Laser-initiated chemical reactions: total absolute reaction rate constants for Cl+ HBr and Cl + HI

Wodarczyk, Francis J.; Moore, C. Bradley

doi:10.1016/0009-2614(74)80396-9

Cited by 37 publications

(10 citation statements)

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“…Understanding such reactions and relaxations has been critical for the production and maintenance of inverted vibrational populations in chemical lasers. Glenn Macdonald, Steve Leone, Klass Bergmann, and Chang-Chi Mei carried out a series of measurements of halogen + hydrogen halide reaction and relaxation rates (64)(65)(66)(67)(68)(88)(89)(90)(91)(92)(93) because for HCl(v = 2, 1), the total energy is well above the barrier to Cl + OH formation (68, 69). Figure 5 shows the main results: Most (probably two-thirds to three-fourths) of the HCl(v = 2) is relaxed to v = 1 rather than reacting to give OH.…”

Section: Bimolecular Reactionsmentioning

confidence: 99%

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A Spectroscopist's View of Energy States, Energy Transfers, and Chemical Reactions

Moore

2007

Annu. Rev. Phys. Chem.

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This chapter describes a research career beginning at Berkeley in 1960, shortly after Sputnik and the invention of the laser. Following thesis work on vibrational spectroscopy and the chemical reactivity of small molecules, we studied vibrational energy transfers in my own lab. Collision-induced transfers among vibrations of a single molecule, from one molecule to another, and from vibration to rotation and translation were elucidated. My research group also studied the competition between vibrational relaxation and chemical reaction for potentially reactive collisions with one molecule vibrationally excited. Lasers were used to enrich isotopes by the excitation of a predissociative transition of a selected isotopomer. We also tested the hypotheses of transition-state theory for unimolecular reactions of ketene, formaldehyde, and formyl fluoride by (a) resolving individual molecular eigenstates above a dissociation threshold, (b) locating vibrational levels at the transition state, (c) observing quantum resonances in the barrier region for motion along a reaction coordinate, and (d) studying energy release to fragments. GETTING STARTEDI had the good fortune to grow up on a farm in eastern Pennsylvania, where hard work produced good crops, poultry, and livestock; where I could help my father take apart, repair, and reassemble farm equipment; and where I could manufacture and experiment with gun powder. In those days, parents could still give chemistry sets to their children, and the East Coast sky was often clear enough to observe shooting stars while lying flat on the bed of a hay wagon. This constituted my first spectroscopic observations of chemistry in action. My initial in-class chemistry lab was a study of sulfur combustion carried out by placing a fumigation candle in the ink well of my third-grade desk and lighting it on departure for recess. This early initiative was not encouraged on my return from the playground. One of Princeton Professor Hubert Alyea's renowned lectures on the marvels of chemistry at a nearby high school provided my first look at cryogenics as he exhaled through a mouth full of dry ice. By the time I finished a series of integrated courses in the physical sciences, a one-week visit by J. Robert Oppenheimer, and a challenging course in analytical/inorganic chemistry in high school (Phillips Exeter Academy in New Hampshire), I was well on my way to becoming a physical chemist. The launching of Sputnik during my first month of college (October 1957) at Harvard sharply increased federal funding for scientific research and greatly encouraged scientific career paths. That fall, the intensity of lab courses in physics and organic chemistry, a fourth-semester calculus course, and a humanities course quickly ended my aspiration to extend my high-school crew experience to intercollegiate rowing. A series of research projects in Paul D. Bartlett's personal lab at Harvard and summer jobs at Arthur D. Little and General Electric's corporate research lab deepened my interest and experi...

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Section: Bimolecular Reactionsmentioning

confidence: 99%

“…All these rates were of great value in developing the hydrogen-halide chemical lasers as practical IR sources. These studies set the stage for measuring chemical-reaction rates (66) and studying the branching between reaction and relaxation for vibrationally excited reagent molecules (67)(68)(69)(70).…”

Section: Chemically Reactive Collision Partnersmentioning

confidence: 99%

A Spectroscopist's View of Energy States, Energy Transfers, and Chemical Reactions

Moore

2007

Annu. Rev. Phys. Chem.

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“…The chemical generation of J*(2p112) and subsequent lasing is based on a sequential process in which Cl and I atoms are produced, F + DC1 -+ DF + Cl, k 1 X 1O cm3/s (7) (1) Cl + Hi -+ HC1 + I (2P312), oo K 1 .0 X 1 O' cm3ls, (8) (2) followed by NC1 (a1A) production, Cl + }jJ3 -_ HC1(v)+ N3, 300 K 1 x 1012 cm3/s (9) (3) Cl + N3 -NC1(a'A, b1, X3) + N2(X'), k300K 2 x 10h1 (10,11) …”

Section: Resultsmentioning

confidence: 99%

New chemically pumped I(²P 1/2 →²P 3/2 ) laser at 1.315 μm

et al. 2001

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“…. The excited isotopic molecule AnB(v = i) may react with reactant C, AnB(v = i) + C =At CnB (2) undergo vibrational deactivation (V -T, R),…”

Section: (La)mentioning

confidence: 99%

“…In general, the enrichment is a trade-off between the isotope ratio in the products and the yield of products. If reactions of the type of Reaction (2) (v > 0) totally dominate all other processes, both the ratio and yield are 2-…”

Section: (La)mentioning

confidence: 99%

Modeling study of vibrational photochemical isotope enrichment. [HBr + Cl/sub 2/; HCl + Br/sub 2/]

Badcock¹,

Hwang²,

Kalsch³

1978

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THE IVAN A. GETTING LABORATORIES The Laboratory Operations of The Aerospace Corporation is conducting experimental and theoretical investigations necessary for the evaluation and application of scientific advances to new military concepts and systems. Versatility and flexibility have been developed to a high degree by the laboratory personnel in dealing with the many problems encountered in the nation's rapidly developing space and missile systems. Expertise in the latest scientific developments is vital to the accomplishment of tasks related to these problems. The laboratories that contribute to this research are: Aerophysics Laboratory: Launch and reentry aerodynamics, heat transfer, reentry physics, chemical kinetics, structural mechanics, flight dynamics, atmospheric pollution, and high-power gas lasers. Chemistry and Physics Laboratory: Atmospheric reactions and atmospheric optics, chemical reactions in polluted atmospheres, chemical reactions of excited species in rocket plumes, chemical thermodynamics, plasma and laser-induced reactions, laser chemistry, propulsion chemistry, space vacuum and radiation effects on materials, lubrication and surface phenomena, photosensitive materials and sensors, high precision laser ranging, and the application of physics and chemistry to problems of law enforcement and biomedicine.

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Laser-initiated chemical reactions: total absolute reaction rate constants for Cl+ HBr and Cl + HI

Cited by 37 publications

References 10 publications

A Spectroscopist's View of Energy States, Energy Transfers, and Chemical Reactions

A Spectroscopist's View of Energy States, Energy Transfers, and Chemical Reactions

New chemically pumped I(²P 1/2 →²P 3/2 ) laser at 1.315 μm

Modeling study of vibrational photochemical isotope enrichment. [HBr + Cl/sub 2/; HCl + Br/sub 2/]

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Laser-initiated chemical reactions: total absolute reaction rate constants for Cl+ HBr and Cl + HI

Cited by 37 publications

References 10 publications

A Spectroscopist's View of Energy States, Energy Transfers, and Chemical Reactions

A Spectroscopist's View of Energy States, Energy Transfers, and Chemical Reactions

New chemically pumped I(2P 1/2 →2P 3/2 ) laser at 1.315 μm

Modeling study of vibrational photochemical isotope enrichment. [HBr + Cl/sub 2/; HCl + Br/sub 2/]

Contact Info

Product

Resources

About

New chemically pumped I(²P 1/2 →²P 3/2 ) laser at 1.315 μm