Reactions of nickel (Ni−n, n=3–10), palladium (Pd−n, n=3–8), and platinum (Pt−n, n=3–7) cluster anions are investigated in a flow tube reactor. Rate coefficients are measured for reactions with N2, O2, CO2, and N2O. Reactions with O2, CO2, and N2O have rates that are greater than 10% of the collision rate for most clusters of four atoms or larger, while N2 reactions generally exhibit much lower reaction efficiencies. All the reactions studied show a strong dependence on cluster elemental composition. Many of the palladium cluster reactions are significantly faster than the corresponding nickel and platinum cluster reactions, while Ni−n and Pt−n have similar rate coefficients. Pt−6 is observed to have anomalously low rate constants for reactions with N2, CO2, and N2O compared to neighboring platinum clusters sizes and the nickel and palladium hexamers. N2, CO2, and O2 reactions are generally association reactions with varying degrees of cluster fragmentation observed. N2O reactions result in sequential addition of O atoms to the cluster. The extent of cluster fragmentation for the various reagents can be correlated with the estimated exothermicities of the adsorption processes.
REFERENCES
1.
T. D.
Klots
, B. J.
Winter
, E. K.
Parks
, and S. J.
Riley
, J. Chem. Phys.
92
, 2110
–2111
(1990
).2.
E. K.
Parks
, B. J.
Winter
, T. D.
Klots
, and S. J.
Riley
, J. Chem. Phys.
94
, 1882
–1902
(1991
).3.
B. J.
Winter
, E. K.
Parks
, and S. J.
Riley
, J. Chem. Phys.
94
, 8618
–8621
(1991
).4.
T. D.
Klots
, B. J.
Winter
, E. K.
Parks
, and S. J.
Riley
, J. Chem. Phys.
95
, 8919
–8930
(1991
).5.
B. J.
Winter
, T. D.
Klots
, E. K.
Parks
, and S. J.
Riley
, Z. Phys. D.
19
, 375
–380
(1991
).6.
E. K.
Parks
, B. J.
Winter
, T. D.
Klots
, and S. J.
Riley
, J. Chem. Phys.
96
, 8267
–8274
(1992
).7.
8.
D. M.
Cox
, K. C.
Reichmann
, D. J.
Trevor
, and A.
Kaldor
, J. Chem. Phys.
88
, 111
(1988
).9.
M. R.
Zakin
, R. O.
Brickman
, D. M.
Cox
, and A.
Kaldor
, J. Chem. Phys.
88
, 6605
–6610
(1988
).10.
A.
Kaldor
and D. M.
Cox
, J. Chem. Soc. Faraday Trans.
86
, 2459
(1990
).11.
12.
13.
D. M.
Cox
, R.
Brickman
, K.
Creegan
, and A.
Kaldor
, Z. Phys. D
19
, 353
–355
(1991
).14.
B. C.
Guo
, K. P.
Kerns
, and A. W.
Castleman
, Jr., J. Chem. Phys.
96
, 8177
–8186
(1992
).15.
P.
Fayet
, M. J.
McGlinchley
and L. H.
Wöste
, J. Am. Chem. Soc.
109
, 1733
(1987
).16.
X.
Ren
, P. A.
Hintz
, and K. M.
Ervin
, J. Chem. Phys.
99
, 3575
(1993
).17.
18.
M. D.
Morse
, M. E.
Geusic
, J. R.
Heath
, and R. E.
Smalley
, J. Chem. Phys.
83
, 2293
–2304
(1985
).19.
W. F.
Hoffman
, III, E. K.
Parks
, G. C.
Nieman
, L. G.
Pobo
, and S. J.
Riley
, Z. Phys. D
7
, 83
–89
(1987
).20.
E. K.
Parks
, T. D.
Klots
, and S. J.
Riley
, J. Chem. Phys.
92
, 3813
–3826
(1990
).21.
B. J.
Winter
, T. D.
Klots
, E. K.
Parks
, and S. J.
Riley
, Z. Phys. D
19
, 381
–394
(1991
).22.
D. J.
Trevor
, R. L.
Whetten
, D. M.
Cox
, and A.
Kaldor
, J. Am. Chem. Soc.
1985
, 518
–519
(1985
).23.
D. J.
Trevor
, D. M.
Cox
, and A.
Kaldor
, J. Am. Chem. Soc.
112
, 3742
–3749
(1990
).24.
P.
Fayet
, A.
Kaldor
, and D. M.
Cox
, J. Chem. Phys.
92
, 254
–261
(1990
).25.
M. P.
Irion
and A.
Selinger
, Ber. Bunsenges. Phys. Chem.
93
, 1408
(1989
).26.
M. P.
Irion
, P.
Schnabel
, and A.
Selinger
, Ber. Bunseges. Phys. Chem.
94
, 1291
(1990
).27.
M. P.
Irion
, A.
Selinger
, and P.
Schnabel
, Z. Phys. D
19
, 393
(1991
).28.
T. F.
Magnera
, D. E.
David
, and J.
Michl
, J. Am. Chem. Soc.
109
, 936
–938
(1987
).29.
M. B.
Knickelbein
and W. J. C.
Menezes
, J. Phys. Chem.
96
, 6611
(1992
).30.
L.
Lian
, C. X.
Su
, and P. B.
Armentrout
, J. Chem. Phys.
96
, 7542
(1992
).31.
K. M.
Ervin
, J.
Ho
, and W. C.
Lineberger
, J. Chem. Phys.
89
, 4514
–4521
(1988
).32.
G.
Ganteför
, M.
Gausa
, K.-H.
Meiwes-Broer
, and H. O.
Lutz
, J. Chem. Soc. Faraday Trans.
86
, 2483
–2488
(1990
).33.
34.
35.
36.
R. P.
Messmer
, S. K.
Knudson
, K. H.
Johnson
, J. B.
Diamond
, and C. Y.
Yang
, Phys. Rev. B
13
, 1396
–1415
(1976
).37.
38.
C. F.
Melius
, T. H.
Upton
, and W. A.
Goddard
, III, Solid State Commun.
28
, 501
–504
(1978
).39.
H.
Basch
, M. D.
Newton
, and J. W.
Moskowitz
, J. Chem. Phys.
73
, 4492
–4509
(1980
).40.
R.
Hoogewijs
, G.
Dalmai
, and J.
Vennik
, Phys. Status Solidi A
59
, 461
–468
(1980
).41.
42.
43.
M. A.
Nygren
, P. E. M.
Siegbahn
, U.
Wahlgren
, and H.
Akeby
, J. Phys. Chem.
96
, 3633
–3640
(1992
).44.
M. R. A.
Blomberg
and P. E. M.
Siegbahn
, J. Am. Chem. Soc.
115
, 6908
–6915
(1993
).45.
M. S.
Stave
and A. E.
DePristo
, J. Chem. Phys.
97
, 3386
–3398
(1992
).46.
47.
48.
49.
50.
K.
Horn
, J.
DiNardo
, W.
Eberhardt
, H.-J.
Freund
, and E. W.
Plummer
, Surf. Sci.
118
, 465
–495
(1982
).51.
M.
Grunze
, P. A.
Dowben
, and R. G.
Jones
, Surf. Sci.
141
, 455
–472
(1984
).52.
P. A.
Dowben
, Y.
Sakisaka
, and T. N.
Rhodin
, Surf. Sci.
147
, 89
–102
(1984
).53.
Y.
Kuwahara
, M.
Jo
, H.
Tsuda
, M.
Onchi
, and M.
Nishijima
, Surf. Sci.
180
, 421
–432
(1987
).54.
Y.
Kuwahara
, M.
Fujisawa
, M.
Jo
, M.
Onchi
, and M.
Nishijima
, Surf. Sci.
188
, 490
–504
(1987
).55.
Y.
Kuwahara
, M.
Fujisawa
, M.
Onchi
, and M.
Nishijima
, Surf. Sci.
207
, 17
–35
(1988
).56.
57.
58.
59.
60.
J.
Chatt
, J. R.
Dilworth
, and R. L.
Richards
, Chem. Rev.
78
, 589
–625
(1978
).61.
T.
Yamabe
, K.
Hori
, T.
Minato
, and K.
Fukui
, Inorg. Chem.
19
, 2154
(1980
).62.
H.
Huber
, E. P.
Kündig
, M.
Moskovits
, and G. A.
Ozin
, J. Am. Chem. Soc.
95
, 332
–344
(1973
).63.
G. A.
Ozin
and W. E.
Klotzbücher
, J. Am. Chem. Soc.
97
, 3965
–3974
(1975
).64.
S. G.
Lias
, J. E.
Bartmess
, J. F.
Liebman
, J. L.
Holmes
, R. D.
Levin
, and W. G.
Mallard
, J. Phys. Chem. Ref. Data
17
, Suppl. 1
(1988
).65.
M.
Grunze
, R. K.
Driscoll
, G. N.
Burland
, J. C. L.
Gomish
, and J.
Pritchard
, Surf. Sci.
89
, 381
(1979
).66.
67.
G. A. Somorjai, Chemistry in Two Dimensions: Surfaces (Cornell Univ. Press, Ithaca, NY, 1981).
68.
M. R. A.
Blomberg
and P. E. M.
Siegbahn
, Chem. Phys. Lett.
179
, 524
–530
(1991
).69.
J. P. Collman, L. S. Hegedus, J. R. Norton, and R. G. Finke, Principles and Applications of Organotransition Metal Chemistry (University Sci ence, Mill Valley, CA, 1987).
70.
C. N. R.
Rao
, P. V.
Kamath
, and S.
Yashanath
, Chem. Phys. Lett.
88
, 13
(1982
).71.
P.
Vishnu Kamath
and C. N. R.
Rao
, J. Phys. Chem.
88
, 464
–469
(1984
).72.
73.
J.
Schmidt
, Ch.
Stuhlmann
, and H.
Ibach
, Surf. Sci.
284
, 121
–128
(1993
).74.
D.
Brennan
, D. O.
Hayward
, and B. M. W.
Trapnell
, Proc. R. Soc. London Ser. A
256
, 81
–105
(1960
).75.
76.
J.
Kiss
, D.
Lennon
, S. K.
Jo
, and J. M.
White
, J. Phys. Chem.
95
, 8054
–8059
(1991
).77.
78.
79.
80.
D. E. A.
Gordon
and R. M.
Lambert
, Surf. Sci.
287/288
, 114
–118
(1993
).81.
Z. M.
Liu
, Y.
Zhou
, F.
Solymosi
, and J. M.
White
, Surf. Sci.
245
, 289
(1991
).82.
M. F. H.
van Tol
, A.
Gielbert
, R. M.
Wolf
, A. B. K.
Lie
, and B. E.
Neiuwenhuys
, Surf. Sci.
3287/288
, 201
(1993
).83.
84.
L.
Zhu
, J.
Ho
, E. K.
Parks
, and S. J.
Riley
, J. Chem. Phys.
98
, 2798
–2804
(1993
).85.
J. C.
Calabrese
, L. F.
Dahl
, P.
Chini
, G.
Longoni
, and S.
Martinengo
, J. Am. Chem. Soc.
96
, 2614
(1974
).86.
J. C.
Calabrese
, L. F.
Dahl
, A.
Cavalieri
, P.
Chini
, G.
Longoni
, and S.
Martinengo
, J. Am. Chem. Soc.
96
, 2616
(1974
).87.
G.
Longoni
, P.
Chini
, and A.
Cavalieri
, Inorg. Chem.
15
, 3025
(1976
).88.
89.
G.
Nagaki
, L. D.
Lower
, G.
Longoni
, P.
Chini
, and L. F.
Dahl
, Organometallics
5
, 1764
(1986
).
This content is only available via PDF.
© 1995 American Institute of Physics.
1995
American Institute of Physics
You do not currently have access to this content.
