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At least 253 records · Page 14

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DOE OSTI2020

Mapping the Temperature-dependent and network site-specific onset of spectral diffusion at the surface of a water cluster cage

We explore the kinetic processes that sustain equilibrium in a microscopic, finite system. This is accomplished by monitoring the spontaneous, time-dependent frequency evolution (the frequency autocorrelation) of a single OH oscillator, embedded in a water cluster held in a temperature-controlled ion trap. The measurements are carried out by applying two-color, IR-IR photodissociation mass spectrometry to the D3O+?(HDO)(D2O)19 isotopologue of the “magic number” protonated water cluster, H+?(H2O)21. The OH group can occupy any one of the five spectroscopically distinct sites in the distorted pentagonal dodecahedron cage structure. The OH frequency is observed to evolve over tens of milliseconds in the temperature range (90-120 K). Starting at 100 K, large “jumps” are observed between two OH frequencies separated by ~300 cm-1 indicating migration of the OH group from the bound OH site at 3350 cm-1 to the free position at 3686 cm-1. Increasing the temperature to 110 K leads to partial interconversion among many sites. All sites are observed to interconvert at 120 K such that the distribution of the unique OH group among them adopts the form one would expect for a canonical ensemble. The spectral dynamics displayed by the clusters thus offer an unprecedented view into the molecular-level processes that drive spectral diffusion in an extended network of water molecules.

Yang, Nan↗

DOE OSTI2023

High-resolution vibrational predissociation spectroscopy of I - ·H 2 O by single-mode CW infrared excitation in a 3D cryogenic ion trap

We describe the integration of a tunable, single-mode, continuous wave infrared laser into a cryogenic ion spectroscopy experiment to measure the rovibrational spectrum of the I - ∙H 2 O complex in the OH stretching region. These upper levels lie about 300 cm -1 above the dissociation threshold. The measurements are carried out by loading the ions in a radiofrequency ion trap at 10 Hz and cooling them to 5 K with pulsed He buffer gas. IR photodissociation (PD) of the I - ∙H 2 O complex is monitored by recording the I - product yield by time-of-flight mass spectrometry as a function of laser wavelength. Very narrow (Δν~75 MHz) rotational lines are observed throughout the spectrum, indicating long (ca. 2 ns) lifetimes for the excited metastable rovibrational levels. Rotational analysis of the band arising from the K”=1 to K’=2 transition of the free OH stretching fundamental yields the structure of the complex for the first time. Over 50% of the trapped ion ensemble in the trap can be photodissociated upon excitation of a single rotational line. This enables very high signal-to-noise in the PD spectrum, and is traced to a mechanism in which the ground state rotational levels are rapidly equilibrated by collisions with the buffer gas.

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2021

Mammalian complex III heme dynamics studied with pump-probe spectroscopy and red light illuminations

The electronic or molecular mechanisms which initiate photobiomodulation (PBM) in cells are not yet fully understood. Porcine complex III (C-III) of the electron transport chain was characterized with transient absorption spectroscopy (TAS). Then we applied our recently developed continuous wave laser coupled TAS procedure (CW-TAS) to investigate the effect of red light irradiances on the heme dynamics of C-III in its c 1 reduced state. The time constants associated with the axial ligand photodissociation were found to be 3.3 ± 0.3 ps for the oxidized state and 4.9 ± 0.4 ps for the c 1 reduced state. The analysis of the CW-TAS procedure yielded no significant changes in the C-III heme dynamics. We rule out the possibility of 635 nm CW light at 4.7 mW/cm 2 inducing a PBM effect on the heme dynamic of C-III, specifically with the photodissociation of its axial ligand.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2020

Lyα Observations of Comet C/2013 A1 (Siding Spring) Using MAVEN IUVS Echelle

The close approach of comet C/2013 A1 (Siding Spring) to Mars in 2014 October provided a unique opportunity to observe a dynamically new Oort cloud comet with potential for interaction with a planet’s atmosphere. The water-originating hydrogen coma of the comet extended to over 20 million km from the nucleus. Determining the properties of this coma contributes to characterizing the comet’s water content and production rate. The present study analyzes a unique data set of high spectral resolution UV observations of comet C/2013 A1 Siding Spring measured by the Mars Atmosphere and Volatile Evolution spacecraft. The Siding Spring observations capture Lyα emissions from the Martian corona, the interplanetary medium, as well as the cometary H and D reservoirs. The isolated cometary spectra are analyzed to reveal a velocity distribution of H atoms that are consistent with model estimates of H{sub 2}O photodissociated H emissions and of OH photodissociated H emissions, Doppler shifted from the main comet H emission line center by 18 km s{sup −1} and 8 km s{sup −1}, respectively. The variations in comet H brightness with distance from the nucleus are used to constrain cometary water production to a rate of 0.5 × 10{sup 28} molecules s{sup −1} at a time when Siding Spring was at 1.5 au, pre-perihelion.

79 ASTRONOMY AND ASTROPHYSICS↗

NASA NTRS1974

An assessment of the potential impact of solid-fueled rocket engines in the stratosphere

The effects of shuttle-emitted HCl on stratospheric ozone are reported. A one-dimensional model of the distribution of trace constituents in the stratosphere and mesosphere is described, and chemical reactions and photodissociation rates in the chlorine chemistry are listed. Analysis of mathematical models is presented, and the results show ozone depletion when emissions are considered to be spread uniformly in the horizontal over a hemisphere and an increase in ozone when emissions are considered in a zone 1000 km wide centered at Cape Kennedy. Sensitivity studies to determine the effects of some assumptions in the model and comparisons with nitric oxide reactions are described. The importance of a two-dimensional model for a proper long term study is noted. Lists of reaction rate coefficients and photodissociation rates for the O-H-N system are included.

Whitten, R. C.↗

NASA NTRS1976

Laser induced photoluminescence spectroscopy of cometary radicals

Flash photolysis together with laser excitation of the product fragments was used in laboratory studies of cometary radicals. The LIPS method has been applied to the CN radical to determine: (1) Radiative lifetimes of individual rotational levels in the zeroth vibrational level of the B state; (2) energy partitioning during photodissociation of C2N2; and (3) vibrational and rotational excitation during formation of CN radicals in the photodissociation of dicyanoacetylene.

Jackson, W. M.↗

NASA NTRS1976

Photocatalytic generation of hydrogen from water

A concept designed to overcome the problems encountered when using photodissociation for the generation of hydrogen is discussed. The problems limiting the efficiency of photodissociation of water are the separation of the photolysis products and the high energy photons necessary for the reaction. It is shown that the dissociation energy of a large number of molecules is catalytically reduced when these molecules are in intimate contact with the surface of certain metals. It is proposed to develop a surface which will take advantage of this catalytic shift in dissociation energies to reduce the photon energy required to produce hydrogen. This same catalytic surface can be used to separate the reaction products if it is made so that one of the dissociations products is soluble in the metal and others are not. This condition is met by many metal systems such as platinum group metals which have been used commercially to separate hydrogen from other gases and liquids.

Bottoms, W. R.↗

NASA NTRS1978

Apparatus for extraction and separation of a preferentially photo-dissociated molecular isotope into positive and negative ions by means of an electric field

Molecules of one and the same isotope were preferentially photodissociated by a laser and an ultraviolet source, or by multiphoton absorption of laser radiation. The resultant ions were confined with a magnetic field, moved in opposite directions by an electric field, extracted from the photodissociation region by means of screening and accelerating grids, and collected in ducts.

Wilhelm, H. E.↗

NASA NTRS1981

Solar-pumped gas laser development

The direct conversion of solar radiation into an inverted population for extraction in an optical cavity holds promise as a relatively simple system design. Broad-band photoabsorption in the visible or near-UV range is required to excite large volumes of gas and to ensure good solar absorption efficiency. The state excited must be a metastable state which is not quenched by the parent gas. The emission bandwidth must be less than approximately 10 A. The system should show chemical reversibility and an insensitivity to increasing temperature. Other properties such as good quantum efficiency and kinetic efficiency are also implied. A search of electronic-vibrational transitions in diatomic molecules satisfying these conditions is now in progress. A photodissociation-pumped atomic iodine laser is now being tested under solar pumping conditions. Photodissociation studies for thallium spin-flip metastable formation will begin in the near future.

Wilson, J. W.↗

NASA NTRS1982

Molecular processes in comets

Potential energy curves for the two lowest 2 sigma- states of OH are computed at the configuration-interaction level using four different basis sets. Electronic transition dipole moments connecting the excited 1 2 sigma- and 2(D) 2 sigma- states with each other and with he ground X2pi state are presented as functions of internuclear distance. The theoretical absorption oscillator strengths for the D 2 sigma-(v prime=0) reverser to X 2pi (v prime prime=0) transition are in good agreement with the empirical value derived from astronomical measurements. The photodissociation cross sections for absorption rom the v prime prime=0,1, and levels of the ground state into the continuum of the 1 2 sigma- state are calculated, and the interstellar and cometary photodissociation rates are derived.

Dalgarno, A.↗

NASA NTRS1984

The dissociation of OH and OD in comets by solar radiation

Calculations of the radiative lifetimes of cometary OH are presented as a function of the radial velocity of the comet and of the velocity distributions of the hydrogen and oxygen atoms produced by photodissociation of OH. The contribution of the photodissociation of OH to the emission of the red and green lines of atomic oxygen is assessed. An estimate is made of the lifetime of OD and of the velocity distribution of the deuterium atoms.

Van Dishoeck, E. F.↗

NASA NTRS1985

Design and chemical synthesis of iodine-containing molecules for application to solar-pumped I* lasers

This work is directed toward the design and chemical synthesis of new media for solar-pumped I* lasers. In view of the desirability of preparing a perfluoroalkyl iodide absorbing strongly at 300 nm, the relationship betwen perfluoroalkyl iodide structure and the corresponding absorption wavelength was reexamined. Analysis of existing data suggests that, in this family of compounds, the absorption maximum shifts to longer wavelength, as desired, as the C-I bond in the lasant is progressively weakened. Weakening of the C-I bond correlates, in turn, with increasing stability of the perfluoroalkyl radical formed upon photodissociation of the iodide. The extremely promising absorption characteristics of perfluoro-tert-butyl iodide can be accounted for on this basis. A new technique of diode laser probing to obtain precise yields of I* atoms in photodissociation was also developed.

Shiner, C. S.↗

NASA NTRS1985

A model for the CI (609 micron) emission of Orion

A numerical model energy balance and chemical equilibrium in the photodissociation regions at the edge of molecular clouds is presented. The model is used to calculate the emergent intensities of the following fine-structure lines: OI (at 63, 145 microns); CI (at 609, 370 microns); C II (at 158 microns); and the low-lying rotational transitions of CO. It is shown that column densities in the range 2 x 10 to the 17th to 2 x 10 to the 18th per sq cm can be obtained for the C(+)/C/CO transition region at the edges of molecular clouds. The difference in the column densities is attributed to changes in the charge exchange reactions of C(+) with SiO and S, and to the process of carbon self-healing. It is found that the calculations are in good agreement with the observed conditions in the photodissociation regions behind Orion (1) C Ori, and near the surface of OMC 1.

Tielens, A. G. G. M.↗

NASA NTRS1985

The internal state distribution of CN radicals produced in the photolysis of HC2CN and CH3CN

The energy partitioning in CN radicals produced by the vacuum ultraviolet photodissociation of HC2CN and CH3CN is studied by means of laser-induced fluorescence of the B-X transition. Experiments are performed in two collision regimes: (1) in the low-collision number regime, the energy partitioning in CN(X) is measured; (2) in the high-collision number regime, the formation of CN(A) is monitored. It is shown that photodissociation of HC2CN in its linear predissociative 1Sigma(+) state produces predominantly ground-state CN in rotationally and vibrationally excited states. The vibrational population ratios and the temperatures computed from a Boltzmann fit of the rotational levels are given in a table. The excitation of CH3CN produces CN radicals almost entirely in the first excited A-state with vibrational excitation.

Cody, R. J.↗

NASA NTRS1985

Detection of [SiLL] (34.8 micron) emission in Orion-KL: A measurement of the silicon abundance in dense interstellar gas

The first detection of the ground state fine structure transition of Si+ at a rest wavelength determined to be 34.815 + or - 0.004 micron are reported. These observations were obtained with the facility spectrometer on NASA's Kuiper Airborne Observatory. A 6' NW-SE strip scan across the Orion-KL region shows SiII emission from both the extended photodissociation region surrounding theta 1 Ori C and from the shocked gas NW of BN-KL. The inferred gas-phase silicon elemental abundance relative to hydrogen in the dense 10 to the 5/cc primarily neutral photodissociation region is approximately 2.6 x to the -6, a factor of 0.075 times the solar value and 3.4 times greater than the abundance in the moderate density approx. 10 to the 3/cc cloud toward zeta Oph. The silicon abundance in the shocked gas is approximately solar, indicating that any pre-existing grains have been destroyed in the shock wave or that the preshock gas carries a near solar abundance of gas phase silicon. The shock-excited SiII (34.8 micron) emission may arise from shocked wind material in the outflow around IRc2, with wind velocities approx. 100 km/s.

Haas, M. R.↗

NASA NTRS1985

Accurate quantum yields by laser gain vs absorption spectroscopy - Investigation of Br/Br(asterisk) channels in photofragmentation of Br2 and IBr

Various techniques have been used to study photodissociation dynamics of the halogens and interhalogens. The quantum yields obtained by these techniques differ widely. The present investigation is concerned with a qualitatively new approach for obtaining highly accurate quantum yields for electronically excited states. This approach makes it possible to obtain an accuracy of 1 percent to 3 percent. It is shown that measurement of the initial transient gain/absorption vs the final absorption in a single time-resolved signal is a very accurate technique in the study of absolute branching fractions in photodissociation. The new technique is found to be insensitive to pulse and probe laser characteristics, molecular absorption cross sections, and absolute precursor density.

Haugen, H. K.↗

NASA NTRS1986

Detection of (Si II) (34.8 micron) emission in Orion-KL - A measurement of the silicon abundance in dense interstellar gas

The first detection of the ground state fine structure transition of Si+ at a rest wavelength determined to be 34.815 + or - 0.004 micron are reported. These observations were obtained with the facility spectrometer on NASA's Kuiper Airborne Observatory. A 6' NW-SE strip scan across the Orion-KL region shows Si II emission from both the extended photodissociation region surrounding theta 1 Ori C and from the shocked gas NW of BN-KL. The inferred gas-phase silicon elemental abundance relative to hydrogen in the dense 10 to the 5/cc primarily neutral photodissociation region is approximately 2.6 x 10 the -6, a factor of 0.075 times the solar value and 3.4 times greater than the abundance in the moderate density aprox. 10 to the 3/cc cloud toward Zeta Oph The silicon abundance in the shocked gas is approximately solar, indicating that any pre-existing grains have been destroyed in the shock wave or that the preshock gas carries a near solar abundance of gas phase silicon. The shock-excited Si II (34.8 micron) emission may arise from shocked wind material in the outflow around IRc2, with wind velocities approx. 100 km/s.

Haas, M. R.↗

NASA NTRS1990

Warm dense gas in the reflection nebula NGC 2023

A photodissociation region (PDR) with a known UV excitation source was studied by examining emission from atomic and molecular material. In agreement with models of externally excited PDRs, the photodissociation region southwest of HD 37903 contains both atomic and excited molecular material and arises close to the exciting star than does the bulk of the molecular cloud. The C(+) emission arises closest to the star but is 1.5 x 10 to the 17th cm or less from the peaks in the excited CO and fluorescent H2 emission regions. The (C-18)O J = 2 - 1 line, which traces molecular column density, has its emission peak about 4 x 10 to the 17th cm beyond the C(+) peak. Even in a source with an incident UV flux as low as about 1000 times the mean interstellar radiation field, there is a significant amount of CO 7 - 6 emission arising from regions with T(gas) greater than 85 K which is substantially greater than T(dust).

Jaffe, D. T.↗