Sodium doped silicon clusters (SinNam;1⩽n⩽14,1⩽m⩽5) produced by two types of laser vaporization were studied. The adsorption of Na atoms on the Sin clusters leads the substantial lowering of the ionization energy, Ei, of SinNam clusters. Their reactivity toward NO molecules was measured with a fast flow reactor, and the anticorrelation between the Eis and the reactivity was clearly observed; species having low Ei exhibit high reactivity and vice versa. Moreover, the clear parallelism between the Eis of SinNa and the EAs of Sin is found. This is consistent with the fact that the structure of SinNa clusters keeps the frame of the corresponding Sin cluster unchanged and that the electronic structure of SinNa is similar to that of the corresponding negative ion Sin. In addition to the experimental studies, the geometries, adsorption energies, and vertical ionization energies of SinNa(n=1–7) were investigated with ab initio MO calculations including electron correlation; The Mo/ller–Plesset perturbation theory was used and the configuration interaction (CI) calculation was carried out, particularly for a diatomic molecule, SiNa.

1.
M. F.
Jarrold
,
Science
252
,
1085
(
1991
).
2.
M. F.
Jarrold
,
J. Phys. Chem.
99
,
11
(
1995
).
3.
(a)
L. A.
Bloomfield
,
M. E.
Geusic
,
R. R.
Freeman
, and
W. L.
Brown
,
Chem. Phys. Lett.
121
,
33
(
1985
);
(b)
J. R.
Heath
,
Y.
Liu
,
S. C.
O’Brien
,
Q.-L.
Zhang
,
R. F.
Curl
,
F. K.
Tittel
, and
R. E.
Smalley
,
J. Chem. Phys.
83
,
5520
(
1985
);
(c)
D. J.
Trevor
,
D. M.
Cox
,
K. C.
Reichmann
,
R. O.
Brickman
, and
A.
Kaldor
,
J. Phys. Chem.
91
,
2598
(
1987
).
4.
E. C.
Honea
,
A.
Ogura
,
C. A.
Murray
,
K.
Raghavachari
,
W. O.
Sprenger
,
M. F.
Jarrold
, and
W. L.
Brown
,
Nature
366
,
42
(
1993
).
5.
S.
Li
,
R. J.
Van Zee
,
W.
Weltner
, Jr.
, and
K.
Raghavachari
,
Chem. Phys. Lett.
243
,
275
(
1995
).
6.
L. A.
Bloomfield
,
R. R.
Freeman
, and
W. L.
Brown
,
Phys. Rev. Lett.
54
,
2246
(
1985
).
7.
(a)
Y.
Liu
,
Q.-L.
Zhang
,
F. K.
Tittel
,
R. F.
Curl
, and
R. E.
Smalley
,
J. Chem. Phys.
85
,
7434
(
1986
);
(b)
Q.-L.
Zhang
,
Y.
Liu
,
R. F.
Curl
,
F. K.
Tittel
, and
R. E.
Smalley
,
J. Chem. Phys.
88
,
1670
(
1988
); ,
J. Chem. Phys.
(c)
S. M.
Beck
and
J. M.
Andrews
,
J. Chem. Phys.
91
,
4420
(
1989
).,
J. Chem. Phys.
8.
W.
Begemann
,
R.
Hector
,
Y. Y.
Liu
,
J.
Tiggesbäumker
,
K. H.
Meiwes-Broer
, and
H. O.
Lutz
,
Z. Phys. D
12
,
229
(
1989
).
9.
M. F.
Jarrold
and
E. C.
Honea
,
J. Phys. Chem.
95
,
9181
(
1991
).
10.
(a)
M. L.
Mandich
,
V. E.
Bondybey
, and
W. D.
Reents
,Jr.
,
J. Chem. Phys.
86
,
4245
(
1987
);
(b)
M. L.
Mandich
,
W. D.
Reents
,Jr.
, and
K. D.
Kolenbrander
,
Pure Appl. Chem.
62
,
1653
(
1990
);
(c)
M. F.
Jarrold
,
U.
Ray
, and
K. M.
Creegan
,
J. Chem. Phys.
93
,
224
(
1990
);
(d)
J. M.
Alford
,
R. T.
Laaksonen
, and
R. E.
Smalley
,
J. Chem. Phys.
94
,
2618
(
1991
); ,
J. Chem. Phys.
(e)
U.
Ray
and
M. F.
Jarrold
,
J. Chem. Phys.
94
,
2631
(
1991
).,
J. Chem. Phys.
11.
K.
Fuke
,
K.
Tsukamoto
,
F.
Misaizu
, and
M.
Sanekata
,
J. Chem. Phys.
99
,
7807
(
1993
).
12.
O.
Cheshnovsky
,
S. H.
Yang
,
C. L.
Pettiette
,
M. J.
Craycraft
,
Y.
Liu
, and
R. E.
Smalley
,
Chem. Phys. Lett.
138
,
119
(
1987
).
13.
M. R.
Nimlos
,
L. B.
Harding
, and
G. B.
Ellison
,
J. Chem. Phys.
87
,
5116
(
1987
).
14.
(a)
T. N.
Kitsopoulos
,
C. J.
Chick
,
A.
Weaver
, and
D. M.
Neumark
,
J. Chem. Phys.
93
,
6108
(
1990
);
(b)
T. N.
Kitsopoulos
,
C. J.
Chick
,
Y.
Zhao
, and
D. M.
Neumark
,
J. Chem. Phys.
95
,
1441
(
1991
); ,
J. Chem. Phys.
(c)
C. C.
Arnold
and
D. M.
Neumark
,
J. Chem. Phys.
99
,
3353
(
1993
); ,
J. Chem. Phys.
(d)
C. C.
Arnold
and
D. M.
Neumark
,
J. Chem. Phys.
100
,
1797
(
1994
).,
J. Chem. Phys.
15.
K.
Raghavachari
and
V.
Logovinsky
,
Phys. Rev. Lett.
55
,
2853
(
1985
).
16.
K.
Raghavachari
,
J. Chem. Phys.
83
,
3520
(
1985
).
17.
K.
Raghavachari
,
J. Chem. Phys.
84
,
5672
(
1986
).
18.
K.
Raghavachari
and
C. M.
Rohlfing
,
J. Chem. Phys.
89
,
2219
(
1988
).
19.
C. M.
Rohlfing
and
K.
Raghavachari
,
Chem. Phys. Lett.
167
,
559
(
1990
).
20.
K.
Raghavachari
and
C. M.
Rohlfing
,
J. Chem. Phys.
94
,
3670
(
1991
).
21.
C. M.
Rohlfing
and
K.
Raghavachari
,
J. Chem. Phys.
96
,
2114
(
1992
).
22.
W.
von Niessen
and
V. G.
Zakrzewski
,
J. Chem. Phys.
98
,
1271
(
1993
).
23.
N.
Binggeli
and
J. R.
Chelikowsky
,
Phys. Rev. Lett.
75
,
493
(
1995
).
24.
R.
Kishi
,
M.
Gomei
,
A.
Nakajima
,
S.
Iwata
, and
K.
Kaya
,
J. Chem. Phys.
104
,
8593
(
1996
).
25.
(a)
G. S.
Glander
and
M. B.
Webb
,
Surf. Sci.
222
,
64
(
1989
);
(b)
G. S.
Glander
and
M. B.
Webb
,
Surf. Sci.
224
,
60
(
1989
).,
Surf. Sci.
26.
R.
Souda
,
W.
Hayami
,
T.
Aizawa
,
S.
Otani
, and
Y.
Ishizawa
,
Phys. Rev. Lett.
69
,
192
(
1992
).
27.
(a)Physics and Chemistry of Alkali Adsorption, edited by H. P. Bonzel and G. Ertl (Elsevier, Amsterdam, 1989);
(b)
A.
Namiki
,
S.
Suzuki
,
H.
Kato
,
Y.
Babasaki
,
M.
Tanaka
,
T.
Nakamura
, and
T.
Suzaki
,
J. Chem. Phys.
97
,
3781
(
1992
).
28.
(a)
J. E.
Northrup
,
J. Vac. Sci. Technol. A
4
,
1404
(
1986
);
(b)
I. P.
Batra
,
Phys. Rev. B
39
,
3919
(
1989
);
(c)
K.
Kobayashi
,
S.
Blügel
,
H.
Ishida
, and
K.
Terakura
,
Surf. Sci.
242
,
349
(
1991
);
(d)
S. N.
Ekpenuma
and
A. K.
Ray
,
J. Phys. Condensed Matter
4
,
5077
(
1992
);
(e)
Y.
Enta
,
T.
Kinoshita
,
S.
Suzuki
, and
S.
Kono
,
Phys. Rev. B
36
,
9801
(
1987
).
29.
A.
Nakajima
,
K.
Hoshino
,
T.
Naganuma
,
Y.
Sone
, and
K.
Kaya
,
J. Chem. Phys.
95
,
7061
(
1991
).
30.
K.
Kaya
,
T.
Sugioka
,
T.
Taguwa
,
K.
Hoshino
, and
A.
Nakajima
,
Z. Phys D
26
, S,
201
(
1993
).
31.
R.
Kishi
,
A.
Nakajima
,
S.
Iwata
, and
K.
Kaya
,
Chem. Phys. Lett.
224
,
200
(
1994
).
32.
R.
Kishi
,
A.
Nakajima
,
S.
Iwata
, and
K.
Kaya
,
Surf. Rev. Lett.
3
,
365
(
1996
).
33.
S.
Nonose
,
Y.
Sone
,
K.
Onodera
,
S.
Sudo
, and
K.
Kaya
,
J. Phys. Chem.
94
,
2744
(
1990
).
34.
(a)
M. E.
Geusic
,
M. D.
Morse
,
S. C.
O’Brien
, and
R. E.
Smalley
,
Rev. Sci. Instrum.
56
,
2123
(
1985
);
(b)
D. M.
Cox
,
D. J.
Trevor
,
R. L.
Whetten
, and
A.
Kaldor
,
J. Phys. Chem.
92
,
421
(
1988
).
35.
Electronic-mail address: kaya@iw.chem.keio.ac.jp.
36.
H. B.
Schlegel
,
J. Chem. Phys.
84
,
4530
(
1986
).
37.
Gaussian Basis Sets for Molecular Calculations, Physical Sciences Data, edited by S. Huzinaga (Elsevier, New York, 1985), Vol. 16.
38.
S.
Iwata
,
Chem. Phys. Lett.
83
,
134
(
1981
).
39.
M. W.
Schmidt
,
K. K.
Baldridge
,
J. A.
Boatz
,
J. H.
Jensen
,
S.
Koseki
,
M. S.
Gordon
,
K. A.
Nguyen
,
T. L.
Windus
, and
S. T.
Elbert
,
QCPE Bull.
10
,
52
(
1990
).
40.
M. J. Frisch, G. W. Trucks, M. Head-Gordon, P. M. W. Gill, M. W. Wong, J. B. Foresman, B. G. Jhonson, H. B. Schlegel, M. A. Robb, E. S. Replogle, R. Gomperts, J. L. Andres, K. Raghavachari, J. S. Binkley, C. Gonzalez, R. L. Martin, D. J. Fox, D. J. Defrees, J. Baker, J. J. P. Stewart, and J. A. Pople, GAUSSIAN 92, Revision E. 3, Gaussian, Inc., Pittsburgh, PA, 1992.
41.
M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez, and J. A. Pople, GAUSSIAN 94, Revision B. 2, Gaussian, Inc., Pittsburgh, PA, 1995.
42.
R. Kishi, H. Kawamata, Y. Negishi, S. Iwata, A. Nakajima, and K. Kaya, J. Chem. Phys. (submitted).
43.
H.
Hotop
and
W. C.
Lineberger
,
J. Phys, Chem. Ref. Data
4
,
539
(
1975
).
44.
R. L.
Whetten
,
D. M.
Cox
,
D. J.
Trevor
, and
A.
Kaldor
,
Phys. Rev. Lett.
54
,
1494
(
1985
).
45.
W. J. C.
Menezes
and
M. B.
Knickelbein
,
Chem. Phys. Lett.
183
,
357
(
1991
).
46.
K.
Hoshino
,
T.
Naganuma
,
Y.
Yamada
,
K.
Watanabe
,
A.
Nakajima
, and
K.
Kaya
,
J. Chem. Phys.
97
,
3803
(
1992
).
47.
(a)
A. I.
Boldyrev
and
J.
Simons
,
J. Phys. Chem.
97
,
1526
(
1993
);
(b)
A. I.
Boldyrev
,
N.
Gonzales
, and
J.
Simons
,
J. Phys. Chem.
98
,
9932
(
1994
).,
J. Phys. Chem.
48.
Reference Data on Atoms, Molecules and Ions, edited by A. A. Rodzig and B. M. Smirnov (Springer-Verlag, Berlin, 1985).
49.
Constants of Diatomic Molecules, edited by K. P. Huber and G. Herzberg (Van Nostrand Reinhold, New York, 1979).
50.
(a)Analysis of Optical Spectra, NSRDES-NBS 34, edited by C. E. Moore National Bureau of Standards, 1971;
(b)Handbook of Chemistry and Physics, edited by R. C. Weast (CRC, Boca Raton, 1980), Vol. 61, p. E-69.
51.
(a)
C. B.
Winstead
,
S. J.
Paukstis
, and
J. L.
Gole
,
Chem. Phys. Lett.
237
,
81
(
1995
);
(b)
C. B.
Winstead
,
S. J.
Paukstis
, and
J. L.
Gole
,
J. Mol. Spectrosc.
173
,
311
(
1995
).
52.
K. Fuke (private communication).
This content is only available via PDF.
You do not currently have access to this content.