Chcmktl Phgics 35 (1978) 129-140

ONorrh-I lulldnd Publishing Curnpa1.v

ON THE POTENTIAL SURFACE DEPENDENCE OF THE H + F2 REACTION.

I. QUANTUM MECHANICAL AND INFORMATION THEORETIC
INVESTIGATIONS FOR VARIOUS EXTENDED LEPS-SURFACES

Werner JAKUBETZ

Rcccivcd 28 April 1978

EtTwts of putcutial surhcc variations liir the ti + 1’2 (u = 0) - IiF + 1: reaction have been investigated by a combination
of collinwr qu;mtum calculations and an inl’omration thcorctic ID to 3D transformation. First cullincar quantum wlcu-
lxions using the swtc pnth sum method have been pcrformcd for five estcnded LEPS surfaces with different combinations
of S;tto p:tmmcters. Total reaction probabilities :tt Etrans = 0. IO9 cV increase with decreasing barrier height. The average
vibrational product excitation (12 ) is found to be u linear function of the attractivity index .<YJ~. The collinear vibrational
distriburions have been subjcctcd to nn information tlworctic 1 D to 3D tronsfornmrion. Resulting 3D vibrational product
distributions show :Ipprosim:~tel~ the s;~me breadth for nil surfaces, with ( fu’) a;clin lincarlv r&ted to .c/l. The breadth of
the cAxlated distributions is nxruwcr tlran the cspcrimental one. Deviations from cspcriment, and the problem of
sclccting an “optittjal” LEPS surt:~ce. ;Lr,:discussed. It is argued that the deviations might stem from 3 failure of the LEI’S
surfaces tu ;Iccount for sonic distinctive non-collinear rexlive wllisions.

1. Introduction Pohnyi aid co-workers [3,4,71, derived frown

classical trajljcctory calculations. Some otlicr studies
Due Lo lack ot’ sufficicu:ly ;tccur3te or sufficiently about factors governing reaction dynamics are
complete nb initiu potential surfaces for (neutral) reviewed in rec. 141.
xactive A t BC systems, otller than H + Hz [I ,2] ,semi- For the title reaction
enipirical or enipirical surt‘aces are coriimortly used in
c3lcu1~tioris on reaction dytlaniics I_;,41 . Among thcsc, H + F, + HF + F, (1)
surfaces of the LEPS variety [4.5] play ;I nxljor part.
If the dytiuniical calculations are 10 go beyond 9 pure trajectory calculations using a number of diKerent
niodel chxxter, adjustable pamnxters like the Sate LEPS-type Potential surfaces have explicitly been
paranieters in estctldcd LEPS-surhws 14.61 , have to carried both Jonathan ct al. IS] and Polanyi.et
out:
bc introduced either in order to reproducu sow al. 191 havearrived at surfaces leading to acceptable,
(often only vaguely known) Propcrtics of tile ;issumed but not at 311pert’cct agrcment bctwcen trajectory
“correct” surflrsc (e.g. barrier location and kigiit), or calculations and espcririiental pmduct distributions
else to yield ;qqxoxiniate agecmcnt with esperimental 18- 171 (see also ref. 1I;] ). III particular the breadth
results in, say, classical trajectory calculations. Tllus, of the vibrational distribution W;LSconsistently
agrecnient will be sought for macroscopic kinetics or, obtained too narrow in these calculations 3s well as in
tiiost frequently, vibrotational or vibrational product other trajectory calculations reported for reaction (1)
distributions. A fitting proccdurc of this kind is [14- 161 . One of the reasons for this kind of
Ikilitated by ;I ~INAxI~~ about the potential surfxe discrep;n~cy might of course be B possible neglect of
dependence of tile resulting distributions. There esist quantum eftccts 1171 . t-hcver, collinear quantum
a number of rather successt’~d qualitative and scmi- calculations [l&19] followed by an information
qurrntitative rulesabout correlations between surface theoretic ID to 3D transfornlation [19--Z?] also
topology and product distributions, mainly due to produce a too narrow vibrational distribution For the
 I Ii’lhis work 6.11 0.917 2.219
ref. 131 6.12 0.917 2.119
ref. 191 6.09 0.9 17 _7.125

“)i%ornWC= 917 cm-’ 1’9 I.

espt2rinietit and tlicary. wrc :iblc to wcwcilc all

auilablc iiilimiation with ;I valit~ of.!&=1 h50 f 0.00
cV. Fom :III~ Kmfrn~~l 1301 iurtlicr i~muwcd rhc
cstiinatr: to D,=I .044 ? 0.01 eV. All utltcr rclcvant
ht:t fur 1:~ :111dI It- Iwt’ bwn wll cstablishl for
sww tilne aid he bwii iiscd ~3mitio1iIy. A rwiltiiig
set d Morse priranwters is listtd in table I Usilg
tliw rtsyniptatil: pmwtc’rs. five cstc~~dcdLEI’S
surtces deiigiiatal Ll to L5. wcrc ch0se11 with
Titc putcrttial stdaccs uscti in the prcscnt irtvcsti- Sate pmiwtcrs in the vicinity ot’ tlwsc [or Jo~~atl~;~n’s
!gition xc spccitir‘d in s&on 1. In sr’stion 3. ct :A. “bcsr” sllrl;lcc‘ I I IS 1_ 7’1~2latter ws cottsitlerctl
**ivw twetiwr
~~~i~i~~iit;itioii~Iriictliuils xc = _ with :I :ln :tppropriatc sturtiiig point t;lr 311irivcstiytioii ut’ the
dissitssioii 01‘the ;~uxrx~ 0i tlie cp~i111111ti dArilio1ts ptcntial surinw depcnh~~ ot’ reactioit ( I ). 311d
I<csi~lts arc’ iii wctioil 4. The pr0bkiI~ uf sckctiitg a11 cvc111it~11l~;I fine u~ljiistnici~t dSutu paraiiietcrs.
~optirnal- pa3itid surth is trtxttd iii ttw dis~iissioii bccalisc iii dmic3l trrtjcitory c:ilciil:itiuits it yieldctl
iI1 sc~fjoti 5. A brief suininary and conclusims arc cross w~tioiis. astiv:iti~i~ ciicrgics :md vibratiw:il
34vcn in scstioii 0. pmlwt Jistributiotis wllich art‘ nut ithmtipatil~l~ with
csperimcntal results [7.1 O-- 12.3 1.;‘_I . (Jlicsc poiiits
will be rliScusscil fwther iii scctiun 5.1 Also. its v:1lut3
t;)r the asyttiptofiz III~IL’~~II~~ :trc ~tot tar trotti the
rr’cwt rcctmmcdcd values. III particular. D, (F, ) =
I-ctc ilc’siyiii~ xid prdni~tririty (s~~~ii)~itipiric~ll I .0X eV \KIS tucd by .twarlt~~~~et al. (The LEl’S
potciltial surhw it is clcsirabk to titilize all ;tv~iil~iblc’ surtise A 01‘ Manyi c‘t al. 191 _which pt’rt’c,rms
dirc<t ~speritticiitul iilfi,rin;ttion ;ibuut rcactallts alid rqually well. tws uldcr data. e.s_ D,(F?) = I ,750 eV
prrdusts. i.e. diss~hAti~~il eucrgier artil specrruswpis wliidi is uiitsidt‘ the ~spcriiiisnt31 rmgc I .64-i 2 0.0 I
wlstants. Ibis will dso :tittuiti;tticnlly result iii tlie cv [SOI.)
curtcct reactiwi csutl~crniicit~- mid iii tlx c0rrwt Stirfax 1.2 ()I‘the prt’scnt study iws dircstly the
cttcrg kvrls ior the irldiVidtial rtxkzt:ii~t arid prudiic‘t Sate parmctcrs ut‘tlw Jo~uthn ~‘1 al. II stlrt’;u
st;itc’s. which 1ti3y bc criici31 for tile charJct~ri~JtiW1 d (SIIIc = 0.00. S,:,: = -0.35) and tluis difikrs ml~
;I rextiuri (sw e.g. rcfs. 177.15) ). mittimally t‘rurti the rdxwce surfax. A colituur plot
For I!IC F,/IlF systcru it is irtlpurtant to IWIC that of surface L?- in tlte skewed mss-weiglttetl coorditixc
the long-stail&iig cwtruvcrsy abmt tlw clissaciatiort systctii is sl~twi iii iig. I _Surf&s LI ml U art’
eiterg’ uf F, 11~ fin;ill~ beeii resolvcit. Berli~:~~it7.:tUil obttlined by rcspcctivdy ittcrcasing md decreasitig
Wahl [?I] _iivirtg ;1 cmhil discussion of both S,:t: hy 0.02. This rcsults in s~tirtll changes of :~ttractivity
 0.104 cV is chse 10 the cspcrimcntal activation
r cticrg~ [;I 221 at 300 I<.) 111vic\v of tlte fititlitigsol’
Polatiyi et 31. [YJ (their surface 13with 3 cotisitlerably
lower hurrier is fnr too reactive) it was dcciderl not to
allow too drastic vurinliotis in tile barrier Itciglt~s.
3- S~mc dkt of surfws LI to LS :tre collcckd in
table 2 itkmg with the corrcspontling values of
Jonathan’s ct al. sitrlkc II and Pohyi’s et al.
>- surface A. As cm be sce11 hrricr heights arc ahost
quaI for surfxcs L2, L4 and L5. Surface LI with :t
2-
slightly lower barrier my be espectcd to be SOIIIC-
what nme reactive: the reverse is true for surfxe
U. Tlic pcrcctttnges of atrrxtivity,.dl [Z] . vary
from 32% to about 45%. Thus from Pohnpi’s rules for
the light-heavy-heavy (LHH) mns combination
[$6] ;Lnotable varhtiott in the corrrspotdingaverage
vibrational product cscitatiott ~311be cspecwd with
surface W showing the lowest value 9tid stirfax L4
the highest one.
Ott a nwre detailed level. differences between the
surfxcs cati be studied in iig. 7_irom the variatiuta in
the eqttipotetttial lines in tlw barrier- untl ittterxtiun
regions. To avoid co~~fusiot~.only the lines at
k-dx = -1 .485 eV (which is the cticrgy used iii rlw
cnlculations rcprlcd baluw) arc shuwn for surfxes
LZ, L4 and L5. Tints tlw regions between the
cqitipoletitial lirics x-c the dnssic;tl allowd parts of
Ihe potential surfaces at the cticrgy cotisidrrctl.
The corresportding eqttipotentially lines for Ll
wvot~ltlfall in betwecti the ones f<)rsurbces L2 ;IIKI
L4: tltusc for Lj woultl fall betweeti the otics for
sttrtaies L1 :ttitl L5. 111 the inter;tction region. surf&es
II sttrthcc IS] . In lig. 3 deviations betwcetl LIx
urigitial LEPS surtuct2 L2 and its IUlCS fit are shuwo
it1 furm uf 3 wtituitr plot in the rcgiun used fur the
litting pwcedUre (i.e. fcxbs <--I _t 35 cV), wliiclt
currespuiids to the chsshl railge ul‘all open and the
most itnpurt:ttit clusd clia~iids. As can be seen,
devi;ltiuw do nuwhere reach O.OOSeV iti this c‘;ise.
l<esults wuuld luuk very sitidsr Uur the other sdaces.

Previuus cullitwar qiw~tii~~i sttttiies of reactiurl (1)

\lS,l’,] using Junuthan’s et A. sur!he II 181 gave ;III
apprusitiiately urhmged vibratiarlal product distri-
bution Over a considerable range of initial translational
energies, i.e. the rmgc tht wotild contribute
sigdimntly to a thermd rextion 31 300 K. This
kature has been exploited in the present calculatiuns.
Results at E3t,s = -I .455 e\‘. which correspds to a
tronslatiunal energy dEtrlIls = 0.109 cV, may be
cunsiclerecl 2s characteristic fur the whole thern~al
range. Collinear qwmtnni cakulatiuns II:IVCbeen
performed at this particular value u~‘E:,~~fur each
putcntial SUiliCC using the stute palli sum metl~od [35 ]
(seeAs0 ref. 1341 ). Computational techniques and
cietails are the s;unc 2s clexribeil iii ref. [2S] _
Since results for rather similar surfaces were to
be compared. the significawze of variations in the
results had to be established. Therefore, ;I number of
clMis on cunvergencc and accuracy had t‘;, be cxriccl
wt. It ws strrliglltf~)rward tu achicvc convergence of
the resulting reaction prob:lbilities with respect tcj
integixtion stcpsize (this statrrnent will have to be
qiiulificcl iii ;I moment) did potential swtur width.
Results reported bclw IIWCbeen ubt;lined using
vkble iritegratiun stepsize giving rise’ to up tu 490
integrution points fur rxlial wtivet‘imctiuns and uver-
lup intcgruls. The putcn tiul surt‘xes were divided into
425 sectors :iluii~ tlw reaction path. Regardiiig the
inclusion of closed channels cunvergence prupcrties
were less hvuurable. Due to the hrge number ul
intern:il vihtiunal states present in the curved part
ut’ lhe puteiitisl surtkcs (up to 24 open cliamds)
r;iclial waduncriumi currespo~icliiig to the upper
closed d~ur~riels. which penctrale into the Ilatter
regions of the potentid. are nut obtained sufficiently
xcurate with the sccuiid order finite dil’fereucc method
used to solve rile mchl differential equariun [34,36] .
2s already nutctl in ref.. [IS] .
One might ;~ssunic that this shortcoming could
eventually be rcmeclied by decreasing the integration
stepsize. Now, 3s stated above, the resulting reaction
prohbilitics dicl not slla~~gc sigrdicuntly when cun-
vergncc against integration stcpsizc w;is checked.
TINIS possibly :I decrease by order(s) ol‘mrignitude m:ty
actually be required, leacling to prohibitive computer
ilem~nds. The clifliculties with upper closed clwnncls
have the consequence, that inclusion of ;L greater
number ot' closed cliamiels will nut necessurily lcad to
an improvement of the calcthted reaction prub-
abilities, and convcrgnce of the results cannut be
established definitely. liowcvcr. ;1 number oT features
remuin stable with varying closed channel rwmbers
and c;m be cunsidered converged. First of ull, total
reaction probabilities
Pi =CPJl,,
V’
wllich are insensitive tu lhe curved region 0T the
potential surhcc~, xc well converged. Furthermore.
of the individual state-to-st:lte reaction probabilities,
all the sriialler ones arc fairly slable. iii dditiun, the
avcruge vibratiunul cscitatiun (fV’) turns out to be stable
tu within 2 0.005. The individual reaction probabili-
lies Psto for the (usually three) must populated
st;ltes are nut so stable. As implied by the constancy
of P;f mci (I;,), variations in these inclividual prob-
abilities are strongly correlated. In sumnlary, total
rextiw probabilities, as well as average vibrational
excitations uml the overall breadth of the vibrational
distributions are cunvcrged with respect to closed
cl~anncls whereas the shpc of the distribution near
the center is possibly nut. Results reported for 311
energetic txtuffcritcriun fur closed cfiannels uf’Eabs =
-0.78 cV, should be taken with tllc reservation that
the fully cunvergccl distributions might actudly be
inure sharply peaked or less sharply peaked (estimated
uncertainty in the largest Pzco < 20%).
Finally, the cunvergcnce with respect to the clwicc
uf turning puint in the RhlCS t’it will be discussed.
Now 3 vari:ltiun of the turning point is linked to ;I
kwiatiun ol the iiitcrnul vibrational states along the
reaction cuordin~itc and ultimately also to a
variatiun in the number of ~IKIIUICIS involved. lienzc
the illlluencc uf the turning point cannot be treated in
isuluriun of closed-channel considerations. Indeed
with varying turning puint the reaction probabilities
wry in the same wuy ;LSdescribed above. From this
behuviuur and t‘rom the smdlness ot’ the deviations
between originA and tittecl surrxes [see fig. 3) it
mup be conchdell indirectly that, within 3 reasonable
arca, the actual choice ot’ turning point has unly little
influence 0~ the results.
The cullincar vibr~tiund distributions IIWC been
subjected to an information theoretic ID tu 3D
transformation along the lines of Bernstein Ltnd
Levine I’_O]_As fur all reactions of the LHH type,
angular ntunlentunt constr;kts must csplicitly bc
included [37] _The method of ref. [:! I ] is usctl.
fThis is due to the special fcaturcs of the prcscnt potential
surhws. i.e. barriers cxly in the enlrancr valleys. For tlte
brltaviour of surfxcs nitlwut early barriers see e.g.
Salligan~urthy ct al. (631
where lhe colistrrtint is acluall~- inipuscd 011 the average 4. Results
ro13tio~~al escit:~tiuii (),.). which is required lo eqwl
2 prcd~t~rriiirled value (Ii .)l,re. Furthernwrc, the sh;tp~\
d 11112rotxliaiial distrihiitiun within edI vibratioiial
product st;ite is assiinird to IIWC ;i caiionisal iorm [2 I ] _ TIE results of collirwsr cpnt~~111 ~lcnlatio~ls 31 XI
In this study, (1’ K, 1I,rc is set either to the eqmimiital initial tr;iiislatiorial energy of I:‘tr,ns = 0. IO!, eV are
wli~e (0.03) [I 1] or to tlic wlue obt~inctl in ntost stiiwiarizcd in tublc 3, iltlll k~ it1 figs.4 alld 5.
hsicd XI trtljtxtory dciilatioiis using LtYS Totul reaction probabilities art‘ fourtd to be strongly
surfaces (0.015) [9.15]. wrrclaterl to tllc barrier height, with surface LI (having
A siiiikir. but soiiicwh;~t mow ~eticral wrsiun 01‘ tltc lowest barrier) being the most rcxtive one.
tlic iiiodilkxl ID 10 3D transforiitation Iias alsa been Surliices LZ. L4 :iricl L5. with ecpl barrier heights,
ptiblislicii [?I]. where rlic cntrupy dcficiciizy l.Xl Iwc altwst esactl~ the wne values for Pi. This
is iiiitiittiizcd dircc1ly ;ml no assumption 113s to be belwiuw is in rtccordance with the conclusion ot’
ni:~‘:c aboW tlic shpc of the rotation:tt distributions. ret‘. 1191that at low (tlierni31) trmlational energies,
tlowever, this ii~~tliotl was tlwiylil 10 lx less well decision about transmission or rctlection is entirely
suited for 111~prcserlt problm of cuqxhg distribu- mrle in the barrier region. antI thl potcn tial surface
tioiis for different surfxcs. tmxus~ of artificial bumps regions bcyund the barrier arc only respmsible for
ilitrotlhd tlirougl~ tlic cu1rw gruinilig of prdud the wlistrib~~tion of reaction energy mung the
states. These wo~~lii c‘;iiisc arlilitiorial sni;ill v;lriatioris products qtwlttm s1;ltes. The ixt that the results
in tlw results. Furtlwrmorc. both versions of 111e ID xc’ ultderst:iri~lnblc iii terms of llic barrier lwipht
to 3l.l trrlnst;)riiiali~ii wrc sliowi to yicltl sirnilx done. in part retlects the similarity of the general
results for rerictiw ( I I ariywriy 12I ] _ topology uf the barrier regions of the live surlllccs.
Uticcrt:iinties in tlw (iiipiit) I D ilislributiims fmi e.g. tlw widths of tlir prulilcs at tlw crest (compxc
oil1 not 10 $vc rise 10 further aniplifictltiuris in the 1 D fig. 2).
to 3D trallsf~,rrllatir)ri~ ix. they art’ carrid over to Vibrational dislributioiis are sliowti iii fig. 4 for
.?D disrributiws more or less ~IIKII:III~XI. Thus the 3D surfaces L?. L4 xid Lj. Agin results fur surfxcs LI
distrihutims rqwrttd Iwrc :w subject to tl~cSIIIW xid L3, which woi~l~l t:dl in between the ones sliow~i.
lirriitalioiis as tlio sallinex uws discussed tlbw2: Ilir: I~JVC’
twen mlittcd for greater clarity. Probabilities in
detailed shprs of tlv vibrritiunul dinributi0ti. but nut fig. 4 have been iior~ualized to
their overdl breadth and pition. may still chg~ in
fully cunvcgtxl dsulalimis. p$, = I.

LI L?, L3 L4 L5 c.\p. WJO K)

/JI u.79 0.72 0.61 0.72 0.73 -

:)& 6 6 5.6 6 5 6
Al;N 0.7' 0.21 0.23 0.x 0.22 -

UJ,, O.5Y5 0.579 0.557 Oh-!:! 0.5UO -

(,$d;,” 0.585 0.569 0.550 0.631 0.495 -
(i&p O.jS:! 0.566 0.517 0.627 O.-l92 0.55-0.W)
 El-
%
HIS-HF+F !!
!’
Li! - ! i
-l.c +---.
VP L5 x._._._
a’
03-
OS -
0.0 0.6
L results.filled circles (0) xc for 1D to 3D transformed
I?:. 4. Collincx qumtuni rcxtion probabilities P$e
(nornlalizcd to 1) at K,bs = -1.485 eV, for surhccs L’_ (-a),
L4 (------+I 3~1 Lj (.-.-xl SW the test t‘ora
discussion of the xcuracy.
in or&r IO give a better impression of the relative
breadth of the distributions. For any of the five
surfaces tfierc are just three vibrational states that are
populated more than 1070,and no more thn five to
six states are populatecl to any significant extent at all.
Here it should be recalled that the three largest values
ofP$ +o may or may not be fully converged (see
section 3), although changes that might have to be
expected would not alter the general characteristics of
the results as shown in fig. 4. For surface L3, however,
(fbv 1 falls about half way between U’= 5 and 6. Mere
computational uncertainties are large enough to
prcvcrtCil final riecision which of the two levels is the
preferentially populatL‘d state. For surface L5,
u’ = 5 is the most populated state, for surfaces Ll,
LIZand L4, U’= 6 is preferred.
In order to obtain 3 more quantitative measure of
the brcadtll of the distributions, gussians have been
fitted to the calculated values of P;f,o. (Lower
weights have been assigned to the less certain
probabilities.) The resulting distribution widths for all
five surFJces (where the probability equals the eth
part of its ni;lximunl value) Falls in the range A&. =
OX to 0.24, corresponding to Au’ = 2.5. Obviously
there are no significant variations amon% the surfaces
172. 5. Plot of(fv’) versus .cJl for surfaces I_1 to L5.
Also included itre results for Jonathan’s et al. surface II
taken from ref. [ 191. Open circles(01ilre for collinear
results with (fR1)prc= 0.030.
concerning the breadth of the vibrational product
distributions.
Fig. 5 shows a plot of the average vibrational
excitation (fop >versus the attractivity index .dl
An host perfect linear relation is found for the
quantum results. There is 311 equally perfect linear
correlation of <ful ) with ( -drn + -Nm), the sum of
nonrepulsive energy release in a minimum path
analysis (see ref. [33])_ For LHH reactions, a linear
relation of this kind has been obtained before [3,6]
from various classical trajectory studies. Recently,
Fischer and Venzl [41_] were able to infer this result
generally for the LHH case from a simple analytical
model for triatomic exchange reactions.
Two different constraints (fRJpn: 1211 have been
used in the 1D to 3D transformation procedure 120-
211. In classics1 trajectory calculations for reaction
(1) at 300 K, (fR ,) = 0.01 to 0.02 is obtained for
many potential surfaces [9,lS] _It is usually
assumed that classical trajectory calculations are well
suited to calculate such average magnitudes correctly,
and the same values should thus result from a full
(3D) quantum treatment. The constraint (fRJPre =
0.0 15 would then be the appropriate choice for a
simulation of the correct (3D quantum) resuits for the
surfxcsconsidered by 3 collinear qtIXttuIl1 calclh !hc 53111C error). Necessary conditiott for the v:ilidity
!ion phs mforrnation thcorrric 1D to 3D trmsf’orma- uf the 1D to 3D trarlsfurrtu~tiurl is :t “typically
tier?. On the other hand. the csperi1ncnt:d V3llW Of culhear dyumics” cvcn in 3D. 3s is s11ggested fL)r
(&,) is 0.03; using this xi wnsklint 11q be tlloupht reacliwi (I) at luw trcmslatiuiial energies by trajectory
of as correcting implicitly for iiiailr’qlixit’s in the results (very iowJ’, strun, 0 forwmi pertking of the
!iuwxilliriear part ui the putentid surtkes and woulil product-F [S,9]). Higher eacrgics. where tltesc
be pertinent to the question wlietiwr the cofhreur coditiotls my nut Ix ;LSwell fttlfillcd. need not bc
purr &;I given srirt-ice is correctly iiescribing the considcrecl here. The tither wxy ruuni!, ~ollinrar
iiynuniics cilcirc!v ccdlilwffrl~~
da11 tkwir~ard wastim. ijttantiun cdlculatiurls Jo nut show any spec’itic
In tlw present case. the differ& betwcit the two qt~~ntt11n el‘fwt utlw than b~lrriL‘r-tunncllilig 1IS].
KIIU~Sdcjk,)prc is sni;lli xiii dues nut bring abuut Furtlwr~uorc. with tlw wry high u’ Ievcls being UII-
significxlt diiferences in the reqwctive 3D results. important. there are 11001tset cttds 3t tlireslwld (3s
For but11 chui~es. 3D vibrational distriburiow Iwk e.g. in the F + Ii2 reaction [27,X]). Thus classical
ruuch like the 1D OIICS.onlp with (I;.) sltiftsd to c~dcul;ttiu~ts cm bc cspcctcrl tu pruducc correct
slightly her valws (see table: 3). This shit’1 of -0.0 I - tlwml vibratiurlal distributions. Co11seq11e111ly.
0.015 is largest iur surfxe L-l wlicw (j;,) itself is diffmmxs bctwwt eitltcr theoretical procedure
largest. i.e. rliffcrcI1ccs in <f;,) ~niuitg the surl-km m md esperimcnt might be ascribed to the potential
redmxd in 3D. but only to asrnall degree. Fig. 5 shows wrhces used.
ah 3 plot of c/t* ) versus .dl for the 3D rtwlts with A~tu;rll~ diiiermxs 113~ rq7eatedl~ been nuted
(Iti +,r, -- 0.03_ The str3iUJll line resulting 3glin. has rtirtiiil!; with rcspcct tu the brcadtl~ ut’vibratimial
IIUW9 slope rnarginslly tlrttter than iii the collinear distributions IS.V.l‘~.?i .I?! ~and xc also present fur
case. llw five surfxcs cmsidmxi in tllis ppx. Cerluinly
the Sat0 pacimetcrs cm be choscn to yield approsi-
m9te 3uJcement with esperinicnt for the niore
5. Discussion
aiispiciuus features (the pc;k of tlic rlistributiult and
III this section. the rcsuits ofcalctk~tioris I;x tile (11,)): iii this sense surtiiscs Ll mtl L2 agree wit11
reaction (1 ) will bc suiiiparetl with the esperimmtd csperinient. Due to cspcrinwntal and cuniputatiuoal
htx This will 3150 lead to the question of 0ptiitiifing uncertainties 31iil to s~steitt3lir devi:ltiaiis. the choice
patentid parameters with rcspxt to ligrwment with c;lnnut be pirtncd duwn further. The prmuunced wings
espcrilnt‘nt. aid fiwlly to a discussion of tl1e fcasi- in the esperinicnrd distribution (S, I 1,I2 1 are ubscnt
bility at g%sent tu ubtain the currcc~ potential surfax. from tlw dculated tlistributiuns (pthlishl corrcc-
Tliroiigliout. it pill be ~ssurid rextiuri ( I) ai1 be tions reducing the breadth of the distributiun 139.. 41 ]
nxsorlabl~ tlescrihctl using ody the ground st;lte tire iwppwpriate. see rd. [ 131)_As itutcd iri ssctiun 4!
potential wrhce. no more than 5-6 vibrational states arc populated
To ;I guod apPrusiiiiatioi~. the single-energ) significsiitly (>I% of P$) for my of the surfxcs
distributions ofscctiuil 4.2 may lx tlirrdy sunipmtl used. -IIN SXIIC 1~s been fuund by Jonutltan et al. [S]
with morn tmper;Ltw csperiniwts. sirlse clue tu :hc frwn clrtssical trajcctury calculations OII a nlumbrr of
very wedi vari3tiun with energy uf tilt rclxive LEI’S-lypc surU302s in the urigiilal furm 2nd with
vhrrttiunal popihtiuns [ I Y] . tlwrind :!ver3ging will various niodilicariuris, ctiurlging also Sat0 paranietcrs
brush the distributions only slightly [ IS.21 1. Also. sntl even csotlicrniicities. Other invcstigatioiis with
contribotiuns frum vibratiunrtlly escited tluurine LEPS-type surfaces lutl the sme results [9.14,151_
1ttuleu11lesmay br: neglected: at 300 K. ‘X3% of the F, Surhcr B d hlx~yi et al. [9J yielded 311even
~iiolccl~ltx liavr u = 0. lndecd. alluwittg for 3. slight xlrnnver distributioii. Iii ra‘uctall uf the calculutions
bruadriiing. t!Ie tr:tnsioriued qi~ai~t~~rii distributions Id to distrihitiuris uf;l (niutiified) apprusiriutcly
ubt;hd [ IO.7 I .22] for tlw sdxe II af Jo~~utlnrl et gussian shape. Intcrcstingly, culliiitxr analytic
al. IS J wrc in guud qrccnwit with uurrcspunclirig 3D ndels fur LHH typo rextions 141,43j predict
trajectury results IS.Ql. This pruvidcs3 inutual check mdificrl gaussian distributions fur the u’ as well (set
d the qlplisability of the ~~~etlwds (_unless they make also refs. [44LEp5]). Note the flat wings of the esperi-
Mental distributions rule out a fit to a pussian-like
shape.
With the deviations from rsperiment being com-
mon to all the theoretical treatments mentioned, it
might bc more successful 111look fur inadequ;~cics of
the surhscs in their anylar beluviour rather than in
the collinear part. Certainly all the theoretical investi-
!gtions were either strictly collinear or else vastly
dominated by collinear-like dyuamics; hence tlicir
showing similar behuviuur despite of differing sullincar
surface topologies may arise from a commo11 neglect
uf non-collinear reacliun uirchxiisms. There is an
additiorial hint sugges:ing the differences may stem
from a failure of the potential surfaces to account
correctly for non-collinear reactive events. All of the
LEPS-type surfaces yield al too little rotational
product excitation at room temperature [9,15J. With
a L 2 J’ angular momentum trausforniation rule for
LHH reactions [9] (SW atso refs. [37:46]) this in turn
implies too small impact parameters, on the avcragc,
for reactive cncotmters. ancl might hence be expected
to be a consequence of escessivc collinearity oi the
potential surfaces. (Recently, escessive collinearity of
the LEPS surfaces for the HHF system has been
suggested from a comparison with ab initio SCF-CI
calculations 1471: SWalsu ref. [48] .)There is no
direct evidence from molecular beam differential
cross secliuns concerning the esteur of collinearity of
rcactioll ( I ). Dominantly collinear dynamics an
however be inferred from the trend for the related
reactions of the hvicr halogen diatumics [49.50].
Now it might be speculated that the collinear mrch-
anism would contribute the approsimately gaussian
distribution predicted by the calculatiuus, which
would also have a small partial (J,.). The deticit to
the observed nun-gaussian distribution would be made
up by a superimposed distribution due to non-
collinear dynamics, characterized by considerable
breadth and a larger partial value of (fi* ). A quan-
titative partitioning cannot be attempted, since this
would be very sensitive to the input values, which in
turn show considerable experimental or compu-
tational uncertainties; in particular k(S), which would
be crucial for the shape of the broader distribution,
varies by a factor about two in the experimental
results [S,l 11 (see also ref. [ 131). The experimental
I~ibrotutiolzui distribution displayed in the triangle
plot in fig. 4 of ref. [ 1I] may also be thought as
superposition of a distribution similar to the trajec-
tory results (fig. 7a of ref. [ 121) and a second one
with the features described above.
At this point of the discussion, it may be worth
noting that microscopic branching with two distinct
reaction mechanisms has been proposed for related
reactions of hydrogen with hetero-dillalogens I.5l-531 ;
however. the alternative mechanism could be
rationalized through the differences between the two
ends of the reactant molecule. This does not apply in
the present case, yet interestingly the postulated
non-collinear partial distribution has features remark-
ably similar to those of the partial distributions
assigned to the non-collinear migration mechanism in
the hero-dihalogen reactions [5 l-53) _
If a modification (at least a broadening) of the
distribution through the influence of distinctly IIOU-
collinear reactive encounters actually applied to
reaction (I ): it would be appropriate to compare the
calculated vibrational distributions with the us-
perimental partial distribution due to collinear
dynamics. Then (-f,‘>,, = 0.0 1.5ought to be used in
the ID to 3D transformation, and best agreement
with the main peak of the esperimental distribution
should be sought. Of the five surfaces considered, this
again renders L1 or LZ *best choice” (for a description
of the collinear dynamics).
In fig. 6, ID to 3D transformed vibrational
distributions for surface L?-are showrl using (fR.&,re =
0.015. and are compared with esperimental distributions.
It has already been pointed out above, that the
correlation between vibrational distributions and the
topology of the collinear surfaces seems to be some-
what ambiguous, implying that different surhces will
give the same distribution if they only have the proper
amount of attractive energy release. The possibility of
au even further going insensitivity has been pointed
out by Shapiro and Halavee [54]. So additional
criteria have to be brought in for a surface optimiza-
tion. Now the only additional esperimental informa-
tion available for reaction (1) arc rate constants and
activation energy at room temperature. As mentioned
in section 2: the classical trajectory kinetics on
surface II of Jonathan ct al. [S] were in very reason-
able agreement with the then accepted experimental
values [31] of k(300) = 2.1 x 1012 cm3 mol-l s-l
and EA (300)= 10.0 kJ mol- ‘. Surfaces Ll to ti are
all similar in barrier topology and might be expected
V’
6. Conclusions
Reaction (I) is IJfnvotmble case for ;Ipplpillg 3
conlbilirttion of wllinm qtl;lnttm calculaticms and
iniormhrl rheorctiC I D to SD tr3llst‘.)rill:ltioiI ii1
systciiiatic surfiicc variation 2nd rcstrictcii siirI;tcc
0ptimiz:ltioii problem. even tliotigli the rc~m2iicc
thta di) not conic from corrcspoiitling 17scti ciicrg!
csperiiiicnts. but I‘ruiu tiwirial ones. III xctmlaiicc
with previaus tcrjcctory-basccl l’iorliqs Ilr LHH
rcactioils. the results csliibit :I liiimr (/$) versus
.dL rdution: 0th xpc~ts of the product vibrational
tiistributiw~s 3x111 to bc inserisitivc to jcolliiicx)
siirfxc variatiws. It’tlic stlradivity is suitably
clioseii. there is a~wpt;hle agrceiiiciit betwec~icalcw
lations anil espcrinicnt. with sonic iiutuble tliscrep-
mzics remaining. TIE corresponding cstenclrd LEPS
surhccs arc pr;gm;itically iiscl‘til I‘or rcactinn
ilyiiainics ca!cirlutioiis. At the prcswt cspcrinxiit;li
kriuwicilge he Sat0 p3rxi~cters rccuninieiirieti by
Jonnhrl ct :II. [Xj shuuld bc retained ;~ltl~uugh it is
sug@cd to d~ingc to the iiiust recent vducs fur the
usymptJtic hlorsc pmiiic1crs (surf:m L? ()I’lliis
p;p2r).
Ii1 orb 10 proceed further towards tlic currcst
plenli;d surfxc for Ireactiun ( I ). 3 number of
investiglitions wuiilii be necessary ur hiruble (the
following list is not meant to bc complete).
To state the obvious first. well resolvcti differential
cross sections from crossed beam espcrinwnts woukl
be best suited to clarify tilt importance of mm
collinear reaction mcclianisnis. Also, the esperinicnt3l
situation with rcspcct to the kinetic tluta awaits
clurificution. Interesting idurination could 3lsu be
gained from the dcuteriim isotopic rcactiun.
For KliilblC chilrilctcri~;ltioll Of tllC geiierd
il
SII:I~LTof the potential surfwe, iri p”ticular fur the
;ingiilar dependence. Iiigh qtmlity ab initio calcul;itions
for sslectcd gconictrical configimtions conltl greatly
Iidp to pruviric 3 “skclcton” to adjust enipiric:il
swtkes (there are cstended basis set calculalions for
the collinear sllddle puint region [ 551 , see also ret’.
16I ] : ;I number of collinear and non-collinear
geometries has ulso buen calcul~~tcdwith a smaller
basis set [GO] )_ Finally in mnnestion with the
problem discussed in section 5. ;Lnumber ui systemtic
investigations by me3ns of qwntum- or trajectory
c;llciilatioiis might fxilitate ;1resolution of sonle
discrcpancics. First: will collinear non-LEI’S surf’aces
give vibrational protluct distributions ol’ 3 ditf’crent
shape? A relrttcd question wdJ be: IIUWdo local
wrtitiuns iii the collincx p:lrt uf the surfaces influ-
~IICCthe prurlwt clistribu tion? Tlwc prublms arc
tskeii up in ;I subscc~i~cntpaper [(,‘_I_Other
opeli problem inclui!c the ct’fwt on product dis-
tributions :ml kinetics of:~ coasideralh v:lri:hm in
barrier topology. or ofa vxi;itiori in the angular
bdwiour ot’ tlw surfxes, given ;! I’ised collinear pm.
Minowledgeinent
Support of this rcse:mh by tilt Scicncc’ Resertrch
Cwiicil antI generous supply wilh coniputer time 3t
the University of hlancliesler Regiund Cuiripulcr
Cwtrc’s CDC 7600 xc gr:ltcfully ~cknu~ledged. The
author WOUI~liix tu thnk Prdcssor N. Juni~th~~,
I’W~CSS~I-J.C. I’ohnyi antI Dr. J.J. Sloiln for
corrcspondcnce. Dr. J.N.L. Connor, Dr. J. hhnz ml
Pdcssor J.C. I’olanyi fur discussiam, Dr. J.N.L.
Connor t’or conqmtutional assistance md the Thcor-
etis:ll Chuistry Group :It the University ot
hl:iiichestcr t’or their Iiospit:ility.
Note added in proof
Ref. [‘_I is now virtually supersedecl by the recent
paper of B. Liu nrld P. Siegbdm, J. Chew. I’hys. OS
(1978) 2457. The authors also conment on the
accuracy to be espected for potential barrier calcu-
lations in general.
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