PC GAMESS/Firefly-related discussion club

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Alex Granovsky
gran@classic.chem.msu.su

>My initial idea is to follow IRC along all vibrations of the starting molecule. Most vibration probably would not result in a decomposition under these conditions and I would concentrate on those with activation energy under 1000 K. Do you think this is reasonable? Would I miss some paths this way?

Just my two cents:

The idea isn't too bad, however you do can miss some pathways of
decomposition. The unimolecular decay is usually a complex process,
which includes bimolecular activation stages (e.g., well-known
RRKM theory is one of the  possible theoretical approaches to
unimolecular reactions) and then the redistribution of
vibrational energy.

Another point is that you need to be able to describe barriers
of different pathways of decomposition within approximately the same
accuracy...

Best,
Alex Granovsky