Abstract
When a metal/liquid interface is probed with second-harmonic generation, the experimental data can be severely complicated by mixed signatures of linear and nonlinear optical properties of the interface. This problem is demonstrated and clarified in this report with computer simulations for selected electrochemical systems. A phenomenological framework for these simulations is developed. The first- and second-order surface susceptibilities of the metal are treated on equal footing, and their variations due to adsorbate effects are analyzed. Analytical and simulated results are presented for two specific groups of adsorbates. Representative experimental systems of these two groups (electrodeposited Cu and Te on polycrystalline Au) are analyzed in further detail. The calculations are in full agreement with the previously published experimental data for these systems. The present formalism can be extended to other systems and, in a systematic manner, can facilitate the analysis of second-harmonic data for electrochemical systems.
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References
1.
Shen
Y. R.
, Ann. Rev. Mater. Sci. 16 , 69 (1986 ).
2.
Richmond
G. L.
, Electroanal. Chem. 17 , 107 (1991 ).
3.
Corn
R. M.
and
Higgins
D. A
, Chem. Rev. 94 , 107 (1994 ).
4.
Guyot-Sionnest
P.
Chen
W.
and
Shen
Y. R
, Phys. Rev. B 33 , 8254 (1986 ).
5.
Aers
G. C.
and
Inglesfield
J. E
, Surf. Sci. 217 , 367 (1989 ).
6.
Guyot-Sionnest
P.
Tadjeddine
A.
and
Liebsch
A
, Phys. Rev. Lett. 64 , 1678 (1990 ).
7.
Schmickler
W.
and
Urbakh
M
, Phys. Rev. B 47 , 6644 (1993 ).
8.
Rebentrost
F.
and
Kuchler
M
, Phys. Rev. Lett. 71 , 2662 (1993 ).
9.
McIntyre
J. D. E.
, “Specular Reflection Spectroscopy of the Electron-Solution Interphase” , in Advances in Electrochemistry and Electrochemical Engineering , Vol. 9 ,
Muller
R. H.
, Ed. (Wiley , New York , 1973 ), p. 61 .
10.
Kolb
D. M.
, “Physical and Electrochemical Properties of Metal Monolayers on Metallic Substrates” , in Advances in Electrochemistry and Electrochemical Engineering, Vol. 11 ,
Gerischer
H.
and
Tobias
C. W
, Eds. (Wiley , New York , 1978 ), p. 125 .
11.
Gerischer
H.
Kolb
D. M.
and
Sass
J. K
, Adv. Phys. 27 , 437 (1978 ).
12.
Brodsky
A. M.
and
Urbakh
M. I
, Prog. Surf. Sci. 15 , 121 (1984 ).
13.
Furtak
T. E.
and
Lynch
D. W
, Phys. Rev. Lett. 35 , 960 (1975 ).
14.
Parsons
R.
, Chem. Rev. 90 , 813 (1990 ).
15.
Mizrahi
V.
and
Sipe
J. E
, J. Opt. Soc. Am. B 5 , 660 (1988 ).
16.
Kolb
D. M.
Leutlof
D.
and
Prazasnyski
M
, Surf. Sci. 47 , 622 (1975 ).
17.
Roy
D.
, Electrochim. Acta 39 , 2699 (1994 ); ibid., 40 , 2557 (1995 ).
18.
Corn
R. M.
Ramagnoli
M.
Levenson
M.
and
Philpott
M. R
, J. Chem. Phys. 81 , 4127 (1994 ).
19.
Rojhantalab
H. M.
and
Richmond
G. L
, J. Phys. Chem. 191 , 38 (1985 ).
20.
Campbell
D. J.
Lynch
M. L.
and
Corn
R. M
, Langmuir 6 , 1656 (1990 ).
21.
Tadjeddine
A.
and
Guyot-Sionnest
P
, J. Phys. Chem. 94 , 5193 (1990 ).
22.
Bloembergen
N.
Chang
R. K.
Jha
S. S.
and
Lee
C. H
, Phys. Rev. 174 , 813 (1968 ); ibid., 178 , 1528 (E) (1969 ).
23.
Mendoza
B.
and
Mochan
W. L
, Phys. Rev. B 53 , 4999 (1996 ).
24.
Corvi
M.
and
Schaich
W. L
, Phys. Rev. B 33 , (1986 ).
25.
Sipe
J. E.
So
V. C. Y.
Fuki
M.
and
Stegman
G. F
, Phys. Rev. B 21 , 4389 (1980 ).
26.
Liebsch
A.
, Surf. Sci. 307 , 1007 (1994 ).
27.
Jensen
H. R.
, J. Opt. Soc. Am. B 11 , 2359 (1994 ).
28.
Chizmeshya
A.
and
Zaremba
E
, Phys. Rev. B 37 , 2805 (1988 ).
29.
Persson
B. N. J.
and
Dubois
L. H
, Phys. Rev. B 39 , 8220 (1989 ).
30.
Jiang
M. Y.
Pajer
G.
and
Burnstein
E
, Surf. Sci. 242 , 307 (1991 ).
31.
Salie
G.
, J. Electroanal. Chem. 245 , 1 (1988 ).
32.
Kolb
D. M.
, M. Przasnyski, and H. Gerischer, Electroanal. Chem. 54 , 25 (1974 ).
33.
Gao
R.
Hewitt
T. D.
and
Roy
D
, J. Phys. Chem. Solids 54 , 685 (1993 ).
34.
Kötz
R.
and
Kolb
D. M
, Z. Physik Chem. NF 112 , 69 (1978 ).
35.
Anderson
W. J.
and
Hansen
W. N
, J. Electroanal. Chem. 47 , 229 (1973 ).
36.
Hewitt
T. D.
Gao
R.
and
Roy
D
, Surf. Sci. 291 , 233 (1973 ).
37.
Yerushalemi-Rozen
R.
Klein
J.
and
Berkovic
B
, Langmuir 8 , 1392 (1992 ).
38.
Nagy
G.
and
Roy
D
, J. Phys. Chem. 98 , 6592 (1994 ).
39.
Rosenzweig
Z.
and
Asscher
M
, Surf. Sci. 204 , L732 (1988 ); ibid., 240 , L583 (1990 ).
40.
Wooten
F.
, Optical Properties of Solids (Academic Press , New York , 1972 ).
41.
Boyd
R. W.
, Nonlinear Optics (Academic Press , San Diego, California , 1992 ).
42.
Nagy
G.
and
Roy
D
, Langmuir 11 , 3457 (1995 ); ibid., 12 , 1696 (1996 ).
43.
Rudnick
J.
and
Stern
E. A
, Phys. Rev. B 4 , 4274 (1971 ).
44.
Lovell
M. A.
Walters
M. J.
and
Roy
D
, Electrochim. Acta, paper in press .
45.
Tom
H. W. K.
Heinz
T. F.
and
Shen
Y. R
, Laser Chem. 3 , 279 (1983 ).
46.
Macdonald
J. R.
and
Barlow
C. A
, Surf. Sci. 4 , 381 (1966 ).
47.
Lamperski
S.
, J. Electroanal. Chem. 379 , 445 (1994 ).
48.
Nagy
G.
and
Roy
D
, Surf. Sci. 320 , 7 (1994 ).
49.
Schmidt
L. D.
and
Gomer
R
, J. Chem. Phys. 45 , 1605 (1966 ).
50.
Koos
D. A.
Kellar
S. A.
and
Richmond
G. L
, J. Phys. Chem. 93 , 6434 (1989 ).
51.
Hewitt
T. D.
and
Roy
D
, Chem. Phys. Lett. 181 , 407 (1991 ).
52.
Friedrich
A.
Pettinger
B.
Kolb
D. M.
Lupke
G.
Steinhoff
R.
and
Marowsky
G
, Chem. Phys. Lett. 163 , 123 (1989 ).
53.
Koos
D. A.
and
Richmond
G. L
, J. Phys. Chem. 96 , 3770 (1992 ).
54.
Kim
S.
Zhao
M.
Scherson
D.
Choi
K.-J.
and
Bae
I. T
, J. Phys. Chem. 98 , 9383 (1994 ).
55.
Lakkaraju
S.
Bennahmias
M. J.
Borges
G. L.
Gordon
J. G.
II
Lazaga
M.
Stone
B. M.
and
Ashley
K
, Appl. Opt. 29 , 4943 (1990 ).
56.
Yagi
I.
Lantz
J. M.
Nakabayashi
S.
Corn
R. M.
and
Uosaki
K
, J. Electroanal Chem. 401 , 95 (1996 ).
57.Handbook of Optical Constants of Solids ,
Palik
E. D.
, Ed. (Academic Press , San Diego, California , 1985 ).
58.
Wong
K. L.
and
Richmond
G. L
, J. Chem. Phys. 99 , 5500 (1993 ).
59.
Hale
G. M.
and
Querry
M. R
, Appl. Opt. 12 , 555 (1973 ).
60.
Ikemiya
N.
Kubo
T.
and
Hara
S
, Surf. Sci. 323 , 81 (1995 ).
61.
Kolb
D. M.
and
Kotz
R
, Surf. Sci. 64 , 698 (1977 ).
62.
Powers
D. E.
Hansen
S. G.
Geusic
M. E.
Michalopoulos
D. L.
and
Smalley
R. E
, J. Chem. Phys. 78 , 2866 (1983 ).
63.
Kittel
C.
, Introduction to Solid State Physics (Wiley , New York , 1996 ).
64.
Petukhov
A. V.
and
Liebsch
A
, Surf. Sci. 294 , 381 (1993 ).
65.
Lang
N. D.
and
Kohn
W
, Phys. Rev B 1 , 4555 (1970 ).
66.
Bard
A. J.
and
Faulkner
L. R
, Electrochemical Methods, Fundamentals and Applications (Wiley , New York , 1980 ).
67.
Conway
B. E.
, Prog. Surf. Sci. 16 , 1 (1984 ).