Carbon vibrational energy transfer

Sharma R D and Brau C A 1967 Near-resonant vibrational energy transfer in nitrogen carbon dioxide mixtures Phys. Rev. Lett. 19 1273-5... 

Yardley J T and Moore C B 1967 Intramolecular vibration-to-vibration energy transfer in carbon dioxide J. Chem. Phys. 46 4491-5... 

The dynamics of fast processes such as electron and energy transfers and vibrational and electronic deexcitations can be probed by using short-pulsed lasers. The experimental developments that have made possible the direct probing of molecular dissociation steps and other ultrafast processes in real time (in the femtosecond time range) have, in a few cases, been extended to the study of surface phenomena. For instance, two-photon photoemission has been used to study the dynamics of electrons at interfaces [ ]. Vibrational relaxation times have also been measured for a number of modes such as the 0-Fl stretching m silica and the C-0 stretching in carbon monoxide adsorbed on transition metals [ ]. Pump-probe laser experiments such as these are difficult, but the field is still in its infancy, and much is expected in this direction m the near fiitiire. 

Figure C3.3.12. The energy-transfer-probability-distribution function P(E, E ) (see figure C3.3.2 and figure C3.3.11) for two molecules, pyrazine and hexafluorobenzene, excited at 248 nm, arising from collisions with carbon dioxide molecules. Both collisions that leave the carbon dioxide bath molecule in its ground vibrationless state, OO O, and those that excite the 00 1 vibrational state (2349 cm ), have been included in computing this probability. The spikes in the distribution arise from excitation of the carbon dioxide bath 00 1 vibrational mode.

Electronic excitation from atom-transfer reactions appears to be relatively uncommon, with most such reactions producing chemiluminescence from vibrationaHy excited ground states (188—191). Examples include reactions of oxygen atoms with carbon disulfide (190), acetylene (191), or methylene (190), all of which produce emission from vibrationaHy excited carbon monoxide. When such reactions are carried out at very low pressure (13 mPa (lO " torr)), energy transfer is diminished, as with molecular beam experiments, so that the distribution of vibrational and rotational energies in the products can be discerned (189). Laser emission at 5 p.m has been obtained from the reaction of methylene and oxygen initiated by flash photolysis of a mixture of SO2, 2 2 6 (1 )-... 

Srinivasan122 has shown that the hydrogen atom transferred to the carbonyl carbon comes from one of the two carbon atoms in the 2 positions. Formation of the pentenal appears to be favored at low vibrational energies since the addition of foreign gas improves the yield which is, nevertheless, always small. Reactions (159) and (160) are the classical steps proposed by Norrish and his coworkers and they are found also with the perfluorocycloketones123. 

Chandler DW, Ewing GE. Transfer and storage of vibrational energy in liquids liquid nitrogen and its solutions with carbon monoxide. J Chem Phys 1980 73 4904-4913. 

Anex D S and Ewing G E 1986 Transfer and storage of vibrational energy in liquids collisional up-pumping of carbon monoxide in liquid argon J. Phys. Chem. 90 1604-10... 

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