THERMAL DISSOCIATION AND RECOMBINATION

OF POLYATOMIC MOLECULES
J. TROE
Institut de Chimie-Physique de l'Ecole Polyteehnique Fddtrale, Lausanne, Switzerland
Experimental data and theories of dissociation-recomblnation reactions of polyatomic
molecules are discussed. The relation between low pressure rate constants and energy transfer
is analyzed. Simple expressions for reduced fall-off curves are derived. A statistical model for
high pressure rate constants and for cross sections of bimolecular reactions involving long-lived
intermediates is presented.
Introduction
Dissociation reactions of polyatomic molecules
and the reverse recombination reactions of atoms,
radicals and molecules play an important role
in many combustion systems as well as in atmos-
pheric chemical dynamics. Due in part to the in-
tensive work in these two fields, these processes
are now fairly well understood for a wide variety
of conditions. Temperatures in the range of
10s-104 ~ pressures from fractions of a Torr up
to 1000 atm, and the influence of many different
inert gases have been investigated. In addition,
experiments involving optical, chemical or other
activations have been conducted. Parallel to
experimental progress, theories have been de-
veloped to a point where extrapolations, inter-
polations and predictions of rate consta~lts are
possible with a fair degree of confidence. This
review gives a brief description of the present
state of the art.
Bas i c React i on S c h e me
In the simplest case, the mechanism of a dis-
sociation-reeombination system can be charac-
terized by the simple colllsional activation-
deactivation and dissociation-association se-
quence
A+M~.,~-A*+M (1)(-1)
A ~ , ~ B + C ( 2) ( - 2)
With quasi-stationary A*, this leads to a first
order dissociation rate constant
= k~[MJ{ k ~/ ( k r { - L~[ M] ) } , (3)
and a second order recombination rate constant
- - [ - ( 1 / [ B ] [ C ' ] ) ( d [ ' A ' ] / d t ) = k r eo
= L2{ k - l E M J / ( k 2 + k - l ~ 3 ) b ( 4 )
Equations (3) and (4) apply to the initial stages
of the reaction when the reverse recombination
(for dissociation), or dissociation (for recombina-
tion), are still negligible. If measured under the
same conditions, according to Eqs. (3) and (4)
the ratio of kd~ and kreo is given by
kdi~/kreo = kl~2/k_lk~-2. (5)
According to the principle of detailed balancing
this is, at least in a first approximation, equal to
the equilibrium constant
kd~/ kreo~(CB' ][CJ/ EA' ]). u=K~. (6)
A g a i n u s i n g t h e p r i n c i p l e o f d e t a i l e d b a l a n c i n g ,
i n t h e l o w p r e s s u r e l i m i t E q s . ( 3 ) a n d ( 4 ) g i v e
k d , ~ . o = h F M] ~ ( [ A * J / [ A l ) ~ k - ~ [ M] , (7)
667
668 ELEMENTARY REACTIONS
a nd
--~(EA*J/EB]ECJ)~qk_,[M]; (8)
i n t he hi gh pressure limit,
I c a i ~ . , = ( k { k _ ~ ) ] ~ = ([A*J/[AJ)~qk~, (9)
a nd
k . . . . . = k_~= ( [ A _ * ] / [ ~ ] ~ c ] ) o ~ . (1o)
The "fal l -off r ange" bet ween t he t wo l i mi t i ng
r at e cons t ant s is most conveni ent l y represent ed
usi ng a dimensionless pressure scale
k a i ~ s , o / k a ~ , ~ = ~ [ M J / k s = k ~ , o , / k . . . . . . (11)
Wi t h t hi s pressure scale,
~diss ,0/kdiss ,~
kdisa./kdi~.~: 1 +kdi,s.0/~di . . . . (12)
and
k~,o.,/k . . . . . 0 3 )
]Cree,lkrec., l_~_krr ~
At t he " cent er of t he fall-off cur ve" [' M]r where
k d i , ~ . o / k d i ~ . ~ = 1, t hi s gives k d k , / k a i . , , ~ = 0 . 5 .
I t shoul d be emphasized t h a t t he mechani sm
(1), (-1), (2), (-2), and Eqs. (3)-(13) ar e onl y a
first appr oxi mat i on. On t he one hand, t he basic
(mechani sm ma y be different 1I: like for di at orni c
molecules, t he complex mechani sm Aq - M~ -
BM+ C, BM~.-~-Bq-M in some cases ma y pl ay a
cert ai n role; addi t i onal react i on st eps ma y ent er
i nt o t he mechani sm, e.g., a change of electronic
st at e i n spi n-forbi dden react i ons. On t he ot her
band, t he mechani sm (1), ( - t ) , (2), (-2) i n
r eal i t y is composed of a l arge number of single
processes i nvol vi ng many di fferent i ndi vi dual
st at es of A, B, and C; t herefore t he formal r at e
const ant s kl, k- l , k2, and k-2 can have a r at her
cempl i cat ed meani ng.
Nevert hel ess, experi ment s at t d t heori es are
classified mos t conveni ent l y in t er ms of Eqs.
(3)-(13). Therefore, one must consi der t hr ee basic
quant i t i es:
(i) t he l i mi t i ng low pressure r at e const ant s (7)
and (8), and t hei r dependence on t he t emper at ur e
and on t he i n e r t gas M,
(it) the l i mi t i ng hi gh pressure r at e const ant s
(9) and (10), and t hei r dependence ou t he tern-
per at ur e (eventually, a t ver y hi gh densities, on
t he densi t y and t he medi um M),
(iii) t l m "r educed fall-off ct~rves" (12) and
(13), i.e., / " - - / whi ch
kdiss/kdi~,~--f(kdiss.(}/kai~.m),
i nt er pol at e bet ween kdi~,0 and kai~.| and t hei r
dependence on t emper at ur e, pressure and M.
I n t he following we shal l give some e.xperi-
ment al e xa mpl ~ of t he above t oget her wi t h some
references t o rel at ed syst ems wi t h nont her mal
act i vat i ons; t hen, more det ai l ed t heori es for (i),
(it), and (iii) will be presented.
Experimental Examples
The series of spin-allowed di ssoci at i on-recom-
bi , a t i ons N( G~ NO+ O, NOa ~ NO2 q - O, HN0 3 ~
O H + N O 2 , C H 3 N O : ~ - C H . ~ q - N O ~ , C ~ H ~ - C H ~ q -
CH3, and t he t wo spi n-forbi dden r eact i ons
and
c o ~ ( ' E ) ~ c o ( ' E ) + o( ~e)
are chosen as examples. For t h e e react i ons, some
selected d a t a on low pressure l i mi t i ng r at e con-
s t unt s (i) ar e shown in Tabl e I, on hi gh pressure
l i mi t i ng r at e const ant s (it) i n Tabl e I I , and on
i nt er medi at e fall-off curves (iii) in Tabl e I I I .
The da t a ar e al ways present ed i n t he dissocia-
tion and t he r ecombi nat i on versi on [ us i ng Eq.
(6), for i t s val i di t y see e.g., Ref. 1]. The gi ven
r eact i ons of molecules wi t h 3- 8 at oms have been
accessible a t l east in a sufficiently br oad pa r t of
t he fall-off curve. The da t a of Tabl e I I I i ndi -
cate, wi t h i ncreasi ng compl exi t y of t he mole-
cules, how t he cent er of t he fall-off cm-ve shi ft s
t owar d l ower pressures. For l arge molecules,
olfly t he hi gh pressure end of t he fall-off curve
becmnes accessible, and a n ext r apol at i on t o t he
low pressure l i mi t is difficult. Under nor mal shock
wave condi t i ons ( ~1000~ ~' 1 at m) , for i n-
s t a nc e s t he cent r al par t of t he fall-off curve is
observed in CHsN02 decomposi t i on; mar ked fall-
off still is observabl e in C2H~N02 decomposi t i on;
wi t h C~HTN02 j ust a 50% change of t he r at e con-
s t a nt is meusured when t he pressure vari es by a
f act or of 10; t he decomposi t i on C~H~3N02-"*
C~H~3+N02 is essentially first order. For l arge
molecules, onl y t he l i mi t i ng hi gh pressure r at e
coust ant s ar e known and ext ensi vel y t abul at ed. ~
I n t he present paper we shall concent r at e on
smal l er molecules t o see t he compl et e fall-off
behavi or.
Ther mal di ssoci at i on- r ecombi nat i on r eact i ons
shoul d al ways bc considered i n commct i on wi t h
non- t her mal act i vat i on systems. For t hi s reason
THERM.td~ DISSOCIATION OF
we have added a brief summary of references to
experiments which are directly related to the
reactions reported: NO=.--Information on energy
transfer iu this reaction is also obtah~ed tYom
fluorescence 4d and radiative recombhmtion.~ Pho-
tolysis lifetimes, because of strong mixing of elec-
tronic states, are related to ~ of the ground
state. 4r Thermal cnrission in the visible during
dissociation +~ monitors population of excited
states. Data on (ke, k~) correspond directly to
OI8~-NO 1~ isotope exchange ~h and O-+-NO (v= 1)
vibrational relaxation. ~~ NOz--Again high pressure
recombination (k_2) and isotope exchange O~S+
N(~=, ~ arc directly related. ~h The reactions O+
NO~-:+NO~ and O+NO2--+NO+Ox have been
shown not to involve a common intermediate
structure. ~ For HNO~ and CeH~ dissociation quite
a number of related reactions exist., although they
have not been verified in detail, e.g., HNO~-~II-t -
NOn, H+NOa~.~-OH+NO.~, NO+HO~OH+
NO2, H+ C.~H~.-~CH~+ CH~, CH~+ CH, ~CI I s +
CHa, etc. N~O--(k~, k ~) here include a sh~glet-
triplet transition probability whose order of mag-
nitude corresponds to the spin-orbit splitting of O
atoms2" Electreulc deactivation OQD)+N~--+
O(at' )+Ne, '~b and spin-allowed stabilization
O(tD)+N2--+N~O, ~* involve elementary steps
similar to N20--+Ne+O(~I'), whereas vibrational
relaxation O(~P)+N~ (v= 1)---+O(*P)+N,., (v= O)
apparently does not depend on processes which
are rate determining in dissoeiatiou2 d Whereas
the recombination O(aI')+N~--+N~O involves art
energy barrier of about 25 kcal tool -~, the energy
barrier for O('~P)+CO--+CO~ probably is only
about 5.5 kcai tool -i. Therefore, radiative re-
combination O+CO TM and isotope exchange O:S+
CO ~ (Ref. 10g) arc directly related to C(5~;:
CO-}-O. Furthermore, eleetroulc deactivation
O(~D)q-CO--+O(aI')-t-CO (Ret'. 1Oh) and vibra-
tional relaxation Oq-CO (v= 1), l~ involve similar
partsof {he COz singlet-triplet surfaces as C(5~.~-
COq-O.
In addition to these special considerations, the
general development of thermal activation sys-
tems rmts parallel to progress in chemical activa-
tion, optical activation, analysis of mass-spec-
trometriea] fragmentations and bimolecular re-
actions involving longlivcd intermediate com-
plexes in molecular beams (see below).
Limiting Low Pressure Rate Constants
At the low pressure limit, dissociation and re-
combination are collision determined, and the
effective rate constants kl and k_l of eollisional
activatiomdeactivation arc cssential, if the in-
dividual steps summarized by Eqs. (1) and (-1)
POLYATOMIC MOLECULES 669
are resolved, and if the states of A are distin-
guished by the index i, the dissociation at the
low pressure limit is described by a master equa-
tion with a totally ab~rbi ng barrier at the thresh-
old energy Eo,
dEA~3/dt= ~ k~jFM]['Aj~-- Y~ kJ - M] [ A~
E~.<Eo Er (14)
The rate eotmtants k~: for collisional energy trans-
fer from state i to state j can be represented iu the
fornl
kji = (~kji)(kr (15)
5 i
with a total energy transfer rate constant Z~ and
a collisional transition probability Pj~. Different
from diatomic molecules, the number of state~ i
involvcd in the reaction in polyatomie molecules
is so large that ia the near future no cmnp]ete set
of kj',, and no complete solution of the system of
differe~ttial equations will be av,'filable. For this
reason, one must construct models for Zi and
Ply. Either one nmst combine groups of states i
into a small number of quasi-levels, and solve
the system of coupled differential equations for
these quasi-levels, or one has to "smooth the
i states" and replace Eq. (14) by one integral
equation. Both methods have their merits. The
former works equally well with arbitrary sets of
pj . u the latter provides artalyticaI solutions for
selected models of pj~.t2,~a Exponential models
for Pi~', which peak at E~=Ej or at E~E~,
because of their mathematical simplicity, arc
pat"dcnlarly useful. ~3
i n solving Eq. (14) several points must be
noted. For polyatomic molecules "incubation
periods" with coupling of dissociation and vibra-
tioual relaxation ale difficult to observe. There-
fore, quasistationary (or steady-state) popula-
tioim FA,.J can be assumed for practically all
experiments available. Further, detailed bManc-
ing for the kj~ has to be included in each model,
i.e.
k,~f~=k~.f~ (16)
with the equilibrium populatio~ls fi=([AiJ/
~[Ai])(.q. Finally, the total rate constants k~i~,.0
obtained depend markedly on the average energies
(AE} transferred per collision; however, for
the same (AE), they depend only slightly on
the detailed shal>e of Pr For this reason, the
exponential model of Pii provides a particularly
usefnl basis. In this model, for deactivating col-
lisions
Pj~*: exp[--(E~--E~)/a] at Ej<E~,
(17)
670
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r' ~7
~ r
r~
ELEMENTARY REACTIONS
7
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&
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T H E R M A L D I S S O C I A T I O N O F P O L Y A T O M I C M O L E C U L E S
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i z z
672 ELEMENTARY REACTI ONS
ca
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7
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7
v
$ $ $ $ ~lg
4 N g
A i A I Z i A i
O Z
Z +
0 0 +
+ + 9
THERh~AL DI SSOCI ATI ON OF POLYATOMI C MOLECULES
v
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9

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673
6 7 4
and t he mean energy ( AE) t r ansf er r ed m act i -
vat i ng and deact i vat i ng collisions
(AE)=~(E~--E~)P~-'~--a:/(a+RT). (18)
Y
Fr om Eq. (14), wi t h t he exponent i al model of
Eq. (17), a t E~_Eo a non-equi l i bri um st eady-
s t at e popul at i on dur i ng di ssoci at i on
rA,J/ErA,3=f,{ 1--[RT/ (~+ RT)q
Xexp['(Eo-- EO/RT-] I (19)
is obt ai ned. A depl et i on r ange of t he wi dt h RT
is observed below/~0. For t r ans i t i on probabi l i t i es
whi ch for exampl e peak a t E~<E~, t he depl et i on
r ange can be br oader ) ~ Wi t h t he popul at i on of
Eq. (19), f or small pol yat omi c molecules one
obt ai ns t he r at e const ant
I~e~i~,o ~--[MJZ(p(Eo) RT/Q)
X exp(--Eo/RT)[a/(a"}-RT)] ~ (20)
where Z=Z~ ( at E~. E6) is t he t ot al r at e con-
s t ant f or collisional energy t ransfer of molecules
near Eo. p(Eo) is t he densi t y of st at es, and Q is
t he par t i t i on fi mct i on. For l ar ger molecules,
Eq. (20) is j us t t he first t e r m of a series, and kd~.0
ma y be represent ed by
kdi~s,O = [M]~Zfe~f(E)dE
= E M ?~oZ s o x p ~ - ~ / ~ r ) ~ (2 1 )
where t he "col l i si on ef f i ci ency"/ ~ for t he exponsn-
t i m model is gi ven by a
[ O/ \ 2 [ ' * - - 1 / 8 - 1 \
(I_F. Ez~I-' (RTh"( a ~'2
x, ~o/ kZ/ \ ~) j
9 - 1 s- - 1 ,_ _~
L , ~ \ , / \ o/ \ E o / J
( s = n u mb e r of oscillators, Ez = z e r o ener gy
poi nt ) . The anal agy bet ween t he r a t e const ant
(21) and t he si mpl e model (7) is qui t e evi dent :
([-A*]/I-A])~ a corresponds t o
f ~ f (
E)dE,
ELEMENTARY REACTIONS
k-l[-M' l corresponds t o ~ Z[ - M] . I n t he old
" s t r ong collision" model, one assumed a>>RT
and Be= 1.
The exper hnent al propert i es of/;di~,o and k~, 0
can be well under st ood i n t er ms of Eqs. (20)-(22) :
(a) Collision effleiencies. As t her mal dissocia-
t i ons a t t he l ow pressure l i mi t are r at e det er mi ned
by coffisional energy t ransfer, t he y offer a most
di rect access t o energy t r ansf er . However, t o
obt ai n B~Z f r om ka~,0, accur at e cal cul at i on of
f : f ( E)d E
is requi red. Due t o uncert ai nt i es in anhar moni cl t y
and r ot at i onal cont r i but i ons (see below), t he
accur acy mi ght not be sufficient. Therefore,
st udi cs of rel at i ve collision cfficiencies of ma ny
di fferent .M's in t he same r eact i on of t en are more
useful. The mos t compl et c sets of d a t a are t hose
for NO.~ and NO3 in Tabl e I, t he di ssoci at i on of
NO2 C1 (Ref. 14) and t he i someri zat i on of CHaNC
a nd C,2H~NC. b I n all these cases one observes
t he appr oach of a l i mi t i ng collision efficicncy for
l ar ge pol yat omi c M' s. The most reasonabl e i n-
t er pr et at i on of t hi s obser vat i on woul d be t he
as s umpt i on t h a t f~--~l for a l arge M, and t h a t
Z~'~gas ki net i c collision number i n al most all
cases (except per haps for par t i cul ar l y st r ong in-
t er act i ons wi t h M=H~O or chemi cal i nt er-
act i ons). However, t he i nf or mat i on avai l abl e on
( AE) f r om non- t heml al act i vat i on ( - - ( AE)
<~ 15 kcal tool -1 even for t he most effective M1617)
accor di ng t o Eq. (20) i ndi cat es t h a t fl~ pr obabl y
al ways is bel ow about 0.gM The s t r ong collision
assumpt i on, common t o earlier theories, is gen-
eral l y a n i nadequat e si mpl i fi cat i on. Whencver
collision efficiencies for a sufficiently l arge ~I ar e
avai l abl e, for t he expcri ment al l i mi t of about
( ~ ) ~ x ~ 0 . 9 , ( AE) val ues can be est i mat ed
from Eqs. (18), (20)-(22). At moder at e t emper a-
t ur es ( 30~600~ - (AE)/ RT~0. 3-1 was
f ound f or mono- and di at omi c M, ~ 1 - 3 for 3- 5
at omi c M, > 3 f or Larger M. As in (AE} st udi es
wi t h opt i cal act i vat i on, 17 t hcr e is a pr edomi nant
cor r el at i on bet ween ~ and t he number of at oms
i n M wi t h a n addi t i onal cor r el at i on bet ween fl~
and t he Lem~ard-Jones par amet er e for mono-
and di at omi c M' s. 1T
(b) Absol ut e values. By compar i son wi t h t he
ci t ed comprehensi ve st udi es of collision effi-
eiensies, ~ can be est i mat ed f ai r l y well for a gi ven
M (t he maxi mum var i at i ons of ~ i n general are
bet ween about 0.05 and 0.9). Apa r t f r om t hi s
fact or, kai.,,o is given by t he st r ong collision r at e
cons t ant ~Eq. (21) wi t h fl~= 1] . Toda y excellent
met hods are avai l abl e t o det er mi ne t he densi t y
THERMAL DISSOCIATION OF POLYATOMIC MOLECULES
675
of vi br at i onal st at es, ts For moder at el y complex
molecules, i t can be est i mat ed usi ng
s
p(E) = (E-'l-a(E)Ez)~-I/(s - 1)l~Ir (23)
wi t h 0 < a ( E ) < l and t he qua nt a r of t he s
oscillators. [ For det er mi nat i ons of a(E), when-
ever count i ng is uot feasible, see Ref. 18.3 Wi t h
i nereasi ng number of a t oms i n t he molecule A,
t he f act or p(Eo)RT/Q increases mar kedl y. To
i l l ust r at e t hi s for t he experi ment al e.xamples
gi ven: for nonr ot at i ng NO2 and Cr p(Eo) =
170/ ( kcal reel -1) and 1. 3-10a~ mo l l ) ,
respect i vel y; a t 300~ o(Eu)RT/Q=IO 2 a nd
5. 10 g, respectively. These f act or s ar c mai nl y re-
sponsible for t he var i at i ons of preexponent i al
fact ors of ksi.~,o i u Tabl e I. Addi t i onal cont r i bu-
t i ons arise from anhar moni ei t y correct i ons (e.g.,
see Refs. 18 and 19) and f r om r ot at i on. For a
r ot at i ng non-l i near symmet r i c t op, t he st at es as-
soci at ed t o t he qua nt um number K~ J must be
ful l y included in t he dens i t y of st at es O(E,J)? ~
Fur t her mor e, i n a r ot at i ng molecule, Eo is gi ven
b y t he cent ri fugal barri ers Eu(J) t h a t depend on
t he shape of t he pot ent i al surface a t medi um
i nt er f r agmeut di st ances. As a rule of t humb,
r ot at i onal fact ors are bet ween 1 and (Eo/RT) an.
Therefore, t hey mus t be careful l y anal yzed. 4b.~,21
Gi ven t he act ual knowl edge of moleculax par mn-
eters, st r ong collision r at e const ant s can be
est i mat ed wi t h about 50 per cent accur acy i n t he
best cas ~.
(el A.etivation energies. Accordi ng t o Eq.
(21), t he appar ent act i vat i on energies E,,0 of
kdis~,0 are gi ven by cont r i but i ons from Z ~ and
f r om
~ f ( E)dE.
The Lcnnar d- Jones collision number Z cont ri b-
ut es appr oxi mat el y -{-89 The maxi mum con-
t r i but i on f r om fl~ occurs a t t he weak collision
l i mi t ( - - ( AE) <<RT) where B~ - - ( AE) / RT (or
B~(AE~)/2(RT) 2 as gi ven by tile "di ffusi on
t heor y" , m) Chemi cal a nd opt i cal act i vat i on
st udi es i ndi cat e (AE)cr T~ wi t h pr obabl y --89
a_~-~-89 Therefore, f~ cont r i but es bet ween II and
--~RT. The paxt i t i on f unct i on Q~ib, as det er-
mi ned by t he vi br at i onal frequencies, cont r i but es
--S, n RT = - - U~ i b . Rot at i onal cont ri but i ons
ar e bet ween 0 and --]RT. For l arge molecules,
t he cont r i but i on f r om t he f act or
F= f;~ 5~(E)/p(go)l
X e x p [ - - (E-- Eo)/RT](dE/RT)
has t o be i ncl uded. Wi t h ~----(~E>/ RTo:
T -~l~ and negl ect i ng r ot at i onal cont ri but i ons, a
first r ough est i mat e
E~.o~-Eo"I-RT--Uvlb= Eo--(S~f--1)RT (24)
follows from Eq. (20), i n f ai r agr eement with most
da t a of Tabl e I.
Li mi ti ng Hi gh Pr e s s ur e Rat e Const ant s
I n t he hi gh pressure l i mi t a n equi l i bri um popu-
l at i on of mol ecul ar st at es b y frequent collisions
is established. Thus, kdi~,~ is given by
k |
a~s,| f ' , f(E)k(E)dE. (25)
By di rect anal ogy wi t h Eq. (9), f(E) correspond
t o ( [ A* J / [ A] ) ~, and t he specific r ot e cons t ant
k(E) t o k2. kdi~s,~ can be est i mat ed b y theories
of ver y different degrees of sophi st i cat i on. The
results axe oft en not ver y different, because t he
number of ml known par amet er s of t he pot ent i al
surface is still l arge; oversi mpl i fi cat i ons i n t he
model easi l y can be compensat ed for by changi ng
pot ent i al par amet er s.
(a) The simplest met hod is t o assume t h a t
k d i s s . ~ A~ exp( - - Eo/RT) (26)
(in dissociations wi t hout bar r i er for t he reverse
recombi nat i on, i.e., E~-AHo~ The precxpo-
nent i al f act or A.~ is ext i mat ed by anal ogy wi t h
rel at ed known react i ons. Excel l ent collections of
kdls~.~ are avai l abl e? I n general, A| s -1
for simple bond fission react i ons, A| s - t
for el i mi nat i on react i ons; an aver age singlet-
t ri pl et t r ansi t i on pr obabi l i t y of 10~- 10 "-s has t o
be included for t he spi n-forbi dden dissociations of
t r i at omi c molecules.
(b) Convent i onal t r ans i t i on st at e t heor y gives
k,n~,.~= (kT/h)(Q~/Q) e~.p(--Eo/RT) (27)
A t r ansi t i on s t at e confi gurat i on ~ must be
chosen, separ at i ng t he act i vat ed molecule A*
a nd t he pr oduct B + C cmffigurations. The par t i -
t i on f unct i on of t he act i vat ed complex Q~ is
const r uct ed f r om t he est i mat ed f r equency pa t -
t er n of t hi s confi gurat i on. Ma n y empi ri cal rules
for t hi s procedure have been derived. ~
The usefulness of t r ansi t i on s t at e t heor y
becomes par t i cul ar l y a ppa r e nt when specific r at e
const ant s k(E) axe needed i n syst ems wi t h non-
676 ELEMENTARY REACTIONS
t her mal act i vat i on. Tr ansi t i on s t at e t heory, in
t he versi ons of t he RRKM or t he quasi -equi l i b-
r i um t heor y, gives
k( E)= W~( E) /hp( E). (28)
Wr denot es t he number of q u a n t u m st at es
of t he act i vat ed complex a t energies ~ E. W r
is rel at ed t o Qr by
f ~
Q~=/Eo W~(E) e xp[ - - ( E- - Eo)/ R T] ( d E/ RT)
( 2 9 )
I n t he si mpl est appr oxi mat i on, wi t h a( E) = 1, t he
combi nat i on of Eqs. (23) and (28) gi ves
k( E)~(~__d,~/l~z,d')[ ( E- - Eo~- Ez~) / ( E + Ez) ] ~-1
~ (30)
wi t h t he frequencies u ~ and t he zero poi nt energy
Ez ~ of t he act i vat ed complex. Kassel ' s classical
versi on wi t h Ez " = Ez=O is not appl i cabl e i n
most cases.
(c) Wi t h i ncr easi ng progress i n our knowl edge
on t he pr oper t i es of pot ent i al sm' faces a t medi um
i nt er f r agment distances, si mpl e t r ans i t i on st at e
t he or y oft en becomes insufficient. One cent ral
quest i on concerns t he posi t i on of t he act i vat ed
complex, i.e., t he bot t l e-neck s epar at i ng equilib-
r i um popul at i ons of r eact ant s A* and non-
equi l i bri um popul at i ons of pr oduct s B- ~C. Cal-
cul at i ons of t he local ent r opy, t he local densi t y
of st at es or of bi~(E,q) al ong the r eact i on pa t h
q, show t h a t t hei r mi ni ma for si mpl e bond
fission r eact i ons do not coincide wi t h t he centri-
fugal maxi ma. ~s,~4 Thus, act i vat ed complexes for
a gi ven pot ent i al surface ar e r el at ed mor e rea-
sonabl y t o t he pl aces q~, where
W~( E, q) = mi nl mum a t q=q~. (31)
Oim obt ai ns 2~ energy dependent posi t i ons of
act i vat ed complexes, energy dependences of
k( E) di fferent f r om t he i ni t i al use of Eq. (30) be-
cause of ener gy dependent yd' ( El , and conse-
quent l y act i vat i on energies E , . , whi ch ar e often
smaller t ha n given b y convent i onal t r ansi t i on
st at e t heor y. The l at t er effect possi bl y is re-
sponsible f or probl ems of i nt er pr et i ng t he C2H6~-
2CII~ act i vat i on energies wi t h one act i vat ed
complex, s
(d) Tr ans i t i on st at e t heor y ma y be under-
st ood as a simplified version of a general qua nt um
scat t er i ng t heor y (e.g., see Ref. 25,) i n which
pa r t of t he difficult dynami c probl em is replaced
by st at i st i cal post ul at es. I n fact , one can t r y
t o represent t he dissociation by a first st r ong
coupl i ng peri od of many di fferent co~ffi~u' ations
followed b y a n adi abat i c t er mi nat i on of t he ~
act i on i n i ndi vi dual specific r eact i on channels.
The aver age t i me t o ent er a special confi gurat i on
dur i ng t he first period is appr oxi mat el y gi ven
by t he mean recurrence t i me of one st at e in a
set of coupl ed st at es (e.g., see Ref. 26)
r = hp(E, J) (32)
At a gi ven ener gy E and t ot al angul ar mome nt um
J (i nel udhl g event ual l y s ymme t r y propert i es), a
cer t ai n number W(E, J) of specific r eact i on chan-
nels ar e open for au adi abat i c r eact i on from t he
r e a c t a nt st at es i nt o pr oduct st at es. Ot her chan-
nels are closed because of t oo hi gh ener gy bar -
ricrs. Assumi ng equal st at i st i cal wei ght for all
react i on channels, arat t r ansmi ssi on coefficients
of 1 for all open react i on chamlels, t he specific
r at e const ant s are given by ~~
k(E, . / ) ~ W( E , J) / hp( E, J) (33)
The di r ect anal ogy t o Eq. (28) is qui t e evident,
al t hough W( E, J) is not rel at ed t o a par t i cul ar
act i vat ed complex confi ~i rat i on, i nst ead, wi t h
a gi ven pot ent i al surface, t he adi abat i c r eact i on
channel s correl at i ng all i ndi vi dual r e a c t a nt and
pr oduct st at es have t o be cal cul at ed, and se-
par at ed i nt o open and closed ones. ,~1 essential
advant age of t hi s appr oach is t he possi bi l i t y of
st r i ct l y irtc]uding conservat i on of t ot al angul ar
mome nt um and s ymme t r y in each r eact i on chan-
nel3 ~ Appl i ed t o bi mol ecul ar reactiorLs t hi s up-
pr each provi des a general l aat i on of phase-space
t heor y (see below).
The choice between t he models (a) (d) cer-
t ai nl y is di ct at ed by t he avai l abl e knowledge of
t he pot ent i al surface aud t he det ai l s requi red.
Today, met hods (a) and (b) of t en are still ade-
quat e. However , t hi s will cer t ai nl y change i n
t he fut ure.
Reduced Fal l -Off Curves
I n t he limiving low pressure and hi gh pressure
r at e const ant s, collisional ener gy t r ansf er and
specific di ssoci at i on r at e const ant s ar e separat ed.
Bot h component s are coupled i n t he i nt er medi at e
fall-off range. I n t he reduced form, kdiss/kdiss,~ =
f(kai~.o/kai,~.~), t he i nf or mat i on i nher ent i n
t he l i mi t i ng r at e const ant s is account ed for, and
one mi ght t r y t o i nvest i gat e addi t i onal fact ors
THERMAL DISSOCIATION OF
like t he shapes of k(E), P~, i nt ernal coupl i ng
propert i es, etc. However, i n t he reduced form,
fall-o ff curves are ver y fi~sensitive t o t hese fact ors.
Therefore, t hi s possi bi l i t y is not realizable. I n-
st ead, simple expressions f or t he reduced fall-off
curvcs are adequat c in most cxperi ment al si t ua-
t i ons.
I n tim st r ong collision l i mi t , anal ogons t o Eqs.
(3), (7), and (9), kdi~ is gi ven by
k [~ k(E)f(E)k_t[MJdE
~=J~o k ~ M3 (34)
Two par amet er s, SK and B~, can be defined e7 i n
appr oxi mat e expressions f or W'~(E) and p(E)
a t E~ Eo:
W~" (E) :"~[Q'~/" (SK-- 1 ) I l l ( E - - Eo)/ R '1"] zK-~,
(35)
and
p(E)~p(Eo)['I-F(E-- E~)/BKRT] 's,'c-~. (36)
These appr oxi mat i ons and Eqs. (28), (29), and
(34) give a reduced fall-off curve
kdias 1
x zK-1 exp ( - - x)dx
X fo~.t_(kdi~s,| 1
t h a t has t he form of t he old Kasscl i nt egr al s.
Io(SK,BK) is given b y
ro(&,B~:)= ~. (BK'/~!).
The par amet er SK is rel at ed t o t he experi ment al
observabl e E~.| vi a
~K ~S..+(E .,.~- - E o)/RT
=(Uvlb-'[-E~,~--Eo)/RT (39)
The par amet er B~ can bc fixed tt~ing t he rel a-
t i on
where
F( SK,B~:) = F(s,B')
F(S,B) = [-(S-- 1) !/BZ-~]Io(S,B) (41)
POLYATOMIC MOLECULES 677
l - s - n u mb e r of osci l l at ors and B' ~- ( Eo+Ez) /
RT]. If t he t wo Kasscl par amet er s SK and BK
are chosen accor di ng t o Eqs. (39) and (40),
agr eement bet ween RRKM cal cul at i ous and t he
Kassel i nt egral s is ver y good. These i nt egr al s
have been t abul at ed t oget her wi t h t he f unc-
t i ons Io(S,B) a nd F(S,B) in Ref. 27. The follow-
ing example i l l ust r~t es t he devi at i on bet wecn
t he simple model, Eq. (12), and t he di scussed
reduced fall-off curves: for t he di ssoci at i on
[-N~2CI-~N(-).2~- C1] at 455~ (SK ~ 3 and BK
16) i n t he st r ong collision limit, kdi~+/kdi:~,+~--
0.31 at [ M] = [-M]:, 0.63 a t [ M] - 1 0 [ - M] ~ a nd
kdi~:/kai~.o~0.7 at [ M] =0. 1[ - M] ~. Weak colli-
sion effects resul t i n br oadeni ng of reduced fall-
off curves, equi val ent t o a n increase of SK by
about 1.5 uni t s for fl:--~0.1. :~
The accur acy of t he simple Kasscl i nt egr al s
i n reduced fall-off curves, a t t he present s t at e of
t mcert ai nt i es i n k(E), Pi j ctc., is a t ]cast equi va-
l ent t o t ha t of t he t i me consumi ng RRKM c a n
cul at i ons (for Kassel i nt egral s in non- r educed
fall-off curves see also Ref. 28). For these pr ac-
flea] reasuns, reduced Kassel i nt egral s shmdd be
preferred to t he correspondi ng RRKM cal cu-
lations.
Bimolecular Reacti ons Involving
Bound Intermedi ates
I n t he above discussion of experi ment al sys-
tems, several rel at ed bi mol ecul ar react i ons i n-
vol vi ng excited A* molecules as i nt er medi at es
(37) have been ment i oned. These reactions, of course,
shoul d bc anal yzed t oget her wi t h t he t her mal
di ssoci at i on-recombi nat i ou react i on. For bound
inte,~nediates, t hc st at i st i cal theories of uni mol ec-
ul ar processes have t hei r di rect anal ogy in st a-
t i st i cal theories of bi mol ecul ar processes, like
(38) t he phase space t heor y. Ther mal l y aver aged r a t e
const ant s and det ai l ed cross sections are bot h
accessible. I n t he following, we shall i l l ust rat e
i bi s i n t he f r amewor k of t he model (d) described
above [see Eq. (33)].
As example we consider a birnoleclflar r eact i on
B"FC with at omi c C a nd di at omi c B. We assume
t h a t react i on occurs onl y vi a t he f or mat i on of a
st r ongl y coupled i nt er medi at e complex A*. I n a
st at i st i cal t heor y t he f or mat i on of A* aud i t s
decomposi t i on i nt o f r agment s are i ndcpendent
processes. The pr obabi l i t y of formi ng par t i cul ar
(40) pr oduct st at es fl front A*, a t a given t ot al ener gy
E and t ot al angul ar moment um J , i n t he frame-
work of model d) is gi ven by W(E, Jf l ) / W( E, J) .
W(E,J,~) denotes t he number of open adi abat i c
r eact i on channels l eadi ng t o pr oduct st at es t ,
6 7 8 ELEI~IENTARY REACTIONS
W( E, J ) , the total number of open channels. The
total cross section for formation of a strongly
coupled complex A* by quantum mechanics is
given by
~r = [-~r]~:/'2~r ] ~* (2/"F 1 ) (42)
where #, and Et~(~) are the reduced mass and
initial energy of the relative translation of
B-I-C, 1 is the orbital angular momentum and Y~*
counts all l's which lead to the formation of A*.
By using detailed balancing and by considering
the different possibilities of combining orbital
angular momentum l and angular momentum j~
of the diatomic B before collision to a total an-
gular momentum J, as in phase space theory, :~
o~m obtains ~ a specific cross section for the reac-
tion going from reactant state a to product state/~
{Y ( O / ' ~ ) ~ [ - 7 r ~ 2 / ~ . E . . . . . ( a ) ( 2 j . - F 1 ) ] ~ j ( 2 , , r - ~ - 1 )
X [' W( E, J, a) W( E, J f l ) / W( E, J ) ] . (43)
As in eonveutionaI transition state theory, the
numbers of open channels W( E, J, w) , W( E, Jf l ) ,
and W( E, J ) can be obtained by state counting
at suitable activated complexes or critical sur-
faces. However, as in model (d), they can be
more reasonably obtained from counting open
abiabatlc reaction channels.
The detailed cross section (43) can easily be
thermally averaged ~
/ 8 W: f ~ .
X e xp( - - ~) E . . . . ( ~ ) ~ (44)
with the result
K T / h 2 \3~
X 2-~ ~ exp - - - -
X W(E, J, o~)W(E, J f l ) dEt~aa,(a) (45)
W(E#)
where E= E( w) +Et ~, . ( a) = E(fl)+Etr~, , (fl). If
the states ~ or fl are only partially resolved, k (a~--~)
must be averaged further. :For example, vibra-
tional relaxation of NO (~=1) and 02 ( v=l ) in
thermal collisions with O(3P) is calculated 3~ to
have rate constants of about 10 ~8 cm ~ tool -~ s -~
and 2.10 TMcm s mol -~ s -1 at 300~
In these cases, the potential parameters used
have been obtained from dissociation-recombina-
tion reactions. The uncertainty of these param-
eters still prevents a clear decision as to the
adequacy of the statistical postulates used. An
ultimate test will be provided from measure-
ment8 of detailed cross sections (43) in molec-
ular beams. 8~ It is to be expec~d that statistical
theory works equally well for the reactions con-
sidered involving bound intermediates A* (better
at least than for direct bimolecular processes
involving shortlived intermediates. 29)
i n concluding, ene may state Olat a semi-
quantitative analysis of thermal dissociation-
recombination reactions and the related bimo-
lecular reactions involving bound intermediates
is now possible. Further progress depends on
in,proved knowledge of energy trmlsfer in highly
excited molecules, and of potezLtial surfaces at
medium iuterfragment distances.
A c!cnowledgment
Financial support of our work by the Schweizeri-
scher Nationalfonds is gratefully acknowledged.
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680 ELEMENTARY REACTIONS
COMMENTS
W. Forst, Universit~ Laval, Canada. I am i n
full agr s ement wi t h Prof. Tr ee' s view t ha t
el abor at e fall-off cal cul at i ons, usi ng all t he
par apher nal i a of RRK. ~I t heor y, on t her mal
uni nml ecul ar r at e const ant s ar e unwar r ant ed
because of t he i nsensi t i vi t y of fall-off t o var i at i on
of par amet er s. I wish t o poi nt out t h a t i n addi t i on
t o t he suggest ed use of t abul at ed Kassel i nt egral
val ues wi t h a n "effect i ve" number of oscillators,
t her e exists anot her simple met hod f or recon-
s t r uct i ng fall-off curves whi ch is not l i mi t ed t o
pur el y classical oscillator represent at i on, as t he
Kassel i nt egral is.
The met hod I am referri ng t o [ W. Forst , J.
Phys. Chem. 76, 342 (1972) a nd p. 179 i n Ref. 1
of paper No. 66], sometimes called t he "decon-
vol ut i on" procedure, consists of showi ng t h a t if
k| i n a t her mal syst em is known i n t he f or m
k, = A~ exp (--E.:/RT), t he mi crocanmfi cal uni -
mol ecul ar r at e const ant of specified energy,
k ( E) , can be wr i t t en
k(E)=A~N(E--E| (E>E=)
~here N(E) and N(E--E| is t he densi t y of
st at es of t he r e a c t a nt molecule a t energies E a nd
E--E~, respect i vel y. Thi s f or m of k ( E) is t hen
used i n t he usual RRKM r at e cons t ant i nt egral
t o yield
k/k =Q_1[= N( x) exp( - - x/ RT) dx
~o
1+ AN (x )/ ZPN (x-~ I~|
where Q= par t i t i on funct i on, Z= collision hum-
ber. Numer i cal eval uat i on of t he i nt egral for
several val ues of t he pressure P t hen gives t he
fall-off curve. Admi t t edl y, these cal cul at i ons
cannot be dorm on a slide rule, but anyone wi t h
access t o a comput er can cal cul at e a compl et e
fall-off curve i n about 10 mirmtes ( act ual machi ne
t i me a bout 10 see), usi ng A~, E~ and t he vi br a-
t i onal frequencies of t he r e a c t a nt as t he onl y
i nput . The st eepest -descent r out i ne is used for
t he qua nt um densi t y of st at es eval uat i on. There
are several examples in t he l i t er at ur e t h a t demon-
s t r at e t he usefuluess of t hi s procedure for cal cu-
l at i ng uni mol ecul ar fall-off curves [ H. M. Fr cy,
R. G. Hopki ns and L C. Vinall, J CS Fa r a d a y I
68, 1874 (1972); W. Forst , i u " React i on Transi -
t i on St at es , " 5. E. Dubois, Ed. Gor don & Breach,
London 1972, p. 75, H. M. Fr e y and 1. C. u
I ut . J. Chcm. Ki net . 5, 523 (1973); K. J. Mi nt s
and R. J . Cvet auovi c, Cau. J . Chem. 51, 3386
(1973); K. J . Mi nt s and D. J. LeRoy, Can. J.
Chem. 51, 3534 (1973); L. Ssi rovi csa and R.
Wal sh, J CS Fa r a d a y I 70, 33 (1974)3.
Authors' Reply. The advant ages of t he present
met hod =7 for cal cul at i ng reduced fall-off curves
over t he met hod proposed by Prof. For st are t he
following: (i) t he present met hod does nut
assume t h a t k= = A ~ exp ( - - E~/R T) and k ( E) =
A~N (E-- E~)/ N (E) at E~_ E~. I n gestural such
an assumpt i on is not val i d. (it) The i mpor t ant
weak collision effects can be i nt r oduced i nt o t he
fall-off curve whereas t hi s is a c t possible ~dt h
For s t ' s t echni que. The use of Kassel i nt egral s
is not a t all l i mi t ed t o classical osci l l at or repre-
sent at i ons.