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Li, Hongwei

Publications and source records attributed to Li, Hongwei.

9 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Sulfur ( 3 P) Reaction with Conjugated Dienes Gives Cyclization to Thiophenes under Single Collision Conditions

Here, we combine crossed-beam velocity map imaging with high-level ab initio/transition state theory modeling of the reaction of S( 3 P) with 1,3-butadiene and isoprene under single collision conditions. For the butadiene reaction, we detect both H and H 2 loss from the initial adduct, and from reaction with isoprene, we see both H loss and methyl loss. Theoretical calculations confirm these arise following intersystem crossing to the singlet surface forming long-lived intermediates. For the butadiene reaction, these lose H 2 to form thiophene as the dominant channel, H to form the detected 2H-thiophenyl radical, or ethene, giving thioketene. For isoprene, additional reaction products are suggested by theory, including the observed H and methyl loss radicals, but also methyl thiophene, thioformaldehyde, and thioketene. The results for S( 3 P) + 1,3-butadiene, showing direct cyclization to the aromatic product and yielding few bimolecular product channels, are in striking contrast to those for the analogous O( 3 P) reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Multichannel dynamics in the OH+ n -butane reaction revealed by crossed-beam slice imaging and quasiclassical trajectory calculations

Multidimensional reactions present various channels that can exhibit very different dynamics and give products of varying subsequent reactivity. Here, we present a combination of experiment and theory to reveal the dynamics of hydrogen abstraction by OH radical at primary and secondary sites in n-butane at a collision energy of 8 kcal/mol. Crossed molecular beam slice imaging experiments unequivocally probe the secondary abstraction channel showing backward angular distributions with mild energy release to product translation, which are accurately captured by trajectory calculations using a specific-reaction-parameter Hamiltonian. Additionally, experiments containing both reaction channels indicate a less marked backward character in the angular distribution, whose origin is shown by trajectory calculations to appear as an evolution toward more sideways scattering from the secondary to primary channel. While the two channels have markedly different angular distributions, their energy release is largely comparable, showing ample energy release into the water product. The synergistic combination of crossed-beam imaging and trajectories opens the door to detailed reaction-dynamics studies of chemical reactions with ever-increasing complexity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Universal crossed beam imaging studies of polyatomic reaction dynamics

The marriage between high level quantum calculations and experimental advances in laser technology, quantum state control, and detection techniques have opened the door to the study of molecular collision dynamics at a new level of detail. However, one current challenge lies in adapting these powerful strategies to address questions beyond the scope of the small ground state systems that have largely been the focus of reaction dynamics investigations to-date. For molecules with intermediate or large size (more than 6 atoms), lack of spectroscopic information and spectral congestion limit quantum state preparation, control and detection for experiment, and the large number of degrees of freedom of the system makes accurate quantum dynamics calculations prohibitively expensive. Nevertheless, studies of the chemical dynamics of such systems can reveal novel aspects of reactivity not anticipated based upon the behavior of smaller model systems. This Perspective will highlight applications of soft vacuum ultraviolet photoionization at 157 nm as a universal probe in combination with crossed beams and DC slice velocity map ion imaging to study bimolecular reaction dynamics of molecules of intermediate or large size, illuminated with support of high-level ab initio calculations. In this work, we report on the chemical dynamics of atomic oxygen or chlorine reactions with organic compounds: propanol isomers, alkylamines (N(CH 3 ) 3 and NH(CH 3 ) 2 ), and isobutene ((CH 3 ) 2 CCH 2 ) studied using this approach. The polyatomic radical products from the hydrogen abstraction process have been detected by 157 nm photoionization and their slice ion images embody translational energy and angular information that directly reflect the underlying collision dynamics. Various reaction mechanisms (such as direct abstraction and addition–elimination) along with the involvement of roaming dynamics and novel intersystem crossing pathways are presented. These demonstrate the power of this technique to reveal fundamentally new aspects of reaction dynamics that arise in larger reaction systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1996

Ultraviolet Opacity and Fluorescence in Supernova Envelopes

By the time the expanding envelope of a Type 2 supernova becomes transparent in the optical continuum, most of the gamma-ray luminosity produced by radioactive Fe/Co/Ni clumps propagates into the hydrogen/helium envelope and is deposited there, if at all. The resulting fast electrons excite He 1 and H 1, the two- photon continua of which are the dominant internal sources of ultraviolet radiation. The UV radiation is blocked by scattering in thousands of resonance lines of metals and converted by fluorescence into optical and infrared emission lines that escape freely. We describe results of Monte Carlo calculations that simulate non-LTE scattering and fluorescence in more than five million allowed lines of Ca, Sc, Ti, V, Cr, Mn, Fe, Co, and Ni. For a model approximating conditions in the envelope of SN 1987A, the calculated emergent spectrum resembles the observed one. For the first 2 yr after explosion, the ultraviolet radiation (lambda less than or approximately equals 3000) is largely blocked and converted into a quasi continuum of many thousands of weak optical and infrared emission lines and some prominent emission features, such as the Ca 2 lambdalambda8600 triplet. Later, as the envelope cools and expands, it becomes more transparent, and an increasing fraction of the luminosity emerges in the UV band.

Li, Hongwei↗
NASA NTRS1995

The He I emission lines of SN 1987A

We model the evolution of the He I lines, especially He I 1.083 micrometers and He I 2.058 micrometers, from the envelope of SN 1987A during the first 3 yr after the explosion. The He I metastable 2(sup 3)S and 2(sup 1)S states are populated by fast electrons resulting from energy deposition by gamma rays and depopulated by electron collisions and two-photon decay. The 2.058 micrometer line is excited mainly by nonthermal electrons at all times. The 1.083 micrometer line is excited mainly by thermal electron impact for t less than or approximately = 450 days and by recombination afterward. We can fit the observed evolution of He I 2.058 micrometers with a model in which approximately 3 solar mass of nearly pure helium and approximately 11 solar mass of hydrogen mixed with primordial helium occupy the volume emitting most of the light (v less than or approximately = 2500 km/s). For t less than or approximately = 450 days, trace carbon in the inner part of the helium suppresses the He I 2.058 micrometer line by photoabsorbing He I lambda 584 and depopulating the 2(sup 1) P(sup 0) state. The observed 1.08 micrometer line is a blend of He I 1.083 micrometers and (S I) 1.082 micrometers. We estimate that He I 1.083 micrometers contributes 40% of the observed flux for t less than or approximately = 550 days and approximately 60% thereafter.

Li, Hongwei↗
NASA NTRS1993

Iron, Cobalt, and Nickel in SN 1987A

During the first several weeks after the explosion of SN 1987A, Fe/Co/Ni clumps, containing approx. 1% of the mass of the supernova envelope, absorbed most of the energy release by Ni-56 and Co-56 decay. As a result, the clumps expanded relative to the substrate, forming a 'nickel bubble' of low-density Fe/Co/Ni. Later the clumps captured approx. 10% of the radioactive luminosity of gamma rays and positrons. Assuming that these elements are not mixed microscopically with other elements, we find that the clumps must occupy approx. greater than 30% of the volume of the emitting region (radial velocity approx. less than 2500 km/s). The result indicates that the emission at late times is dominated by an extra source of heating and ionization, most likely photoionization by two-photon continuum from metastable helium in the gas surrounding the clumps. The resulting 'frothy' structure, consisting of bubbles of low-density Fe surrounded by higher-density filaments of H, He, and other elements, will persist and may be seen in the spectra and structure of supernova remnants.

Li, Hongwei↗
NASA NTRS1993

The Ca II emission lines of SN 1987A

We study the evolution of the forbidden Ca II 7300 A and Ca II 8600 A emission lines in the spectrum SN 1987A. We can explain the observations with a model in which (1) the lines come from about 1.7 x 10 exp -4 solar mass of calcium distributed with filling factor about 0.1 in a sphere expanding with velocity 2500 km/s; (2) the electron number density is given by 4 x 10 exp 9/cu cm/(t/100d)-cubed; (3) the gas temperature decreases from T roughly 6400 K at 200 days to T roughly 3900 K at 500 days; and (4) ultraviolet pumping in the Ca II 3934 A, 3969 A (K, H) lines is required to explain the line ratios for t greater than about 350 days. The mass of calcium in our model is consistent with the LMC abundance of calcium in about 5 solar mass of hydrogen in the inner envelope of SN 1987A. If more calcium is produced by supernova nucleosynthesis, it must be in dense clumps that are too cool to emit the forbidden Ca II 7300 A and Ca II 8600 A lines.

Li, Hongwei↗