Combination Of Velocity Map Imaging Research Articles

Impact of a hydrophobic ion on the early stage of atmospheric aerosol formation

Atmospheric aerosols are one of the major factors affecting planetary climate, and the addition of anthropogenic molecules into the atmosphere is known to strongly affect cloud formation. The broad variety of compounds present in such dilute media and their specific underlying thermalization processes at the nanoscale make a complete quantitative description of atmospheric aerosol formation certainly challenging. In particular, it requires fundamental knowledge about the role of impurities in water cluster growth, a crucial step in the early stage of aerosol and cloud formation. Here, we show how a hydrophobic pyridinium ion within a water cluster drastically changes the thermalization properties, which will in turn change the corresponding propensity for water cluster growth. The combination of velocity map imaging with a recently developed mass spectrometry technique allows the direct measurement of the velocity distribution of the water molecules evaporated from excited clusters. In contrast to previous results on pure water clusters, the low-velocity part of the distributions for pyridinium-doped water clusters is composed of 2 distinct Maxwell-Boltzmann distributions, indicating out-of-equilibrium evaporation. More generally, the evaporation of water molecules from excited clusters is found to be much slower when the cluster is doped with a pyridinium ion. Therefore, the presence of a contaminant molecule in the nascent cluster changes the energy storage and disposal in the early stages of gas-to-particle conversion, thereby leading to an increased rate of formation of water clusters and consequently facilitating homogeneous nucleation at the early stages of atmospheric aerosol formation.

Electronic and vibrational relaxation dynamics of NH3 Rydberg states probed by vacuum-ultraviolet time-resolved photoelectron imaging.

Time-resolved dynamics of high-lying Rydberg states of ammonia (NH3) prepared by using a vacuum ultraviolet (VUV) pump (∼9.3 eV) and an ultraviolet (UV) probe (∼4.7 eV) pulse are reported using photoelectron imaging detection. After photoexcitation, two main features appear in the photoelectron spectrum with vertical binding energies of ∼1.8 eV and ∼3.2 eV and with distinctly different anisotropy parameters β of ∼1.3 and ∼0.7, respectively. This information allows the unambiguous assignment of the respective Rydberg states and disentangles the induced electronic and vibrational dynamics. The combination of velocity-map imaging with femtosecond VUV and UV pulses is shown to offer an attractive approach for studying the dynamics of high-lying Rydberg states of small molecules.

Observation of Rainbows in the Rotationally Inelastic Scattering of NO with CH4

Using a combination of velocity-map imaging and resonance-enhanced multiphoton ionization detection with crossed molecular beam scattering, the dynamics of rotational energy transfer have been examined for NO in collisions with CH4 at a mean collision energy of 700 cm-1. The images of NO scattered into individual rotational (jNO') and spin-orbit (Ω) levels typically exhibit a single broad maximum that gradually shifts from the forward to the backward scattering direction with increasing rotational excitation (i.e., larger ΔjNO). The rotational rainbow angles calculated with a two-dimensional hard ellipse model show reasonable agreement with the observed angles corresponding to the maxima in the differential cross sections extracted from the images for higher ΔjNO transitions, but there are clear discrepancies for lower ΔjNO (in particular, final rotational levels with jNO' = 7.5 and 8.5). The sharply forward scattered angular distributions for these lower ΔjNO transitions better agree with the predictions of an L-type rainbow model. The more highly rotationally excited NO appears to coincide with low rotational excitation of the co-product CH4, indicating a degree of rotational product-pair anticorrelation in this bimolecular scattering.

Photofragmentation dynamics of N,N-dimethylformamide following excitation at 193 nm.

N,N-dimethylformamide, HCON(CH3)2, is a useful model compound for investigating the peptide bond photofragmentation dynamics. We report data from a comprehensive experimental and theoretical study into the photofragmentation dynamics of N,N-dimethylformamide in the gas phase at 193 nm. Through a combination of velocity-map imaging and hydrogen atom Rydberg tagging photofragment translational spectroscopy we have identified two primary fragmentation channels, namely, fission of the N-CO "peptide" bond and N-CH3 bond fission leading to the loss of CH3. The possible fragmentation channels leading to the observed products are rationalised with recourse to CASPT2 calculations of the ground and first few excited-state potential energy curves along the relevant dissociation coordinates, and the results are compared with the data from previous experimental and theoretical studies on the same system.

A velocity map imaging study of the photodissociation of the à state of ammonia

NH3(Ã) photodissociation dynamics has been studied using a combination of velocity map imaging (VMI) and resonance-enhanced multiphoton ionization (REMPI) of the H-atom product. H(+) ion images have been recorded after excitation to the first five NH3 (Ã, ν2' = n) ← (X, ν = 0) vibronic transitions (denoted as 0(0)(0) and 2(0)(n) with n = 1-4). The measured high-resolution H-atom kinetic energy distributions (KED) show a dense set of sharp structures related to rovibrational states of the NH2 co-fragment. A careful simulation of the KEDs in terms of the known internal energies of the NH2 fragment has allowed the extraction of the non-adiabatic NH2(X) rovibrational populations for the 0(0)(0), 2(0)(1) and 2(0)(2) transitions, which are in good agreement with previous measurements. For the 2(0)(3) and 2(0)(4) transitions, some features of the KED have been assigned to rovibrational states of NH2(Ã) fragments produced adiabatically. In particular, the sharp feature distinctively observed at very low kinetic energies in the H-atom KED for the 2(0)(4) transition has been undoubtedly assigned to H atoms produced in correlation with rotationally excited NH2 fragments in the à electronic state. For these two transitions, the analysis of the KEDs has allowed the determination of the NH2(X, Ã) rovibrational populations and precise electronic branching ratios, Φ* = [NH2(Ã)]/([NH2(X)] + [NH2(Ã)]). A speed-dependent anisotropy analysis of the H-atom images has been made for all transitions, which provides a picture of the partitioning of the available energy among the NH2 co-product internal modes - including the electronic branching ratios - in terms of a roaming-like mechanism.

UV photolysis of 4-iodo-, 4-bromo-, and 4-chlorophenol: Competition between C–Y (Y = halogen) and O–H bond fission

The wavelength dependences of C-Y and O-H bond fission following ultraviolet photoexcitation of 4-halophenols (4-YPhOH) have been investigated using a combination of velocity map imaging, H Rydberg atom photofragment translational spectroscopy, and high level spin-orbit resolved electronic structure calculations, revealing a systematic evolution in fragmentation behaviour across the series Y = I, Br, Cl (and F). All undergo O-H bond fission following excitation at wavelengths λ ≲ 240 nm, on repulsive ((n∕π)σ∗) potential energy surfaces (PESs), yielding fast H atoms with mean kinetic energies ∼11,000 cm(-1). For Y = I and Br, this process occurs in competition with prompt C-I and C-Br bond cleavage on another (n∕π)σ∗ PES, but no Cl∕Cl∗ products unambiguously attributable to one photon induced C-Cl bond fission are observed from 4-ClPhOH. Differences in fragmentation behaviour at longer excitation wavelengths are more marked. Prompt C-I bond fission is observed following excitation of 4-IPhOH at all λ ≤ 330 nm; the wavelength dependent trends in I∕I∗ product branching ratio, kinetic energy release, and recoil anisotropy suggest that (with regard to C-I bond fission) 4-IPhOH behaves like a mildly perturbed iodobenzene. Br atoms are observed when exciting 4-BrPhOH at long wavelengths also, but their velocity distributions suggest that dissociation occurs after internal conversion to the ground state. O-H bond fission, by tunnelling (as in phenol), is observed only in the cases of 4-FPhOH and, more weakly, 4-ClPhOH. These observed differences in behaviour can be understood given due recognition of (i) the differences in the vertical excitation energies of the C-Y centred (n∕π)σ∗ potentials across the series Y = I < Br < Cl and the concomitant reduction in C-Y bond strength, cf. that of the rival O-H bond, and (ii) the much increased spin-orbit coupling in, particularly, 4-IPhOH. The present results provide (another) reminder of the risks inherent in extrapolating photochemical behaviour measured for one molecule at one wavelength to other (related) molecules and to other excitation energies.

Photodissociation of pyrrole-ammonia clusters below 218 nm: Quenching of statistical decomposition pathways under clustering conditions

The excited state hydrogen transfer (ESHT) reaction in pyrrole-ammonia clusters (PyH·(NH(3))(n), n = 2-5) at excitation wavelengths below 218 nm down to 199 nm, has been studied using a combination of velocity map imaging and non-resonant detection of the NH(4)(NH(3))(n-1) products. Special care has been taken to avoid evaporation of solvent molecules from the excited clusters by controlling the intensity of both the excitation and probing lasers. The high resolution translational energy distributions obtained are analyzed on the base of an impulsive mechanism for the hydrogen transfer, which mimics the direct N-H bond dissociation of the bare pyrrole. In spite of the low dissociation wavelengths attained (~200 nm) no evidence of hydrogen-loss statistical dynamics has been observed. The effects of clustering of pyrrole with ammonia molecules on the possible statistical decomposition channels of the bare pyrrole are discussed.

Photodissociation of pyrrole–ammonia clusters by velocity map imaging: mechanism for the H-atom transfer reaction

The photodissociation dynamics of pyrrole-ammonia clusters (PyH·(NH(3))(n), n = 2-6) has been studied using a combination of velocity map imaging and non-resonant detection of the NH(4)(NH(3))(n-1) products. The excited state hydrogen-atom transfer mechanism (ESHT) is evidenced through delayed ionization and presents a threshold around 236.6 nm, in agreement with previous reports. A high resolution determination of the kinetic energy distributions (KEDs) of the products reveals slow (∼0.15 eV) and structured distributions for all the ammonia cluster masses studied. The low values of the measured kinetic energy rule out the existence of a long-lived intermediate state, as it has been proposed previously. Instead, a direct N-H bond rupture, in the fashion of the photodissociation of bare pyrrole, is proposed. This assumption is supported by a careful analysis of the structure of the measured KEDs in terms of a discrete vibrational activity of the pyrrolyl co-fragment.

Surface three-dimensional velocity map imaging: A new technique for the study of photodesorption dynamics

The authors describe the application of a combination of velocity map imaging and time-of-flight (TOF) techniques to obtain three-dimensional velocity distributions for surface photodesorption. They have established a systematic alignment procedure to achieve correct and reproducible experimental conditions. It includes four steps: (1) optimization of the velocity map imaging ion optics’ voltages to achieve optimum velocity map imaging conditions; (2) alignment of the surface normal with the symmetry axis (ion flight axis) of the ion optics; (3) determination of TOF distance between the surface and the ionizing laser beam; (4) alignment of the position of the ionizing laser beam with respect to the ion optics. They applied this set of alignment procedures and then measured Br(P23/2) (Br) and Br(P21/2) (Br∗) atoms photodesorbing from a single crystal of KBr after exposure to 193 nm light. They analyzed the velocity flux and energy flux distributions for motion normal to the surface. The Br∗ normal energy distribution shows two clearly resolved peaks at approximately 0.017 and 0.39 eV, respectively. The former is slightly faster than expected for thermal desorption at the surface temperature and the latter is hyperthermal. The Br normal energy distribution shows a single broad peak that is likely composed of two hyperthermal components. The capability that surface three-dimensional velocity map imaging provides for measuring state-specific velocity distributions in all three dimensions separately and simultaneously for the products of surface photodesorption or surface reactions holds great promise to contribute to our understanding of these processes.

Photofragment alignment in the photodissociation of I2 from 450to510nm

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.

Velocity map imaging and REMPI study of the photodissociation of CH 3SCH 3 from the first absorption band

The photodissociation of dimethyl sulfide (CH 3SCH 3) at 229 nm has been studied employing a combination of velocity map imaging and time-of-flight resonance-enhanced multiphoton ionization techniques to detect the CH 3 products. Translational energy and recoil angle distributions as well as rotational state populations have been determined for the CH 3 photofragments formed in the ground vibrational state. The electronic excitation of CH 3SCH 3 to the first absorption band is found to produce fast CH 3S+CH 3 ( v=0) recoiling products with a negative spatial anisotropy parameter of β=−0.85±0.05. The CH 3 ( v=0) products are rotationally cold, the rotational distribution peaking at N′′=3–4.