As. Rodgers, CONSERVATION OF ANGULAR-MOMENTUM IN RRKM THEORY - A 3-DIMENSIONAL MODEL FOR NONLINEAR MOLECULES, Chemical physics letters, 219(3-4), 1994, pp. 297-302
The ''usual'' implementation of the unimolecular rate constant in RRKM
theory treats nonlinear molecules as pseudo-diatomics and thus does n
ot conserve total angular momentum. A three-dimensional model for cons
ervation of total angular momentum for vibrator transition states with
the K rotational quantum number either active or adiabatic is present
ed and a comparison made between this model and the ''usual'' one in t
he low-pressure limit for two different reactions. This showed that th
e three-dimensional model resulted in significantly larger rate consta
nts when the K rotor was active, indicating the importance of conserva
tion of total angular momentum.