Hydrogen energy transfer

Another near resonant process is important in the hydrogen fluoride laser, equation (A3.13.37), where vibrational to vibrational energy transfer is of interest ... 

Kreutz T G and Flynn G W 1990 Analysis of translational, rotational, and vibrational energy transfer in collisions between COj and hot hydrogen atoms the three dimensional breathing ellipse model J. Chem. Phys. 93 452-65... 

Stephenson J C, Finzi J and Moore C B 1972 Vibration-vibration energy transfer in C02-hydrogen halide mixtures J. Chem. Phys. 56 5214-21... 

A photoinduced hydrogen atom transfer in cw-l-(2-pyrrolyl)-2-(2-quino-line)ethene was reported (94JA3171).The rate eonstant A (5 —> 4) increases with increasing temperature from 2.1 10 s at 15.8°C to 7.7 10 s at 39.5°C, giving an aetivation energy of 9.4 keal/mol. 

Ne is metastable neon produced by electron impact. Ne transfers its excitation to hydrogen molecules. The hydrogen molecules participating in these energy transfer collisions are produced in highly excited preionized states which ionize after a time lag sufficient to permit the initial neon and hydrogen collision partners to separate. The hydrogen ion is formed in the v = 5 or 6 quantum states and reacts with a second neon... 

Photo-induced Diels Alder reaction occurs either by direct photo activation of a diene or dienophile or by irradiation of a photosensitizer (Rose Bengal, Methylene Blue, hematoporphyrin, tetraphenylporphyrin) that interacts with diene or dienophile. These processes produce an electronically excited reagent (energy transfer) or a radical cation (electron transfer) or a radical (hydrogen abstraction) that is subsequently trapped by the other reagent. 

Similarly, energy-transfer processes, together with electron transfer and hydrogen abstraction reactions could be induced in poly(organophosphazenes) in an intramolecular way by preparing POPs geminally substituted at the same phosphorus with two different substituent groups. 

Figure 5-3. Active site and calculated PES properties for the reactions studied, with the transferring hydrogen labelled as Hp (a) hydride transfer in LADH, (b) proton transfer in MADH and (c) hydrogen atom transfer in SLO-1. (i) potential energy, (ii) vibrationally adiabatic potential energy, (iii) RTE at 300K and (iv) total reaction path curvature. Reproduced with permission from reference [81]. Copyright Elsevier 2002...

Other supramolecular structures such as dendrimers have also been synthesized with zinc-containing porphyrins. Sixteen free base and sixteen zinc porphyrin units were added at the fifth generation of dendritic poly(L-lysine) and intramolecular fluorescence energy transfer was observed.823 Assembly of supramolecular arrays in the solid state has been achieved with the incorporation of an amide group for hydrogen bonding. Zinc meso-tetra(4-amidophenyl)porphyrin... 

The original stabilizer (HBC) was modified as the rapid radiationless deactivation of the stabilizer is (at least partly) due to the intramolecular hydrogen bond, the H-atom was substituted by a methyl group (MBC). This "probe molecule" showed fluorescence and phosphorescence and enabled us to demonstrate the energy transfer to the stabilizer, simply by studying its sensitized luminescence. 

While we used the probe molecule to investigate the energy transfer by sensitized phosphorescence we now turn to the stabilizer itself (e.g. TIN with an intramolecular hydrogen bond) to study its deactivation in the excited states. 

Fig. 13 Energy diagram of hydrogen atom transfer of HBO (above) and HBT (below) (reprint from ref. [108], Copyright 2002 Royal Society of Chemistry)...

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