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By Margaret Robson Wright

The strange process of this article supplies ultimate honors and post-graduate scholars a transparent and explanatory account of 1 of the “harder” parts of actual chemistry. the writer takes care to supply targeted verbal rationalization of the ideas and their value including complete causes of the mathematical advancements. Her reasons are a vital and important function of the textual content, that's scholarly, lucid and well-written with a mixture of intensity of insurance and readability which is helping scholars to paintings via on their own.

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L.. ,0 0 ::;· -=cs· sum over all quantum states i vibration for all modes of a molecule ~ v is the fundaq_i_ental vibration frequency for " i cr' = symmetry number for the internal rotation. I' is the moment of inertia for the internal rotation found from spectroscopic data N II) n{t-exp 1 ( ~d all modes =- 0 v1 are the various fundamental vibration frequencies for the vibrational modes of the molecule ;: ~ .... 0 ~ -= f') cs· j Number of vibrational modes for a linear molecule = 3N-5 Number of vibrational modes for a non-linear molecule = 3N-6 Number of vibrational modes for a non-linear molecule with x internal rotations 0 ....

C. C. C. C. Atom + linear QxQyz q,31/ 3 Aq, Bq, ~ A q, Ill 3 2 q,'fr 3 M qtf/fv3N-5 :s ~. C. 3N-3 AC · · qtJr v A s· :s ~ 0 "'I '< q,3fr3fv3N- 4 qt3qt3 fr3 fv3N-6 KkT &__2 h qt3 10-15 - 10-14 tJrJv A. C. q/_{,3fv w 1 where N = N + 1 . 3 3r3N-4 .. C. C. C. C. f/J}"'-1 where N' = N + N . C. t}N-5 -.... 0 =N+N : I" . C. C. C. -= qt3 fr3 fv3N - 7 KkT qt3 fr3 fv3N- 6 h I 0 .... C. j::. OTHER EXAMPLES BEING CALCULATED SIMILARLY Basic transition state theory 42 [Ch. 1 Reaction of two atoms, A and B, to give a linear diatomic activated complex A + B ~ AB" ~ product where 3 qt3 q1 there are no rotations or vibrations for an atom q/ J,2 a diatomic species has two rotations, and the activated complex has one vibration less than the corresponding diatomic molecule.

1 gives the standard fonns for each individual partition function. trans= "L.. exp(-/;I' (2rtmkn 312 v h Quantities involved other than universal constants and temperature m = mass of molecule sum over all quantum states i r -= fl> ;:;· rotation: linear molecule hot = L exp(- Ek';'. ) 8n 2 IkT cr CJh2 = rotational symmetry number I = moment of inertia found from spectroscopic data sum over all quantum states i -------------------------------------------------------------------------------------------------------------------------------------------------------------------------------· rotation: non-linear molecule hot = L exp(- E;;) sum over all quantum states i 87t 2 (87t 3 I Al nlc )112 (kT)312 ah 3 cr = rotational symmetry number Dl -= ~.

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