Numerical analysis of the "impossible kinetics" in flash absorption spectroscopy

1985 ◽  
Vol 89 (22) ◽  
pp. 4844-4848 ◽  
Author(s):  
Yongchun Tang ◽  
Jared A. Butcher
Keyword(s):  
Numerical Analysis ◽  
Absorption Spectroscopy ◽  
Flash Absorption Spectroscopy

A laser flash absorption spectroscopy study of Anabaena sp. PCC 7119 flavodoxin photoreduction by photosystem I particles from spinach

FEBS Letters ◽  
1992 ◽  
Vol 313 (3) ◽  
pp. 239-242 ◽  
Author(s):  
Milagros Medina ◽  
Manuel Hervás ◽  
José A. Navarro ◽  
Miguel A. De la Rosa ◽  
Carlos Gómez-Moreno ◽  
...  
Keyword(s):  
Absorption Spectroscopy ◽  
Photosystem I ◽  
Laser Flash ◽  
Spectroscopy Study ◽  
Flash Absorption Spectroscopy ◽  
Anabaena Sp

Photochemistry of the o-nitrobenzyl system in solution: effects of distance and geometrical constraint on the hydrogen transfer mechanism in the excited state

1991 ◽  
Vol 69 (8) ◽  
pp. 1193-1200 ◽  
Author(s):  
D. Gravel ◽  
R. Giasson ◽  
D. Blanchet ◽  
R. W. Yip ◽  
D. K. Sharma
Keyword(s):  
Excited State ◽  
Triplet State ◽  
Molecular Mechanics ◽  
Absorption Spectroscopy ◽  
Structural Parameters ◽  
Hydrogen Abstraction ◽  
Hydrogen Atom Transfer ◽  
Structural Constraints ◽  
Excited Triplet ◽  
Flash Absorption Spectroscopy

Two rigid nitrobenzene derivatives, 5-nitro-1,2,3,4-tetrahydro-1,4-methanonaphthalene (6), and 5-nitro-1,2,3,4-tetra-hydro-1,4-ethanonaphthalene (7), have been synthesized and studied by picosecond flash absorption spectroscopy, steady-state irradiation, and MMX molecular mechanics calculations. Transients with lifetimes of 770 and 410 ps have been detected and assigned to the excited triplet states of 6 and 7, respectively. Consistent with prediction, the o-quinonoid intermediate is not detected in the time domain between the laser excitation and the end of decay of the triplet state. Intramolecular abstraction of the bridgehead benzylic hydrogen by the cited triplet state proceeds with relative rates of 1:125 for 6 and 7, respectively. Since structural constraints prohibit the formation of an orthoquinonoid intermediate in these systems, formation of the usual nitrosoalcohol 13 represents the first substantiation of the biradical route to product (3′ → 4, Scheme 1). Absorption of the intermediate triplet biradical resulting from hydrogen abstraction by the triplet excited state was not observed, and is therefore believed to be either very weak in the 400–700 nm region, or located outside the detection region. The kinetic results together with structural parameters determined by molecular mechanics show good correlation between structure and reactivity. Hydrogen atom transfer can proceed at up to 53° deviation from linearity of the C—H—O nuclei, with transfer rates decreasing sharply as the [Formula: see text] distance increases from 1.3 to 1.6 Å. It is suggested that the conditions of the reaction from the excited triplet state meet those required for a hydrogen tunneling mechanism. Key words: o-nitrotoluene photorearrangement, mechanism of; o-nitrobenzyl systems, mechanism of photorearrangement; [Formula: see text] distance, influence of, in hydrogen abstraction mechanism; picosecond flash absorption spectroscopy study of o-nitrobenzyl photorearrangement; radical pathway to product in o-nitrotoluene photorearrangement.

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