Temperature Dependent Part kTR of the Reaction Rate


The temperature dependent part
kTR of the reaction rate is given by

                                                                kTR = k(T) - k(T = 0) - kTG(T) ,

where
k(T) is the measured acridine T1 triplet state decay rate and kTG(T) ist the intramolecular triplet to ground state decay rate at
temperature T.

In the limit  of low temperatures k(T = 0) = kTR(T = 0) + kTG(T = 0) = 13.88 s-1 (ODMR data point at 1.5 K)
with kTG(T) = 28.75 s-1exp(-501.5 K/T) (from acridine-d9 data in fluorene-d8D2 below 200 K)


For the H-transfer a value of kTR(T = 0) = 1.25 s-1  could be evaluated separately from the low temperature  (< 200 K) pressure dependent measurements. For the D-transfer this was not possible, as in this case kTR(T = 0) is expected to be substantially  smaller.

To obtain the complete H-transfer reaction rate
the value of kTR(T = 0) = 1.25 s-1 should be added to the temperature dependent rate data kTR presented here.

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