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Langmuir 1985, 1, 443-452

the characterization and catalytic properties of a variety of highly dispersed bimetallic entities, it may be anticipated that the above program when applied to such systems will lead to a more detailed understanding of hydrocarbon conversion over metal alloys/clusters. Having noted these reservations, it still remains that the experimental studies on the hydrogenolysis/dehydrogenation reactions cited above lead to general conclusions

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on the importance of reactive-site clusters on reaction efficiency. In the same spirit, it may be hoped that the details of the reaction mechanism in each case do not invalidate the general theoretical conclusions that follow from our study of the distribution and concentration of active sites, although, to be sure, they will certainly refine the understanding of the problem once they are incorporated into the model.

Influence of Structure on Reaction Efficiency in Surface Catalysis. 2. Reactivity at Terraces, Ledges, and Kinks
G. Joseph Staten,+Matthew K. Musho,t and John J. Kozak*
Department of Chemistry and Radiation Laboratory,$ University of Notre Dame, Notre Dame, Indiana 46556 Received September 11, 1984. I n Final Form: January 25, 1985
In this paper we continue our development of a lattice-based theory of reaction efficiency on catalytic surfaces. The specific problem dealt with in this paper is the role of lattice imperfections in influencing the efficiency of diffusion-controlled reactions on such surfaces. We consider a set of reaction centers distributed on a surface on which there are terrace, ledge, and kink sites and calculate numerically using our Markovian (implicit function) approach the changes in the efficiency of the process (as monitored by calculating the average walklength ( n ) )in three distinct situations: (1)we consider a single reaction center imbedded on a surface (of up to 121 sites) and located first at a terrace site, then at a ledge site, and finally at a kink site of the lattice, (2) we consider a single reaction center (at a terrace vs. ledge vs. kink site) in competition with a whole set of reaction centers distributed uniformly over the surface of the support, and (3) we consider a single reaction center (again at a terrace/ledge/kink site) in competition with a set of competing reaction centers but where the latter are positioned at the ledge sites of the lattice, with the remaining sites of support assumed to be neutral (or nontrapping) sites. We introduce simple arguments (in which the trapping (or reaction) probability is correlated with the ligation number) to allow us to compare directly the interplay between entropic and energetic factors in influencing the overall efficiency of the reaction-diffusion process. The possible relevance of these calculations to the experimental studies of Somorjai and co-workers in which turnover number was studied as a function of step density and kink density for hydrogenation and hydrogenolysis reactions of hydrocarbons on clean platinum surfaces is brought out and discussed.

I. Introduction The physical problem we wish to address in this paper concerns the role of terrace vs. ledge vs. kink sites in influencing the efficiency of reaction-diffusion processes on surfaces. In the preceding paper1 we portrayed the surface of a pure metal (Cu) or metal alloy (Cu/Ni) as a perfect array of hexagonally close-packed metal atoms; the migration of the reactant was assumed to proceed via “hollow-to-hollow”jumps and the reaction-diffusion process was studied on the dual lattice (v = 3) to this physical array of (surface) coordination number v = 6. In order to characterize more conveniently reactions a t terrace/ ledge/kink sites, we choose here to consider processes on surfaces for which the atoms are packed together in square-planar symmetry with v = 4. Notice that any one of the terrace sites in Figure 1is characterized by a connectivity u = 4, whereas the site labeled T in Figure l a has a valency u = 3, the site labeled T in Figure l b is of valency
Permanent address: Magnavox Corporation, Fort Wayne, IN 46808. Permanent address: Miles Laboratories, Elkhart, IN 46614. #The research described herein was supported in part by the Office of Basic Energy Sciences of the Department of Ehergy. This is Document NDRL-2633 from the Notre Dame Radiation Laboratory.

v = 4, and the site labeled T in Figure ICis of valency v = 5. All labeled sites in the Figure 1 code the physical

’ *

locations of the atoms comprising the surface being studied. Now, notice that if one assumes “hollow-to-hollow” jumps on the terraces of any of these lattices, the number of directions in which the diffusing adatom can migrate is four; since a terrace is effectively a “perfect” squareplanar lattice, its dual will also be a square-planar lattice (v = 4). Consider now the possible motion of an adatom at or on a ledge or in the vicinity of a kink, keeping in mind that we consider here only steps of monatomic height. For such structures we impose no gravitational “preference” for an atom situated a t the top vs. the bottom of a step. Otherwise, as stressed by Beiiard,2 “this may suggest for example, that preferential adsorption at surface steps will occur at the bottom of steps, whereas in reality there may be cases where the strongest binding is at the top”. To bypass a criticism of lattice (or ball and stick) models of reactive surfaces, Beiiard suggests that such models should be viewed “upside down”. Given this, it is evident that all “hollow-to-hollow” transitions on our surfaces, Figure 1, should be characterized by 4-fold degrees of freedom; in
(1) Politowicz, P. A.; Kozak, J. J., preceding paper in this issue. (2) “Adsorption on Metal Surfaces”:Beiiard, J., Ed.: Elsevier: Amsterdam, 1983.

0743-7463/8512401-0443$0l.50/0 0 1985 American Chemical Society

75 \ \ 64 . a unit cell defined by one of the configurations represented in Figure 1)periodically replicated through all space or (2) a finite cluster of sites. changes the energetics in the vicinity of a step or kink.53 .46 . this because a slight symmetry breaking is introduced when one considers the cases v = 3 and 5.80 .4 2 \ ~ 3 1 43 . we shall shift our point of view back to the atoms comprising the actual surface.48 \ \ . a terrace “hollow”)is the number of first. M. K.24 .‘ 3 .3 5 i \ \ \ \ \ \ \ \ .26 . J.70 .9 0 . imposition of either boundary condition leads to the same results with respect to that coordinate direction. i 114 \ . I-100- \ \ \ \ \ 89 .12 \ \ \ \ \ \ \ \ \ 112. a set of traps) positioned at a centrosymmetric site (or.60 .4 7 \ \ 36 .89 . . Chem.34 .86 . Formulation To highlight the importance of lattice imperfections in influencing the efficiency of reaction-diffusion processes on low-dimensional surfaces. compartmentalized in the sense that a diffusing coreactant is (passively) reflected at the boundary of the cluster (via implementation of confining boundary conditions).. by cubic symmetry (v = 6).12 .70 . Y = 3 or v = 5 for a kink site.. the connectivity (valency) of the reaction space remains v = 4.I 1 0 - - 66 ~ 55 . confining boundary conditions are imposed in the x direction (again see Figure 1for the alignment of the coordinate axes).6 4 ..4 - b I I \ \ \ \ \ -\ \ \ \ \ \ \ \ 114-133-92 .51 .56 . 80.8. unbiased random walks only. the number of degrees of freedom available to a reactant at a given point in its trajectory across the surface will be exactly that of the atomic site on the underlying lattice (v = 4 for a terrace or ledge site.57 .2 4 13 .) Since the coordination number n.3 5 .79 . since the reaction center T is positioned a t the center of the lateral face (the y direction in the coordinate system defined in the Figure 1) for each (odd) lattice considered.53 \ \ 42 \ 31 .54 \ ~ 32 ~ 21 \ ~ IO \ \ \ \ ~ \~ \ \ ~ (21 .6 8 . since we wish to expose clearly the consequences of introducing geometrical constraints or imperfections (see above). particular.3 6 . Slight differences can arise. in bulk.59 .e. In general. . l l l l l 8 ll6-IC5-94-63-72-6l -51--40-29-18--7 \ \ \ \ \ \ \ \ \ ~~7-~06-95-04--73-62-52--4l--Y)--19-8 \ \ \ \ \ \ \ \ .107. J.18-107-96-85-74-~3-52-41 \ \ \ -Yi-19\ \ \ 3 \ \ \ \ \ \ \ 119 .2 2 . 4 .27 .. an “electronic factor” can be associated with the number niof “missing” bonds for a surface atom in a lattice characterized.9 0 . a set of sites symmetrically positioned with respect to the boundary of the system). the lattice with edgelength 1 = 11.2 2 ./I \ D O . 79. Phys.97 . potentials may induce jumps between non-nearest-neighbor sites on the lattice (see ref 3) or may bias the motion of the particle in the vicinity of the reaction center (see ref 4).4 3 .96 . In this paper.66- 56- 45- 34-23 \ 12 \ . we shall assume that the reactant jumps from one physical surface site (an atom) to another in its random walk movement.2 5 \ \ \ 1 4 \ - by this device we shall be able to quantify the interplay between entropic and energetic factors in reaction-diffusion processes on surfaces with imperfections. 159..3 5 . with a pronounced distortion of the lattice about tbe reaction center T (for the valencies v = 3 and 5).59 \ \ 26 \ I5 \ 4 \ \ \ Ill-104-93-82-71-T I I I I .4 7 .4 0 . confining).g.5 \ \ \ \ T -53-39-28--17-6 \ . It is important to emphasize that although we have presented each of these cases as a terraced structure.8 6 . In order to be able to distinguish and then to characterize energetic differences among terrace/ledge/ kink sites in terms of a simple convention. second. Phys.8-.6 7 57 .101 . and this.9 5 . as will be documented later in this paper.85 .I 8 .07-96-05-74-63-53-42\ \ \ \ \ \ \ 1 1 9 -108. The central trap is designated T and is situated at a site of valency v = 3 (Figure la). of course. J.109\ \ 90 ~ 37 99 ~ 65 77 .74 .1 0 1 .4 6 .3 3 .5 9 . \ \ 94-83 - 72 \ - T - .4 4 33 . with respect to the two boundary conditions studied in this paper (viz. J. 11.E0 1 7 .20 ‘ - 9 \ \ \ ~ \ 120 .37 . Thus.4 8 .91 .2 9 . \ \ . even for “hollows” a t the bottom or top of a ledge.97 \ .6 9 .I \ \ \ \ 812.54 \ \ \ \ ’\ 31 . K.I03 \ \ \ \ BI 92 \ . a ledge or kink vs. The reaction center (trap)is designated T and is situated at a site of valency v = 3 (a).60 .21 .103 \ \ 81 \ 70 . the numerical differences which arise in the calculation of ( n ) are so slight (at least for lattices of edgelength 1 > 9) that the results reported in this paper may be considered relevant to the following two physical situations: (1)a set of sites with traps (i. In Figure 1 we display the configuration of sites for the largest lattice considered in this paper. one finds that when one considers a single trap (or.. rather than assume a “hollow-to-hollow”diffusion mechanism of a species in the vicinity of a reaction center.108.23 . (4) Musho.2 0 9 \ \ \ \ . As regards boundary conditions. nearest neighbors.4 4 33 22 - II “. J.7 9 .46 .102.97 \ 86 .52 .5 8 ..I 1 - - - - Figure 1.8 \ \ \ \ \ . or for a “hollow” in the vicinity of a kink. or valency v = 5 (Figure IC). however.99- 86- 17 . when one compares results generated when periodic vs.2 \ \ \ \ \ \ \ \ \ \ \ \ \ C ( 1 3 .2 4 . each setting of v is also consistent with a strictly two-dimensional configuration of sites. we construct three lattices. J.. That is.6 1 I I I17 -106..32 .4 110.8 4 .1 \ \ \ \ ‘ \ \ \ \ \ ‘ 110 .7 3 .39 I \ I 1 .41 . more generally. I .2 3 .78 .6 6 55 .Z \ \ \ \ \ \ \ \ \ \ \ t 3 \ 0 -I 0 2 . we consider here particle motion characterized by nearest-neighbor.5 \ \ -44 .20 \ \ 9 \ 120-10938-87-76-65-54-43-32-21 -10 ‘ \ \ \ \ \ \ \ \ \ \ 121. (3) Musho.W .15 . However. Configuration of sites for the largest terraced lattice considered in this paper.16 .91 \~ \ 80 92 \ 69 \ 58 . \ . Kozak.78 \ \ 67 \ 56 \ 45 \ \ \ 3 4 .26 \ 61 15 \ 4 \ \ \ I6 115-104-93 -82-71 -60-49-38 -27 \ \ 5 i \ I \ \ I \ I I I \ \ 50 I \ 416-105- 2 8 .I O \ III \ 120-109I \ \ 98-87 \ -7E \ -65 \ -55 \ \ r.2 \ \ \ \ 112. valency v = 4 (Figure lb). there is no formal difference in the structure of the Markovian equations written down describing these two boundary conditions. Kozak.e. Consider next the trajectory of the diffusing coreactant.19 . 1985 Ill -10- Staten. As will be demonstrated in section IV. periodic vs.67 . 116-105 -49-38-27-16-5 I \ 60 \ 61 \ \ \ 94 \ \ 83 \ 72 I \ \ \ \ \ \ 50 .45 . the site-to-site motion of the particle can be influenced by a variety of potential effects. . The manner in which a vertical ordering can be incorporated in the formulation of the model as it stands will be described in section V.69 \ 114 .39 28 - \ \ \ \ \ I 1 1 \ 1 7 1 \ 6 .2 5 14 3 \ \ \ \ \ \ \ \ \ \ \ 113-132 . Chem.30 .47 \ \ ~ 36 48 \ 25 37 \ 14 \ 3 \ \ \ . e. Vol.17 .75 . 7 \ 111-106-95-84~73-62-51 \ -40-29-18 \ . 4 (b). however.. of atoms a t particular sites of the lattice can be enumerated by inspection.m \ -00-49- \ l l \ \ 115-104-93-82-7’ l 30 . M. or 5 (c).79 . 1984. In implementing the Markov chain theory6 for the underlying lattice-statistical problem.63 . confining boundary conditions. Thus.6 2 .1 1 0 99 . 1983.15 \ \ \ 64 76 88 .1942. Musho.3 1 .444 Langmuir.91 -80 .I3 .I3 . and Kozak a r:3 09. What will change in the problem for an adatom in one of the latter configurations (i. 1 1 9 \ 108 . No. we refer the reader to the preceding paper for a description of periodic vs.5 7 .

0 4. forming the product Z. Given the background of data reported in Figures 2 and 3. Considered here is the case of a reaction center (target molecule).- s a a W Y J 120.- 2 a W a 160. respectively.0 I 1 0 . The behavior of the reaction-diffusion system as a function of a continuously varying reaction parameter s can be studied explicitly provided we specify a given lattice.- > a 100.0 12.0 10. with the latter choice (s = 1.s).0 2. 111.0 8. parts b.4. 0 12. Thus. The N . forms an excited-state complex but one that eventually falls apart with regeneration of the species X. c. competing with a central trap.00 (deep trap).W 2 Y J W W W d d ' a s W 200.with all other lattice sites regarded as nontrapping or neutral sites.- / P 1 500. Results The principal aim of the preceding paper was to demonstrate how constellations of reaction centers. 1985 445 8oo. Figure 2a documents the changes - in the efficiency of reaction. where s scales the degree of reversibility of the reaction x + Y [XU]* z a t the central trap (see the discussion in section I1 of the preceding paper).50. Similarly. Displayed here are the following four cases: (a) s = 0.0 6. we can now begin to explore the consequences as regards .1background sites are assumed to be distributed symmetrically about the target molecule. or 5 (circles)and characterized by a reaction (trapping)probability s. This pursuit is also of central importance in the present study but here. in Figure 2. which subsequently resumes its random walk on the lattice).r . No. situated at a site of valency v = 3 (triangles).0. Specifically. (d) 1.0 1 0 . as gauged by the value of (n). 0 12. and d record the behavior observed as a function of system size for the settings s = 0. 4. the reaction efficiency is studied as a function of s.0 EDGELENGTH( 1 ) EDGELENGTH(1 ) Figure 2.0) corresponding to the case where the species X reacts with Y irreversibly upon first encounter.0 8. centrosymmetric trap. a 75% probability that the diffusing coreactant (X). when there is a 25% probability that the above reaction will proceed at once to completion with formation of the product Z (or.00.75. In Figure 2 we display the average number ( n ) of steps required for trapping on a terraced lattice as a function of system size (as calibrated by the edgelength 1). in order to develop systematically an understanding of the effeds brought in by considering connectivities other than u = 4 around the central trap T. the N .0 ' I ' 8.Influence of Structure on Reaction Efficiency. In this figure our results are displayed as a function of (1.r 400. 0 ' I ' 12.b C Y I I - 320.0 0 1 2. Plot of the average number (n) of steps required for trapping on a terraced lattice vs.- z 240.- y s W 80. the latter positioned at a site of valency u = 3. or 5. we consider first and in some detail the simplest case of a single trap positioned a t site T (see Figure l). could influence the efficiency of the underlying reaction-diffusion process. and 1.- g a a W > a 50. as calibrated by the edgelength (1).50.- : 480.0 I 6.0 4. (b) 0. for a lattice characterized by the edgelength 1 = 11.- I W 2 W I 300.t A a 640.0 6.- % 0 2.0 6. upon confronting the target molecule (Y). The cases illustrated in this figure correspond to four settings of the reaction parameter s.r 9 I Y J 320. 1. - 2 2. the system size.0 EDGELENGTH ( 1 ) 1 0 . Vol.- 0 180. The diffusing coreactant is assumed to encounter confining boundaries in the x direction (see Figure 1) and confining/periodic boundary conditions in the y direction. 2 Langmuir.- w 160. conversely. 4 (squarea).75. I 5 t c c - P I IW 300~r t 240.0 4.0 EDGELENGTH (R) 400.1 background sites are assumed to be strictly nontrapping (neutral) and distributed symmetrically about the target molecule.25. (c) 0. a survival probability for a walker on a lattice characterized (here) by a single.0 8.0 1 1 4. The results of such a study are presented in Figure 3 where.

On a relative basis. Vol. as displayed in Figure 4. a survival probability (1 . 3 is greater than that for u = 4 vs. the sensitivity to nearest-neighbor channels..50. IV. The cage effect studied here.6 0. 26. which arises from a strictly geometrical restriction (or enhancement) in the number of nearest-neighbor channels linking the active site to the remainder of the reaction space of the system. we studied a situation wherein immediate access to the target molecule (situated on a regular lattice with no imperfections) was mandated once a nearest-neighbor site was reached in the random motion of the diffusing coreactant. v = 4).In ~ that work.4 (solid line). and 1. (6) Politowicz. B 1983. There we admit the possibility that all the sites surrounding the target molecule.1 surrounding sites (scaled uniformly by the parameter p ) . Then.2 0. 5549.p ) against background trapping for each of four settings of the reaction parameters.8 1. Rev. J. We consider reaction-diffusion processes taking place on lattices characterized by edgelength 1 = 11. . Attention will be drawn to this point (i. In two of our earlier studies where “perfect” square-planar5 or hexagonal6lattices were considered.0. No. J. Kozak.. the survival The collection of results displayed in Figure 2 provides the point of departure for our discussion. A further study of the effectiveness of background trapping was carried out. it was found that a 5% probability of reaction at these adjacent sites effectively erased distinctions between ( 5 ) Walsh. (1. four. A. it is seen that the separation between results calculated for (nearest-neighbor channels) u = 4 vs. 1. I ’”‘. displayed in Figure 5.50. is of greater consequence than a defect that permits an increase (Av = +1) in the number of such channels. J. in the following section.00.0) studied in Figure 4. Thus...s) are given. Our calculations show that there exist already quantitative differences in the value of ( n ) even for the smallest lattice considered (viz. an 11 X 11 lattice) with a target molecule surrounded by -120 nontrapping sites but linked to its environment by three. Au = -1) in a later paragraph. Phys. Moreover. We now discuss the results presented in Figure 4. 0 0.s). 0. and 1. relative to the overall connectivity of the host lattice (here. 0.. s = 0. the percent difference between the u = 3 and 5 results decreases with increase in the degree of irreversibility of the reaction (as studied by increasing the magnitude of the parameter s).446 Langmuir. we introduce a second reaction parameter p (0 < p < 1) defined as the probability that the diffusing species X may undergo a reaction a t any one of the N . reaction a t the N . We now take up a discussion of the results presented in Figures 2-5 and comment on their possible implications. quantify the dependence of the average walklength ( n ) on the survival probability (1. the percent difference between the v = 3 and 5 results decreases with increase in the lattice size (as calibrated by the edgelength 1 in the figures).0. the trends found are the following: (1)For a given setting of s.75.. we can also calculate for a given lattice the walklength ( n )as a continuous function of s.r I I I 150.1985 Staten. Interpretation of Results The discussion of the results reported in section I11 will be in two parts. especially in the range s < 0. We emphasize that in this series of calculations the remaining terrace sites are assumed to be strictly nontrapping (or neutral) sites characterized by the probability p = 0. A.. These trends document the importance of short-range (here cage) effects in influencing reactiondiffusion processes. we shall attempt to display the relevance of these results to problems of reactivity on solid surfaces. 0. the 5 X 5 lattice) and that (in an absolute numerical sense) these differences tend to increase with increase in the spatial extent of the system. From the results displayed in this figure. and d. Figure 3. Musho. We then consider the interplay between reaction at the central trap (which we continue to parametrize by the reaction probability s) vs.e. We consider a single reaction center (target molecule). This would seem to suggest that a decrease (Av = -1) in the number of nearest-neighbor channels to the active site. The diffusing coreactant is assumed to encounter confining boundaries in the x direction and confining/periodic boundary conditions in the y direction. s = 0. we find that these differences persist when one changes the factor s which gauges the effectiveness of trapping at the active site.25.75. There it is seen that for a lattice of a given size (here ranging from one of edgelength 1 = 5 to one of I = 11) the number of nearest-neighbor routes to a central target molecule is critical in determining the efficiency of a reaction-diffusion process. 4166. one in which the ledge (or step) sites only (e.or 5 (dotted line) and characterized by a reaction (trapping) probability s.25.. P.we plot in Figure 4 the average walklength ( n )vs. and Kozak I $ Y “ F 1430. s = 0. all as a function of the valency v characterizing the connectivity of the lattice in the immediate vicinity of the central trap. situated at a site of valency u = 3 (dashed line). in Figure 3 profiles of the walklength ( n )vs. Plot of the average number ( n )of steps required for trapping on an 1 = 11terraced lattice (seeFigure 1)w. or five channels. 5. C.50. can now with probability p compete with the central trap.g. c. where the quantity (1.25.2.s) is a survival (or escape) probability of a reactant migrating on a lattice (here. respectively. 28. Specifically.p ) against ledge trapping. sites previously assumed to be passive (or “neutral”) chemically. In this section we shall focus on the implications of the results obtained vis-&vis some general problems of reaction-diffusion theory. reaction efficiency of introducing additional reaction centers which may compete with the central trap T.75.s ) probability. 4. To proceed. 0.1 sites surrounding the central trap.0) for lattices of various sizes. b.50-39-28-17-6and sites 116-105-94-83-72-51-40-29-18-7in Figure la) were permitted to compete with the central. B 1982.4 0. these studies quantitate the importance of factors controlling the behavior of the coreactant in the immediate vicinity of the active site. Taken together. Kozak. The background sites are assumed to be distributed symmetrically about the target molecule. (2) For a given setting of 1. Whereas the dependence of the average walklength on the parameter s was displayed in Figure 2 for discrete values (viz. parts a. the independent variable (1. sites 115-104-93-82-71.and 1. target molecule T. for each of the four settings of the reaction parameters (viz. differs from the short-range (chemical/cage) effect identified in our earlier s t ~ d y . J. Reu.0 SURVIVAL PROBABILITY ( I . The results of this study. viz. Phys.

In fact. It is plain from the preceding discussion that the results recorded in Figure 3 vs. rather extreme situations. those in Figure 4 describe two. it is desirable to consider a situation intermediate between these two extremes. In Figure 3 we considered only a single. First. We now draw the reader's attention to the results of Figure 5. 1985 447 b - 80. Both from the standpoint of considering (eventually) the problem of crystal growth and from the considerations of the following section (where problems relating to heterogeneous catalysis are discussed). even when the number of nearestneighbor channels to the target molecule is changed (Av = fl vis-&vis the host lattice of valency v = 4). one notices in both calculations an effective coalescence of results calculated for given settings of (s.C I - I V d I - I - - lattices subject to different boundary conditions or characterized by different valencies. These results pertain to a situation where only the atoms or molecules comprising the ledge of the lattice (see Figure 1)can compete chemically with the molecule situated at the centrally disposed active site. orders of magnitude may separate the values calculated for ( n ) . chemically active target molecule embedded in an array of neutral sites. a change that produced marked changes in ( n ) when only a single reaction center was present (see Figure 2). the smaller the value of p that is effective in erasing distinctions between results calculated for the (nearest neighbor) valencies v = 3 vs. 5. when the background is characterized by a mere 5% reactivity. In fact. 1. 4. No.25 vs. but there are some interesting differences. that is. the results calculated for ( n )tend to coalesce for values of p in the vicinity of 3%. whereas in Figure 4 we assumed the entire array of background sites could compete chemically with the target molecule.Langmuir. 80.p). The results calculated for this intermediate case are reminiscent of those displayed in Figure 4.depending on the value of s. a similar result is found here since. As is evident from the results displayed in Figure 4. Vol. the remaining terrace sites of the lattice are assumed to remain chemically inert.0) that when one studies this effect as a function of s. the smaller the value of s. convergence occurs here for percentages somewhat less than 10% (as opposed to the 5% figure noted in Figure . but here differences persist over a somewhat wider range of values of p characterizingthe ledge trapping probability. Figure 4d where s = 1. the reaction-diffusioh process became kinetically controlled. it is seen clearly (compare Figure 4a for which s = 0. notice that regardless of the setting of s (compare Figures 3 and 4) there is a precipitous drop in the calculated value of (n)when one "turns onn chemically the -120 background sites of the lattice.V E I ' i . as regards similarities. 4 vs. Moreover.

92 0. enhance the possibility that trapping of the diffusing coreactant will occur. Displayed here are the following four cases: (a) s = 0. 9 8 1.00 (deep trap). Thus. 1. when placed in competition with the central trap T. in fact.90 0. with the differences gradually diminishing with increase in 1displayed in lattice size. Musho. or 5 (dotted line) and characterized by a reaction (trapping) probability s.96 0. and Kozak V 350~r a b h C I W I- W z 1 Y I e W W W a K P i0 0. for each setting of s considered.96 0 .98 1.1 t 0 0. the results registered in Tables 1-111 quantify. for p > 3%. the results calculated assuming these two choices of boundary condition can differ.0 0 0. No. 1985 Staten. the ledge sites can. (d) 1.. When one breaks the symmetry of the reaction space.90 " " " " ' * 0. but will be slightly off center with respect to the coordinate direction y for the cases u = 3 and 5. the dashed (v = 3) and solid (v = 4) curves intersect. p = 0). both the value of ( n )and the setting of (1. 4. interact with and trap the random walker.94 0. For the lattices of edgelength 1 Figure 1. when one is dealing with an Id lattice with a centrosymmetric reaction center (and no imperfections) the use of periodic or confining boundary conditions leads to exactly the same results (see our earlier description of these two boundary conditions).75. In the range p < 3% the v = 3 curve yields the largest values of ( n )whereas. One finds.92 0. Although heretofore we have chosen to display the results of this study (and the preceding one) in graphical form. since in this format a further point can be made concerning the boundary conditions subject to which the calculations reported in this paper were performed.p ) at which the crossover occurs are sensitive - to this difference in the number of active ledge sites.0 SURVIVAL PROBABILITY (LEDGE TRAPPING) ( I-p) Figure 5.25. an interesting effect that appears in Figure 5 that is not present in the Figure 4. in case c of Figure 5 where s = 0. There it will be seen that although the number of sites along each edge is 11 for each of the three lattices.75. once again.r 200. The reason for this behavior can be seen by viewing. Furthermore. a survival probability (1. the curve for v = 3 is intermediate between the v = 4 and 5 curves.94 d 0. There is.448 Langmuir. 4. however. whether by moving the target molecule off center or by introducing imperfections (defects).p ) in the vicinity of 0. Vol. the lattices corresponding to v = 3 and 5 have two more ledge sites than is the case for v = 4. The diffusing coreactant is assumed to encounter confining boundary conditions in the x direction and confining/periodicboundary conditions in the y direction.50.the disposition of the trap will be exactly centrosymmetric with respect to the coordinate direction designated x .0 SURVIVAL PROBABILITY (LEDGE TRAPPING) (I-p) SURVIVAL PROBABILITY (LEDGE TRAPPING) (I-p) "O'C "O. as .90 0.92 0. 4 and ref 5 and 6). 1 I I I f 50. These two additional ledge sites.96 0. a "crossover" in the profiles generated for the case v = 3 vs. (b) 0.97 (or p 3%).96 0. while the remaining terrace sites are neutral (i. (c) 0. for (1. situated at a site of valency v = 3 (dashed line).94 0.92 0. the lattices displayed in Figure 1. For example. whereas there is indeed a reduction in the magnitude of ( n )as one "turns on" the ledge trapping probability. The background sites are assumed to be distributed symmetrically about the target molecule.98 1. 4 (solid line). with probability p . In particular. the effect is not as pronounced (quantitatively) as that found when all background sites are activated.90 0.94 0.e.p ) against ledge trapping. it is of interest to tabulate the numerical results for the "intermediate" case described above.98 1. This we have done in Tables 1-111.0 SURVIVAL PROBABILITY (LEDGE TRAPPING)(I-p) 0. of these. Considered here is the case of a reaction center (targetmolecule). Plot of the average number ( n )of steps required for trapping on an 1 = 11 terraced lattice (see Figure 1) vs.

97 0.28 80. well.58 134.s) and competing (ledge) reaction centers ( p ) .93 0. bReactant subject to periodic boundary conditions in the x direction and periodic/confining boundary conditions in the y direction (see Figure 1). Reactant subject to confining boundary Conditions in the I: direction and periodic/ confining boundary conditions in the y direction.26 0.59 OTerraced lattice (1 = 11) with a central.79 s = 0. NY. bReactant subject to periodic boundary conditions in the x direction and periodic/confining boundary conditions in the y direction.03 Langmuir.91 0.13 0.34 82.99 0.96 0.16 0.01 212.38 126.86 0.96 0.39 183.92 162.25 0.59 96.58 88. In certain of these investigations.92 0.73 0.29 0.16 102.96 0. Thus. Somorjai et al.11 80.09 0.66 94. 1985 449 Table 11.12 0. nearest-neighbor channels) characterizing the reaction space on which the reaction-diffusion process takes place.03 78.59 222.78 74.92 0.21 80.99 97.94 77.75 68.39 116.08 75.96 0.22 149.15 0.75 80.79 72.58 75. Comparison of Results for ( n )for Two Choices of Boundary Condition for the Case Y = 3 O (1 .07 83.94 0.08 0.09 0. No.50 0.11 0.57 123.03 0.15 0.27 89.30 222.95 0.34 0.90 0.84 212.67 108.81 72.36 78.05 107.67 0.98 0.35 73.84 73.36 106.33 102.17 107.65 97.17 0.79 0.03 135.07 0.90 84.07 0.90 0.99 0.90 0.96 0. G .41 0.Influence of Structure on Reaction Efficiency.96 0.50 304.14 0.10 84.94 0.95 0.16 0. "infinite" (periodic boundary conditions) clusters when the edgelength of the unit lattice is I = 11.s) and competing (ledge) reaction centers (p).73 0. 4.87 s = 1.92 0.25 0. more-or-less centrally disposed trap T) and amount to about one step when the ledge sites are 'activated.98 0.97 0.95 0.95 0.98 0.97 0.47 252.96 0.59 0. 5 profiles in the vicinity of p 3% for ledge trapping and (2) the near insensitivity of the results calculated for ( n ) to the assumption of finite (confining boundary conditions) vs.94 0.53 217.50 92.04 91.53 116.18 0.90 110.00 162.15 0.22 71.20 0.10 75.90 0.66 114.03 121.52 0.95 0.21 171. Relevance to Heterogeneous Catalysis In this section we wish to display the possible relationship between our model calculations and experimental studies in which the catalytic effectiveness of 1qw vs.08 0.91 0.13 0. Reactant subject to confining boundary conditions in the x direction and periodic/confining boundary conditions in the y direction. the differences in the calculated values of ( n ) essentially evaporate in the limit p 0 (the limiting case of a single.95 0.71 123. Comparison of Results for (n ) for Two Choices of Boundary Condition for the Case Y = 4' s = 0.38 97.70 165.10 0.83 0. 1981.16 0.0 68.80 108.81 0. Cornel1 University Press: Ithaca.57 0.84 135.39 252.13 81.14 125.21 126. see: Somorjai.44 99.19 0.93 0.40 0.22 78.07 s = 0.66 0.53 101.14 0.94 163.53 329.99 77.16 0.47 139.75 0.96 83.90 0.96 304.66 67.91 0.96 0.26 88.75 91.93 0.87 0.90 0. the results recorded in Tables 1-111 quantify numerically (1) the crossover point in the v = 3 vs.15 89.28 107.18 0.93 0.93 71.15 0.45 0.12 78.62 184.92 0.82 111.91 134.10 88.92 0.98 0.94 0.' noticed a remarkable difference in catalytic (7) For a comprehensive summary of this work.67 0. target molecule (Y.45 s = 0.60 0.13 0.50 0.57 0.93 0.92 115.54 0.50 72.99 0.33 149.96 0.93 0.17 82.17 0.91 0.91 0.91 0.92 0.50 0.12 108.89 125.74 78.05 0.46 0.13 107.22 97.98 0.67 217. these results document the delicate interplay between chemical factors influencing the fate of a diffusing reactant (as reflected in the studies of competitive trapping) and the strictly geometrical factors (system size.66 86.05 0.94 70.17 0.0 67.15 184.12 0.66 s = 0. nature of the boundaries.74 138.17 0.99 0.97 0. 1.98 0.17 120.94 0.13 0. As 1s seen from the data.18 103. As a point of reference.97 0.93 0.75 75.29 88.13 0.94 0.86 212.46 0.90 0.78 0.19 135.09 0. the extent of the differences found upon imposing the two different sorts of boundary conditions in the y direction.89 84.45 146.71 101.99 73.61 87.37 212.60 0.04 83.08 67. OTerraced lattice (1 = 11) with a central.21 93.53 75.99 0.91 0.39 0. 2 Table I.16 0.69 148.91 0.32 146. high Miller index surfaces has been studied.67 81.54 165. - - V. A.17 0.92 83.08 162.99 0. Taken together.94 0.61 73.39 119.03 133.78 103.95 0.65 68.98 0.49 183.06 166.15 0.46 121.46 90.65 329.97 0.32 116.91 70.76 188.09 78.62 71.62 171.28 84.24 70.99 77.64 0.27 99.90 0. Vol.58 91.94 141.15 0. target molecule (Y.98 0.95 149.14 0.87 116.12 0. we shall focus on the studies of Somorjai and co-workers' on dehydrogenation (of cyclohexene to benzene and of cyclohexane to benzene) and hydrogenolysis (of cyclohexane to n-hexane) in which turnover number was studied as a function of step density and kink density on clean platinum surfaces.92 0.26 0.92 0. "Chemistry in Two Dimensions: Surfaces".50 70.44 141.56 0.94 0.62 0.75 69.67 75.44 96.16 86.78 87.93 0.31 0.77 77.69 0.38 188.P) (fl)Ib (n)rrC A(fl) s = 0. .55 96.00 97.32 92.97 0.97 0.71 9 = 1.49 116.

99 110.27 0. topologically. Although.75 64.25 0.72 146.38 s = 1.93 81. it is. 4 . i. one entropic ( u ) and one energetic (nl). On the other hand. Thus. however. when a single ledge site is considered.95 0.49 0. concentration of reaction centers) being held constant. it codes the number of ways of reaching a target site from the immediate (nearest-) neighbors of that site. they are topologically equivalent sites.98 0.24 75.92 0. in Figure IC. to denote the overall coordination number of a given site and the symbol nl to denote the number of unsatisfied bonds (consistent with a given symmetry).35 0.31 s = 0.31 0. and nl = 0.93 85.98 144.19 0.35 0.19 0.50 267. Specifically.90 0.86 94. planar surface.41 0. = 5.35 105. We now recast the data presented in Table IV into a form in which contact can be made with the sort of results reported by Somorjai et aL7 in their studies of hydrocarbon conversion over platinum. with the missing nearest neighbor resulting in electronic “unsaturation” at that site. The energetic characterization of the two sites is quite different. Vol. bReactant subject to periodic boundary conditions in the I direction and periodic/confining boundary conditions in the y direction.31 127. is the effective electronic or ligating character of an atom positioned at that site.60 s = 0.96 0. 1. = 4.81 153.29 0.00826.65 0.98 0.33 71.20 0. In order to study the interplay between these two factors.96 0. and Kozak a ledge site from a terrace site.86 1.39 68.25 0.18 164.96 0. there are four nearest-neighbor paths to the site T.09 73. Somorjai estimates the number of surface platinum atoms to be 1.19 64.98 0.50 with nl = 1. and 11 is presented in Table IV. = 6. a terrace atom would be coded u = 4.s) and competing (ledge) reaction centers @). (n)-I is proportional to a turnover number.04 71.54 0. target molecule (Y. cReactant subject to confining boundary conditions in the I direction and periodic/ confining boundary conditions in the y direction.96 0.95 0. n.25 0.63 88.85 109.19 0.92 0.86 71.98 81. Musho. 1985 Table 111.98 0.19 0.36 133. depending on the location of the step site. we convert the concentration of traps in our model to an effective site density.43 81. n.22 0. In this symmetry.75 98. Accordingly. and nl = 1 while site 62 would be coded u = 5. n.58 126. the valency u of site T as well as all of the remaining (120) sites is 4.82 88.35 90.95 0. as noted several times already. suppose we associate different settings of the parameter s in our model with the nl. we shall identify the setting s = 1. the sites labeled T and 61 in Figure l a are both of valency u = 3 and.nl) for lattices with edgelength 1 = 5.95 0.28 85. imagine the lattice to be a rubber “sheet” and notice that a simple diffeomorphic distortion [pulling the sheet in opposite directions from the top (1-12-23-34-4556-66-77-88-99-110) and bottom (11-22-33-44-55-66-7687-98-109-120)] converts the figure into an 11 X 11 square-planar configuration with a centrosymmetric trap T.93 0.99 90.80 69. n. In this notation. one entropic and one energetic.75 1.. activity (turnover number) with increase in the concentration of step or kink atoms.69 93.77 126.25 105. n. As in the preceding paper. 7.65 88. the factor identified as nl in the above is reflective of the electronic unsaturation (ligating ability) at a particular site.94 0.82 114.60 196.90 0.19 0. 9.34 71. = 6.22 0.92 0. No. The ledge site denoted T in Figure l b would be coded u = 4.21 73.25 with nl = 0.32 100. We begin by referring to Figure 1 and consider the Figure l b first.70 100. and we wish to explore whether our lattice-based calculations also reveal differences in reaction efficiency when such surface imperfections are considered.41 0. Comparison of Results for ( n ) for Two Choices of Boundary Condition for the Case Y = 5 O s = 0. s = 0.62 67.82 190. and nl = 1.97 0. inspection of Figure l a shows that for site T. The numerical specificationslaid down in the preceding paragraph have been developed in order to separate and contrast two distinct ideas.41 67. a site buried in the bulk of a crystal possessing cubic symmetry will be six-coordinated. codes the connectivity of the lattice (or a particular site).98 0. then. = 6. For example. it is a measure of the accessibility of a given site to a diffusing reactant and controls the catalytic efficiency of the process (see Figures 2-5).22 0.20 0.92 0.12 127. In particular.90 82. the site labeled T is equivalent to any of the terrace sites.73 113.e. the concentration relative to the total cluster (of 121 sites) would be 1/121 = 0.17 81.450 Langmuir.25 Staten.27 0. The valency u.22 0.93 0. From this last example.03 0.01 62.41 0.10 150.99 71.58 78. A tabulation of the average walklength ( n )for all possible combinations of {v. i. we argue that since ( n ) is the average number of steps required for trapping then.20 0. 0.91 0.64 0.99 0.5 X l O I 5 atoms.91 0.90 0.29 0. let us use the notation n. = 3.97 0.24 0.35 0.99 “Terraced lattice (1 = 11) with a central. and nl = 0 while for site 61 we find u = 3.75 with nl = 2. for convenience of illustration.91 0.39 195. in effect. and finally s = 0. Thus.0 with the value nl = 3.92 163.24 0. n..70 82.00 0. In the present context.66 109.91 0. and nl = 3.53 76.81 97. although they occupy (apparently) different positions on the lattice as drawn.94 0.97 0.12 121.32 0.57 190.26 0. u = 3.93 0. s = 0. of a step site may be less or greater than a simple terrace site. a parametrization of the strength of interaction at that site. In the hydrocarbon conversion experiments.53 152.26 65. we have drawn the surface with a step or ledge.0 62.95 76. it is evident that the surface is topologically equivalent to a flat. Similarly. on an 11 X 11 lattice.19 0.34 75. = 5. it is clear that the coordination number n. For definiteness.14 67.63 76.13 65.94 0.90 0. while the ledge site labeled 61 in that figure would be coded u = 4.58 1. however.c for u = 3 and 5 proceeds in a manner similar to that outlined above for the case v = 4.e.70 71. The characterization of surface kink sites in Figures la.52 78.57 88.89 121.93 0.97 0.n. What can distinguish . nl = 0. an atom situated a t a terrace site will be fivecoordinated.site T would be characterized by the specifications u = 5. all other things (energetics.and nl = 2.17 133.85 267.50 67.32 150.85 97.99 0.94 0.71 75.02 109.66 97. given a mean jump time for the stepwise motion of the reactant.

75 1.15 154.54 209.50 0. the percent differences calculated for ( n ) for the valencies v = 3. Langmuir 1986.25 0. (10) See especially contributions by: Roelofs. was found to depend critically on the number and configuration of reaction centers defining a multiplet or ensemble.. planar surface. as s 1). J.50 0. and 5 persisted but decreased with increase in lattice size.20.73 78. against the same terrace site. D. Centrally Positioned Reaction Center b . Comparison of Results for (n) for Lattices with a Single.13 752.e. Lagally.00 0.85 116.75 1. In brief.58 572. For example.75 1. 281. that for which the target site was embedded in a lattice all sites of which could compete with the target.25 0.1° Accordingly. two limiting cases and one intermediate case were studied in this paper. Chem.50 0.75 1. While these particular structural effects are undoubtedly of great importance they are not the only ones thought to play a role in affecting the efficiency of reaction-diffusion processes on a catalytically active surface. Discussion The influence of structure on reactivity.40 56. A. we considered an intermediate case.00 294. 5(T) and 5(62). as stressed recently by Cardillo: absorbates sample all defects on the underlying lattice. s ) 5 x 5 3 6 5 4 3 6 5 4 3 6 5 4 3 6 5 4 3 6 5 4 3 6 5 4 3 6 5 4 3 6 5 4 3 6 5 4 3 6 5 4 3 6 5 4 3 6 5 4 3 Langmuir. M. Phys. in the spirit of the preceding paper.50 0.25 0. 5 and calculated the lattice-statistical quantity ( n ) as a function of increasing system size.75 1. 1.99 129. 1985 451 ledge site 4(T) (see Table V) produces a higher calculated turnover number than the terrace site but the ledge site 4(61) yields a lower turnover number than this (same) terrace site.37 495. If we regard the terrace site as portraying the “perfect” two-dimensional.25 0.20 249.99 113.22 218. Here we found that the consequences of considering the presence of a banded ensemble of competing - (9) Cardillo.20 330. 4.82 167.25 0.08 276. Phys. Springer Ser. against a terrace site and the v = 5 kink sites. In the first case. whereas for a given lattice size the percent difference decreased as the reaction assumed more and more of an irreversible character (i. 1. J.00 0.20 476. we considered only a single reaction center positioned at a site of valency v = 3 vs.50 0.78 264. L.’ on high Miller index surfaces or in studies on the consequences of surface reconstruction and the selvedge effect8).25 0. ledge vs. we have explored the consequences of assuming configurations of reaction sites in competition with each other and have studied the net effect of these sites on the reaction efficiency. We found that for a given trapping probability (s) at the reaction center.75 1.09 71. Springer Ser. The data recorded in Table V (constructed from the data in Table IV as described above) allow one to compare the relative effectiveness of terrace.or 5.20. 24. 1.36 47.00 0. Chem. the (8) See: Forty. 0 1 2 3 0 1 2 3 0. 1983.50 0. M.13 427. and kink sites when both accessibility and ligating ability (respectively entropic and energetic effects) are taken into account. J.e. the latter situated at a central site characterized by a valency v = 3. 1982.20. viz. i.56 4 5 0 1 2 3 0 1 2 3 0 1 2 3 7 x 7 3 4 5 0 1 2 3 0 1 2 3 0 1 2 3 0 1 2 3 0 1 2 3 0 1 2 3 0 1 2 3 9 x 9 3 4 5 1 1x 1 1 3 4 5 when multiplied by 1. G.24 X 1013atoms/12.25 0.73 31. A similar distinction can be seen upon comparing the v = 3 kink sites. kink sites in affecting the reactivity of the system.71 134.50 0.16 318. ledge vs.00 0.49 71.19 281. 1982. the estimate listed in Table V. Springer Ser. assuming a -5% reactivity a t the N .04 160. with the data on ledge and kink sites reflecting the influence of “imperfections” on the catalytic process (as revealed in the studies of Somorjai et al. Of importance as well is the presence of defects and surface reconstruction. in this paper we have relaxed the assumption that the surface of the support is an idealized d = 2 surface and have considered explicitly the role of terrace vs.75 1.99 309.50 0.00 147. factors under intense investigation today.00 0. 271.then our calculations show that step and kink sites may be more or less effective than terrace sites depending on the location of the former.37 43.1 site surrounding the central trap effectively erased distinctions among lattices (or here sites) of different valencies in the same dimension. kink sites in influencing the kinetics of surface reactions.50 0.15 120.82 178. VI. 4. 4 vs.00 0. These calculations show convincingly that the overall catalytic activity of a particular site rests on a delicate balance between energetic and entropic factors. 1982.75 1. 3(T) and 3(61).75 1.40 89. M. Phys.39 372.66 203.40 39.4. A second limiting case. that for which only the ledge sites competed with the target molecule. 149.82 106. 4.00 0.Influence of Structure on Reaction Efficiency.99 210..79 33.25 0. No..44 94.25 0. Chem.12 216. ledge. Then. 2 Table IV.99 156. was studied and found to yield results similar to those reported in our earlier studies on square-planar and hexagonal lattices in d = 2. then the sensitivity to structure documented in the above calculations may be taken as a calibration of the relative importance of terrace vs. this gives the site density.00 0.25 0.50 0. If.00 0.47 55. Contemp.00 0.08 183.75 1.50 0.93 27.00 0. Vol.15 X 1015atoms.25 0. Phys.62 94.75 1. as explored in the preceding contribution.75 1. 219. See also: Cardillo.15 87. between the ligating ability of a particular site (as represented in the present study by nl)and its accessibility to a diffusing coreactant (as monitored here by distinguishing among the possible number of channels v to the active site). .37 61.25 0. Finally.50 0.

(11)We are thankful to the referee for bringing this study to our attention.00 x 1013 6. it is evident from the above discussion (and from remarks in section VI of the preceding paper) that a principal goal of future studies must be to fold into our model the results of electronic structure calculations on absorbate-metal atom clusters in order to place the specification of the site trapping probability on a rigorous basis. 1.) 1984.. for example.23 x 1013 1. Klein. in particular.82 X 1=5 5.77 x 1013 22.85 x 6.lI .85 x 4. J.77 x 1013 11. ledge.00 x 1013 site terrace ledge ledge kink(s) kink(s) kink(s) kink(s) U n l 1 4 4(T) 4(61) 3(T) 3(61) 5(T) 5(62) 2 0 0 3 1 0 lattice site density turnover no. R. conclusions drawn from their experimental studies on low vs. Furthermore. although the distribution of reactive sites in our model was designed to handle situations of increasing complexity (moving from a consideration of single sites to domains of active sites distributed over the surface).23 x 1013 3. it would be very instructive to compare the kinetic consequences of the sort of model developed here with calculations of the rate constant based on transition state (or other) theories.43 X 1=7 3. S. calculations were performed in which the various settings of the reaction parameter s were placed in correspondence with the number of “free” bonds nl characterizing the “electronic unsaturation” at particular sites of the Iattice. we argued that these data were in qualitative accord with the conclusions reached by Somorjai and Cardillo and their co-workers concerning the critical influence of ledges (and other defects) on reactivity. and Kozak turnover no. ledge vs.C. “Chemistry of the MetalGas Interface”. Clarendon Press: Oxford.78 x 10-3 1 = 11 1. since the efficiency of the overall process changed dramatically (increased) when <lo% of the background ledge sites were activated.23 x 1013 2. see: Roberts.83 x 3.1 sites of the lattice).24 x 1013 1.01 x 10-3 E = 11 1. Surf. it cannot be claimed that any one of these configurations represents a particular physical system.3. 430 cited in section 8.1background sites were activated. When taken in conjunction with the valency u (describing the number of channels linking the particular site to the remaining N . First.223. it was found that the pair ( n p ) provided a convenient way of organizing the energetic and entropic factors governing the efficiency of reaction a t the given site. .58 x 10-3 1=7 3.23 x 1013 3.74 x 10-3 1 = 11 1. (12)See. 1attice site density turnover no. certain defects characterized by a given (nl.77 x 1013 6. relative to processes on clean low Miller index surfaces. (-(n)-’) vs.v’)may suppress the conversion to products.83 x 5.33 x 10-3 1 = 11 1. with the net effect of these lattice imperfections reflected in the (ensemble-averaged) turnover number determined experimentally.77 x 10-3 1=5 5.97 x 1=9 1..24 x 1013 4. Yet. even here. 1978. C.06 x 1013 11.73 X 1=5 6.40 x 10-3 1=5 5. 445.63 X 1=7 3.10 x 10-3 1=9 1. that is.00 x 1013 25. W.85 x 2.06 x 1013 8.00 x 1013 10.92 X 1=5 5. as shown by studies of Hzon W using field ion microscopy. by Cardillo and Tully. Again. kink) sites were more effective than terrace sites in leading to reaction but that there were cases where terrace sites remained more effective than ledge or kink sites in enhancing the efficiency of the underlying process. Musho. the delicate interplay between energetic and entropic factors in influencing the efficiency of reaction on a catalytically active surface with defects. ledges. kinks) may certainly alter the turnover number determined experimentally. Cardillo.02 x 1=9 1. See. Vol..5 X 10l6 atoms) 1=5 6.60 x 1=9 1. 1 = 11 1. Science (Washington.83 x 2. McKee. As in the previous study. Furthermore. we found that certain defect (ledge. lattice site density turnover no.06 x 1013 4.00 x 1013 9.17 X 1=5 6. No. C. as have been reviewed. M. chemical interactions (both adsorbate-adsorbate and adsorbate-substrate) may be so strong that adsorbates will not readily diffuse across certain planes. lattice site density turnover no. site density (-(1/12) Table V. as regards the present contributions. 4. These calculations dramatize.’l such constraints are only weakly implied by the class of boundary conditions employed in our study. the references cited in: Tully.32 x 10-3 1=7 3. lattice site density turnover no. for example. Centrally Positioned Reaction Center ( V a l ) X 1.40 x 10-3 1=7 3. high Miller index surfaces. it may be hoped that our calculations provide some insight into the relative importance of chemical interaction vs. Sci.00 x 1013 10.19 x 10-3 reaction centers were not quite as extreme as for the case where all N . They suggest that although the presence of defects (ledges.68 x 1=9 1.77 x 1013 20.23 x 1013 10-3 1013 1013 10-3 1013 10-3 1013 10-3 1013 10-3 1013 10-3 1=7 3.I2 These generalizations of our approach are under development but.24 x 1013 3. and kinks.56 x 10-3 1=1 1 1. lattice site density turnover no.452 Langmuir. the net alteration should probably be interpreted as a trade off of effects.37 X 1=9 1. ComDarison of Turnover Numbers for Lattice with a Sin&. lattice site density turnover no. physical diffusion on surfaces with multiplets of active sites or surfaces with distinguishable terrace. J. we believe.u) may enhance while other types {nl’. In order to provide a more detailed characterization of the effects found a t terrace vs. 1968. M. most catalytic processes of interest occur on highly defect surfaces of supported crystallites in which the support-crystallite interaction can exert a considerable influence on the efficiency of the catalytic process.61 X 1=7 3. D.74 x 1=9 1. the discussion of the work of Folman.03 x 10-3 1 = 11 1. and kink sites of differing catalytic activity.47 x 10-3 17.83 x 5.00 x 1013 3. 1985 Staten. it is important to evaluate critically the approach taken in this paper in assessing the difference in reactivity at steps. When both (nbvJ were considered. M. kink sites.