and potential dysfunctions. A powerful approach for studying [Ca²⁺]_i is the use of fluorescent Ca²⁺ indicators. In addition to the fluorescence intensity as a common recording parameter, the fluorescence lifetime imaging microscopy (FLIM) technique provides access to the fluorescence decay time of the indicator dye. The nanosecond lifetime is mostly independent of variations in dye concentration, allowing more reliable quantification of ion concentrations in biological preparations. In this study, the feasibility of the fluorescent Ca²⁺ indicator Oregon Green Bapta-1 (OGB-1) for two-photon fluorescence lifetime imaging microscopy (2P-FLIM) was evaluated. In aqueous solution, OGB-1 displayed a Ca²⁺-dependent biexponential fluorescence decay behaviour, indicating the presence of a Ca²⁺-free and Ca²⁺-bound dye form. After sufficient dye loading into living cells, an in situ calibration procedure has also unravelled the Ca²⁺-free and Ca²⁺-bound dye forms from a global biexponential fluorescence decay analysis, although the dye's Ca²⁺ sensitivity is reduced. Nevertheless, quantitative [Ca²⁺]_i recordings and its stimulus-induced changes in salivary gland cells could be performed successfully. These results suggest that OGB-1 is suitable for 2P-FLIM measurements, which can gain access to cellular physiology.

State-selected imaging of HCCO radical photodissociation dynamics

We present a dc sliced ion imaging study of HCCO radical photodissociation to CH and CO at 230 nm. The measurements were made using a two-color reduced Doppler probe strategy. The CO rotational distribution was consistent with a Boltzmann distribution at 3500 K. Using the dc slice ion imaging approach, we obtained CO images for various rotational levels of CO (v=0). The results are largely consistent with earlier work, albeit with a significant 0.9 eV peak seen previously in the translational energy distributions absent in our state-selected imaging study.     

Spectroscopic observation of vibrational Feshbach resonances in near-threshold photoexcitation of X-.CH3NO2 (X- = I- and Br-)

We report the observation of resonance structure in the absorption and X-/NO2- photofragment action spectra of the X-.CH3NO2 (X- = I- and Br-) complexes in the region above the electron detachment threshold. The resonance structure corresponds to peaks which appear at the onsets for vibrational excitation of the -NO2 wag, scissors, and stretch modes of neutral CH3NO2, the modes which most strongly distort upon electron capture into its pi* lowest unoccupied molecular orbital. We attribute the peaks to excitation of vibrational Feshbach resonances of the CH3NO2- transient negative ion, where near-threshold excitation of X-.CH3NO2 spectroscopically accesses states of the free electron-CH3NO2 system.     

Time-resolved observation of product ions generated by 157 nm photodissociation of singly protonated phosphopeptides

Vacuum UV photodissociation tandem mass spectra of singly charged arginine-terminated phosphopeptides were recorded at times ranging from 300 ns to ms after photoexcitation, to investigate when the phosphate group falls off from the precursor and product ions and whether loss of phosphate can be eliminated in tandem mass spectra. For peptide ions containing phosphoserine and phosphothreonine, little loss of 98 Da from the product ions was observed up to 1 μs after photoexcitation. However, neutral losses from the precursor ions were considerable just 300 ns after photoactivation. Loss of 98 Da from product ions first appears about 1 μs after laser irradiation and becomes more common 13 μs after photoexcitation. Consistent with previous reports, phosphotyrosine was more stable than either phosphoserine or phosphothreonine.     

A photodissociation study of CH2BrCl in the A-band using the time-sliced ion velocity imaging method

Employing a high-resolution (velocity resolution deltanu/nu<1.5%) time-sliced ion velocity imaging apparatus, we have examined the photodissociation of CH2BrCl in the photon energy range of 448.6-618.5 kJ/mol (193.3-266.6 nm). Precise translational and angular distributions for the dominant Br(2P32) and Br(2P12) channels have been determined from the ion images observed for Br(2P32) and Br(2P12). In confirmation with the previous studies, the kinetic-energy distributions for the Br(2P12) channel are found to fit well with one Gaussian function, whereas the kinetic- energy distributions for the Br(2P32) channel exhibit bimodal structures and can be decomposed into a slow and a fast Gaussian component. The observed kinetic-energy distributions are consistent with the conclusion that the formation of the Br(2P32) and Br(2P12) channels takes place on a repulsive potential-energy surface, resulting in a significant fraction (0.40-0.47) of available energy to appear as translational energy for the photo fragments. On the basis of the detailed kinetic-energy distributions and anisotropy parameters obtained in the present study, together with the specific features and relative absorption cross sections of the excited 2A', 1A", 3A', 4A', and 2A" states estimated in previous studies, we have rationalized the dissociation pathways of CH2BrCl in the A-band, leading to the formation of the Br(2P32) and Br(2P12) channels. The analysis of the ion images observed at 235 nm for Cl(2P(32,12)) provides strong evidence that the formation of Cl mainly arises from the secondary photodissociation process CH2Cl + hnu --> CH2 + Cl.     

Change in Volume Properties of and Complex Formation in the System Hg(NO3)2-KX-H2O (X- = Cl-, Br-, I-)

The chemical nature of the anions in step complex formation in Hg(NO₃)₂-KX-H₂O systems (X^- = Cl^-, Br^-, I^-) manifests itself in different trends in variation of the molar volumes of the solutions.     

Time-resolved spectroscopy at the picosecond laser-triggered electron accelerator ELYSE

ELYSE is a fast kinetics center created for pulse radiolysis with picosecond time-resolution. The facility is a 4–9 MeV electron accelerator using a subpicosecond laser pulse to produce an electron pulse from a Cs₂Te semiconductor photocathode and RF gun technology for the electron acceleration. The pulse duration is around 5 ps at low charge (<2 nC) and high energy (9 MeV), and is under routine conditions 10 ps at higher charge (5 nC) and >8 MeV. The dark current at the target is less than 1% of the pulse photocurrent.Time-resolved absorbance measurements in cells placed in front of the electron beam are achieved using pulsed laser diodes, or a xenon flash lamp as light sources, and photodiodes connected to a 3 GHz transient digitizer or a streak camera (250–800 nm range and 3.7 ps time resolution) as detection instruments. In addition, the synchronization between the laser beam and the electron beam is exploited to measure the absorbance by a pump-probe set-up, the pump being the electron pulse produced by the laser pulse, and the probe being part of the laser beam (120 fs–3 ps) delayed by a variable optical line.