Biomedical subjects

Arthur G Suits

Publications and source records attributed to Arthur G Suits.

14 recordsLinked to original sources

PubMed2006

S(1D2) atomic orbital polarization in the photodissociation of OCS at 193 nm: Construction of the complete density matrix.

The absolute velocity-dependent alignment and orientation for S(1D2) atoms from the photodissociation of OCS at 193 nm were measured using the dc slice imaging method. Three main peaks ascribed to specific groups of high rotational levels of CO in the vibrational ground state were found, with rotationally resolved rings in a fourth slow region ascribed to weak signals associated with excited vibrational states of CO. The observed speed-dependent beta and polarization parameters support the interpretation that there are two main dissociation processes: a simultaneous two-surface (A' and A") excitation and the initial single-surface (A') excitation followed by the nonadiabatic crossing to ground state. At 193 nm photodissociation, the nonadiabatic dissociation process is strongly enhanced relative to longer wavelengths. The angle- and speed-dependent S(1D2) density matrix can be constructed including the higher order (K = 3,4) contributions for the circularly polarized dissociation light. This was explicitly done for selected energies and angles. It was found in one case that the density matrix is sensitively affected by the rank 4 terms, suggesting that the higher order contributions should not be overlooked for an accurate picture of the dissociation dynamics in this system.

Journal Article↗

PubMed2006

Rotationally resolved reactive scattering: imaging detailed Cl+C2H6 reaction dynamics.

The hydrogen atom abstraction reaction of Cl (2P3/2) with ethane has been studied using the crossed molecular beam technique with dc slice imaging at collision energies from 3.2 to 10.4 kcal/mol. The products HCl (v,J) (v = 0, J = 0-5) were state-selectively detected using 2+1 resonance enhanced multiphoton ionization. The images were used to obtain the center-of-mass frame product angular distributions and translational energy release distributions. Two general features were found in all probed HCl quantum states at 6.7 kcal/mol collision energy, and these features have distinct translational energy release and angular distributions, as described for HCl (v = 0, J = 2) in a recent preliminary report [Li et al., J. Chem. Phys. 124, 011102 (2006)]. The results for HCl (v = 0, J = 2) at four collision energies were also compared to investigate the energy-dependent dynamics. We discuss the reaction in terms of a variety of models of polyatomic reaction dynamics. The dynamics of this well studied system are more complicated than can be accounted for by a single mechanism, and the results call for further theoretical and experimental investigations.

Journal Article↗

PubMed2006

Two-color reduced-Doppler ion imaging.

We demonstrate a two-color reduced-Doppler probe for ion imaging that, in many applications, offers advantages over conventional 2+1 resonance-enhanced multiphoton ionization detection. Using counterpropagating beams of two different colors, one of which is broadband 266 nm, we achieve convenient and sensitive D atom detection without the need for Doppler scanning. We demonstrate the approach using 224 nm photodissociation of DBr. This method improves the sensitivity and signal-to-noise ratio and presents advantages and opportunities for use in the other systems.

Journal Article↗

PubMed2006

Doppler-free/Doppler-sliced ion imaging.

We demonstrate a hybrid Doppler-free/Doppler-sliced ion imaging approach that is well-suited for detection of H or D atoms. The method relies on 2 + 1 resonant ionization with identical, nearly counterpropagating beams that are coplanar but directed at a small angle relative to the detector face. This results in Doppler selection of the velocity component along the time of flight axis but Doppler-free detection in the plane perpendicular to this axis. The results show high signal level and excellent slicing ( approximately 5%), yielding velocity resolution completely determined by cation recoil in the ionization step.

Doppler Effect↗

PubMed2006

Correlated v(H(2) ) and j(CO) product states from formaldehyde photodissociation: dynamics of molecular elimination.

A detailed study of the photoinduced molecular elimination pathway of formaldehyde on the ground state surface was carried out using high-resolution dc slice ion imaging. Detailed correlated H(2) rovibrational and CO rotational product quantum state distributions were measured by imaging spectroscopically selected CO velocity distributions following photodissociation at energies from approximately 1800 to approximately 4100 cm(-1) above the barrier to molecular elimination. Excitation to the 2(1)4(1), 2(1)4(3), 2(2)4(1), 2(2)4(3), and 2(3)4(1) bands of H(2)CO are reported here. The dependence of the product rovibrational distributions on excitation energy are discussed in light of a dynamical model which has been formulated to describe the strong product state correlations observed.

Journal Article↗

PubMed2006

The roaming atom pathway in formaldehyde decomposition.

We present a detailed experimental and theoretical investigation of formaldehyde photodissociation to H(2) and CO following excitation to the 2(1)4(1) and 2(1)4(3) transitions in S(1). The CO velocity distributions were obtained using dc slice imaging of single CO rotational states (v=0, j(CO)=5-45). These high-resolution measurements reveal the correlated internal state distribution in the H(2) cofragments. The results show that rotationally hot CO (j(CO) approximately 45) is produced in conjunction with vibrationally "cold" H(2) fragments (v=0-5): these products are formed through the well-known skewed transition state and described in detail in the accompanying paper. After excitation of formaldehyde above the threshold for the radical channel (H(2)CO-->H+HCO) we also find formation of rotationally cold CO (j(CO)=5-28) correlated to highly vibrationally excited H(2) (v=6-8). These products are formed through a novel mechanism that involves near dissociation followed by intramolecular H abstraction [D. Townsend et al., Science 306, 1158 (2004)], and that avoids the region of the transition state entirely. The dynamics of this "roaming" mechanism are the focus of this paper. The correlations between the vibrational states of H(2) and rotational states of CO formed following excitation on the 2(1)4(3) transition allow us to determine the relative contribution to molecular products from the roaming atom channel versus the conventional molecular channel.

Carbon Monoxide↗

PubMed2006

Multiphoton processes of CO at 230 nm.

High resolution kinetic energy release spectra were obtained for C(+) and O(+) from CO multiphoton ionization followed by dissociation of CO(+). The excitation was through the CO (B (1)Sigma(+)) state via resonant two-photon excitation around 230 nm. A total of 5 and 6 photons are found to contribute to the production of carbon and oxygen cations. DC slice and Megapixel ion imaging techniques were used to acquire high quality images. Major features in both O(+) and C(+) spectra are assigned to the dissociation of some specific vibrational levels of CO(+)(X (2)Sigma(+)). The angular distributions of C(+) and O(+) are very distinct and those of various features of C(+) are also different. A dramatic change of the angular distribution of C(+) from dissociation of CO(+)(X (2)Sigma(+), nu(+) = 1) is attributed to an accidental one-photon resonance between CO(+)(X (2)Sigma(+), nu(+) = 1) and CO(+)(B (2)Sigma(+), nu(+) = 0) and explained well by a theoretical model. Both kinetic energy release and angular distributions were used to reveal the underlying dynamics.

Algorithms↗

PubMed2006

Photoelectron imaging of propanal by resonant multiphoton ionization via the 3s Rydberg state.

We report the conformationally- and vibrationally-selected photoelectron spectroscopy of propanal obtained by resonance-enhanced multiphoton ionization (REMPI) using photoelectron imaging. These photoelectron spectra, employing (2 + 1) ionization via the (n, 3s) Rydberg transitions in the range from 365 to 371 nm, confirm that there are two stable conformer origins in the lowest ionic state, the cis conformer with a co-planar CCCO geometry and a gauche conformer with a approximately 119 degrees CCCO dihedral angle. From ab initio calculations at the B3LYP/6-311++G** level, we find the gauche conformer is slightly more stable, with the energy difference between two conformers determined to be only 65 cm(-1). In our photoelectron spectra, the vertical ionization potential (IP) for the cis conformer of propanal was then determined to be 9.999 (+/-0.003) eV, while that of the gauche conformer of propanal was estimated to be 9.944 eV. A long vibrational progression in the in-plane CCCO deformation vibrational mode, v, for the cis conformer is systematically observed in all photoelectron spectra in which this mode is excited, suggesting that the geometry of the ground ionic state is significantly different from that of the 3s Rydberg state, particularly along the v(15) coordinates.

Aldehydes↗

PubMed2006

Correlated product distributions from ketene dissociation measured by dc sliced ion imaging.

Speed distributions of spectroscopically selected CO photoproducts of 308 nm ketene photodissociation have been measured by dc sliced ion imaging. Structured speed distributions are observed that match the clumps and gaps in the singlet CH2 rotational density of states. The effects of finite time gates in sliced ion imaging are important for the accurate treatment of quasicontinuous velocity distributions extending into the thickly sliced and fully projected regime, and an inversion algorithm has been implemented for the special case of isotropic fragmentation. With accurate velocity calibration and careful treatment of the velocity resolution, the new method allows us to characterize the coincident rotational state distribution of CH2 states as a smoothly varying deviation from an unbiased phase space theory (PST) limit, similar to a linear-surprisal analysis. High-energy rotational states of CH2 are underrepresented compared to PST in coincidence with all detected CO rotational states. There is no evidence for suppression of the fastest channels, as had been reported in two previous studies of this system by other techniques. The relative contributions of ground and first vibrationally excited singlet CH2 states in coincidence with selected rotational states of CO (upsilon=0) are well resolved and in remarkably good agreement with PST, despite large deviations from the PST rotational distributions in the CH2 fragments. At 308 nm, the singlet CH2 (upsilon2=0) and (upsilon2=1) channels are 2350 and 1000 cm(-1) above their respective thresholds. The observed vibrational branching is consistent with saturation at increasing energies of the energy-dependent suppression of rates with respect to the PST limit, attributed to a tightening variational transition state.

Journal Article↗

PubMed2006

ION pair dissociation: Spectroscopy and dynamics.

Ion pair dissociation processes may be studied using coherent vacuum ultraviolet laser sources in a manner entirely analogous to photoelectron spectroscopy, albeit with the anion playing the role of a heavy electron. If the excitation energy is above the dissociation energy and the kinetic energy of the fragment is measured using ion imaging, this approach is termed ion pair imaging spectroscopy (IPIS) and is related to conventional photoelectron spectroscopy. If the excitation energy is just below the dissociation energy and pulsed-field dissociation is employed, this approach is analogous to mass analyzed threshold ionization (MATI) spectroscopy and is termed threshold ion pair production spectroscopy (TIPPS). These approaches provide a novel means of investigating ion thermochemistry and spectroscopy and superexcited state decay dynamics at high resolution.

Journal Article↗

PubMed2005

Universal and state-resolved imaging of chemical dynamics.

We showcase the use of high-resolution ion imaging with complementary state-resolved and "universal" vacuum ultraviolet probes to address a broad range of fundamental problems in chemical reaction dynamics. Examples from our recent work include applications in state-correlated unimolecular reactions, ion pair dissociation dynamics and spectroscopy, crossed-beam reactive scattering, and atomic angular momentum polarization in photodissociation. These studies are all directed to achieving a detailed understanding of atomic and molecular interactions, with particular emphasis on reaction mechanisms outside the scope of transition state theory; on spectroscopy and dynamics of highly excited, transient species; on nonadiabatic reaction mechanisms; and on chemical dynamics in polyatomic systems.

Journal Article↗

PubMed2005

Vibrationally mediated photodissociation of ethylene cation by reflectron multimass velocity map imaging.

A new imaging technique, reflectron multimass velocity map ion imaging, is used to study the vibrationally mediated photodissociation dynamics in the ethylene cation. The cation ground electronic state is prepared in specific vibrational levels by two-photon resonant, three-photon ionization via vibronic bands of (pi, nf) Rydberg states in the vicinity of the ionization potential of ethylene, then photodissociated through the (B 2A(g)) excited state. We simultaneously record spatially resolved images of parent C2H4+ ions as well as photofragment C2H3+ and C2H2+ ions originating in dissociation from the vibronic excitations in two distinct bands, 7f 4(0)2 and 8f 0(0)0, at roughly the same total energy. By analyzing the images, we directly obtain the total translation energy distributions for the two dissociation channels and the branching between them. The results show that there exist differences for competitive dissociation pathways between H and H2 elimination from C2H4+ depending on the vibronic preparation used, i.e., on the vibrational excitation in the ground state of the cation prior to photodissociation. Our findings are discussed in terms of the possible influence of the torsional excitation on competition between direct dissociation, isomerization, and radiationless transitions through conical intersections among the numerous electronic states that participate in the dissociation.

Letter↗

PubMed2004

Orbital alignment in N2O photodissociation. I. Determination of all even rank anisotropy parameters.

We present a general method for determination of the photofragment K=4 state multipoles in an ion imaging experiment. These multipoles are important for determining the full density matrix for any photofragment with j(a)> or =2. They are expressed in terms of laboratory frame anisotropy parameters that have distinct physical origins and possess characteristic angular distributions. The explicit expression for the (2+1) resonant multiphoton ionization absorption signal for the case of arbitrarily polarized probe light is derived and a procedure for isolation of the rank-4 state multipoles from all others is shown. This treatment is applied to the case of O((1)D) produced in the 193 nm photodissociation of N2O. The results show nonzero values for all K=4 anisotropy parameters, indicating the complexity of the photodissociation dynamics in this system.

Journal Article↗

PubMed2004

Superexcited state dynamics probed with an extreme-ultraviolet free electron laser.

We present the first experimental results obtained with a high-gain harmonic generation extreme ultraviolet free electron laser. The experiment probes decay dynamics of superexcited states of methyl fluoride via ion pair imaging spectroscopy. Velocity mapped ion images of the fluoride ion, obtained with excitation via intense, coherent, subpicosecond pulses of 86-89 nm radiation, reveal low translational energy, implying very high internal excitation in the methyl cation cofragment. Angular distributions show changing anisotropy as the excitation energy is tuned through this region. The dynamics underlying the dissociation are discussed with the aid of theoretical calculations.

Journal Article↗