The charge-dependent structure of interfacial water at the n-Ge(100)-aqueous perchlorate interface was studied by controlling the electrode potential. Specifically, a joint attenuated total reflection infrared spectroscopy and electrochemical experiment was used in 0.1M NaClO4 at pH ≈ 1–10. The germanium surface transformation to an H-terminated surface followed the thermodynamic Nernstian pH dependence and was observed throughout the entire pH range. A singular value decomposition-based spectra deconvolution technique coupled to a sigmoidal transition model for the potential dependence of the main components in the spectra shows the surface transformation to be a two-stage process. The first stage was observed together with the first appearance of Ge–H stretching modes in the spectra and is attributed to the formation of a mixed surface termination. This transition was reversible. The second stage occurs at potentials ≈0.1–0.3 V negative of the first one, shows a hysteresis in potential, and is attributed to the formation of a surface with maximum Ge–H coverage. During the surface transformation, the surface becomes hydrophobic, and an effective desolvation layer, a “hydrophobic gap,” developed with a thickness ≈1–3 Å. The largest thickness was observed near neutral pH. Interfacial water IR spectra show a loss of strongly hydrogen-bound water molecules compared to bulk water after the surface transformation, and the appearance of “free,” non-hydrogen bound OH groups, throughout the entire pH range. Near neutral pH at negative electrode potentials, large changes at wavenumbers below 1000 cm−1 were observed. Librational modes of water contribute to the observed changes, indicating large changes in the water structure.
REFERENCES
1.
2.
K. D.
Collins
and M. W.
Washabaugh
, Q. Rev. Biophys.
18
, 323
–422
(1985
).3.
D. T.
Richens
, The Chemistry of Aqua Ions: Synthesis, Structure and Reactivity: A Tour Through the Periodic Table of the Elements
(Wiley
, New York
, 1997
).4.
H. S.
Frank
and M. W.
Evans
, J. Chem. Phys.
13
, 507
(1945
).5.
W.
Blokzijl
and J. B. F. N.
Engberts
, Angew. Chem., Int. Ed. Engl.
32
, 1545
(1993
).6.
N. T.
Southall
, K. A.
Dill
, and A. D. J.
Haymet
, J. Phys. Chem. B
106
, 521
(2002
).7.
M.
Mucha
, T.
Frigato
, L. M.
Levering
, H. C.
Allen
, D. J.
Tobias
, L. X.
Dang
, and P.
Jungwirth
, J. Phys. Chem. B
109
, 7617
(2005
).8.
C.
Lee
, J. A.
McCammon
, and P. J.
Rossky
, J. Chem. Phys.
80
, 4448
(1984
).9.
P.
Jungwirth
and D. J.
Tobias
, J. Phys. Chem. B
106
, 6361
(2002
).10.
T.
Hotta
, A.
Kimura
, and M.
Sasai
, J. Phys. Chem. B
109
, 18600
(2005
).11.
T.
Ishiyama
and A.
Morita
, J. Phys. Chem. C
111
, 721
(2007
).12.
D. B.
Asay
, M. T.
Dugger
, and S. H.
Kim
, Tribol. Lett.
29
, 67
(2008
).13.
W.
Stumm
, Chemistry of the Solid-Water Interface: Processes at the Mineral-Water and Particle-Water Interface in Natural Systems
(Wiley
, New York
, 1992
), pp. 157
–162
.14.
Y.-J.
Feng
, A.
Gago
, L.
Timperman
, and N.
Alonso-Vante
, Electrochim. Acta
56
, 1009
(2011
).15.
K. P.
Gong
, F.
Du
, Z. H.
Xia
, M.
Durstock
, and L. M.
Dai
, Science
323
, 760
(2009
).16.
J. W.
Schultze
and A. W.
Hassel
, “Passivity of metals, alloys, and semiconductors
,” in Encyclopedia of Electrochemistry
, edited by A.
Bard
, M.
Stratmann
, and G.
Frankel
(Wiley-VCH
, Weinheim
, 2003
), Vol. 4, pp. 460
–490
.17.
K.
Bohnenkamp
and H.
Engell
, Z. Elektrochem.
61
, 1184
(1957
).18.
J.-N.
Chazalviel
, A.
Belaïdi
, M.
Safi
, F.
Maroun
, B.
Erné
, and F.
Ozanam
, Electrochim. Acta
45
, 3205
(2000
).19.
R.
Memming
and G.
Neumann
, J. Electroanal. Chem. Interfacial Electrochem.
21
, 295
(1969
).20.
H.
Gerischer
and W.
Mindt
, Surf. Sci.
4
, 440
(1966
).21.
S.
Nayak
and A.
Erbe
, Phys. Chem. Chem. Phys.
18
, 25100
(2016
).22.
F.
Maroun
, F.
Ozanam
, and J.-N.
Chazalviel
, J. Phys. Chem. B
103
, 5280
(1999
).23.
F. E. G.
Güner
, J.
Wåhlin
, M.
Hinge
, and S.
Kjelstrup
, Chem. Phys. Lett.
622
, 15
(2015
).24.
P.
Fenter
and S. S.
Lee
, MRS Bull.
39
, 1056
(2014
).25.
M.
Mezger
, H.
Reichert
, S.
Schöder
, J.
Okasinski
, H.
Schröder
, H.
Dosch
, D.
Palms
, J.
Ralston
, and V.
Honkimäki
, Proc. Natl. Acad. Sci. U. S. A.
103
, 18401
(2006
).26.
M.
Mezger
, S.
Schöder
, H.
Reichert
, H.
Schröder
, J.
Okasinski
, V.
Honkimäki
, J.
Ralston
, J.
Bilgram
, R.
Roth
, and H.
Dosch
, J. Chem. Phys.
128
, 244705
(2008
).27.
M.
Sovago
, R. K.
Campen
, G. W. H.
Wurpel
, M.
Müller
, H. J.
Bakker
, and M.
Bonn
, Phys. Rev. Lett.
100
, 173901
(2008
).28.
C. S.
Tian
and Y. R.
Shen
, Proc. Natl. Acad. Sci. U. S. A.
106
, 15148
(2009
).29.
O.
Teschke
and E. F.
de Souza
, Chem. Phys. Lett.
403
, 95
(2005
).30.
O.
Teschke
and E. F.
de Souza
, Phys. Chem. Chem. Phys.
7
, 3856
(2005
).31.
N.
Kitadai
, T.
Sawai
, R.
Tonoue
, S.
Nakashima
, M.
Katsura
, and K.
Fukushi
, J. Solution Chem.
43
, 1055
(2014
).32.
G. E.
Ewing
, J. Phys. Chem. B
108
, 15953
(2004
).33.
Q.
Du
, E.
Freysz
, and Y. R.
Shen
, Science
264
, 826
(1994
).34.
T. A.
Weber
and F. H.
Stillinger
, J. Phys. Chem.
87
, 4277
(1983
).35.
P. A.
Thiel
, F. M.
Hoffmann
, and W. H.
Weinberg
, J. Chem. Phys.
75
, 5556
(1981
).36.
B.
Maté
, A.
Medialdea
, M. A.
Moreno
, R.
Escribano
, and V. J.
Herrero
, J. Phys. Chem. B
107
, 11098
(2003
).37.
M.
Nakamura
, Y.
Shingaya
, and M.
Ito
, Chem. Phys. Lett.
309
, 123
(1999
).38.
B. W.
Callen
, K.
Griffiths
, and P. R.
Norton
, Phys. Rev. Lett.
66
, 1634
(1991
).39.
W.
Gan
, D.
Wu
, Z.
Zhang
, R. R.
Feng
, and H. F.
Wang
, J. Chem. Phys.
124
, 114705
(2006
).40.
D. A.
Schmidt
and K.
Miki
, J. Phys. Chem. A
111
, 10119
(2007
).41.
L. F.
Scatena
, M. G.
Brown
, and G. L.
Richmond
, Science
292
, 908
(2001
).42.
F.
Niu
, R.
Schulz
, A.
Castañeda Medina
, R.
Schmid
, and A.
Erbe
, Phys. Chem. Chem. Phys.
19
, 13585
(2017
).43.
M.
Rabe
, H. R.
Zope
, and A.
Kros
, Langmuir
31
, 9953
(2015
).44.
S.
Nayak
, P. U.
Biedermann
, M.
Stratmann
, and A.
Erbe
, Phys. Chem. Chem. Phys.
15
, 5771
(2013
).45.
S.
Nayak
, P. U.
Biedermann
, M.
Stratmann
, and A.
Erbe
, Electrochim. Acta
106
, 472
(2013
).46.
See https://edmond.mpdl.mpg.de/imeji/collection/Tr6mbX98OcP9_C0J for “Data package for: Vibrational spectroscopic study of pH dependent solvation at an Ge(100)-water interface during an electrode potential triggered surface termination transition,”
2018
.47.
R. I.
Shrager
, Chemom. Intell. Lab. Syst.
1
, 59
(1986
).48.
R. W.
Hendler
and R. I.
Shrager
, J. Biochem. Biophys. Methods
28
, 1
(1994
).49.
F.
Maroun
, J.-N.
Chazalviel
, F.
Ozanam
, and D.
Lincot
, J. Electroanal. Chem.
549
, 161
(2003
).50.
J. P.
Hoare
, J. Electrochem. Soc.
116
, 1168
(1969
).51.
N.
Wiberg
, Hollemann-Wiberg, Lehrbuch der Anorganischen Chemie
, 101st ed. (Walter de Gruyter
, Berlin
, 1995
), p. 958
.52.
M.
Cardona
, Phys. Status Solidi B
118
, 463
(1983
).53.
S.
Rivillon
, Y. J.
Chabal
, F.
Amy
, and A.
Kahn
, Appl. Phys. Lett.
87
, 253101
(2005
).54.
E.
Crowell
and G.
Lu
, J. Electron Spectrosc. Relat. Phenom.
54-55
, 1045
(1990
).55.
F.
Maroun
, F.
Ozanam
, and J.-N.
Chazalviel
, Surf. Sci.
427-428
, 184
(1999
).56.
C. I.
Ratcliffe
and D. E.
Irish
, Can. J. Chem.
62
, 1134
(1984
).57.
L.
Bencivenni
, R.
Caminiti
, A.
Feltrin
, F.
Ramondo
, and C.
Sadun
, J. Mol. Struct.: THEOCHEM
257
, 369
(1992
).58.
A.
Karelin
, Z.
Grigorovich
, and V.
Rosolovskii
, Spectrochim. Acta, Part A
31
, 765
(1975
).59.
H.
Gobrecht
, A.
De Haan
, and R.
Thull
, Ber. Bunsen-Ges. Phys. Chem.
76
, 602
(1972
).60.
C.
Bohren
and D. R.
Huffman
, Absorption and Scattering of Light by Small Particles
(Wiley
, New York
, 1983
).61.
W.
Kaiser
, R. J.
Collins
, and H. Y.
Fan
, Phys. Rev.
91
, 1380
(1953
).62.
E.
Kane
, J. Phys. Chem. Solids
1
, 82
(1956
).63.
64.
J.
Bertie
and Z.
Lan
, Appl. Spectrosc.
50
, 1047
(1996
).65.
A.
Erbe
, A.
Sarfraz
, C.
Toparli
, K.
Schwenzfeier
, and F.
Niu
, in Soft Matter at Aqueous Interfaces
, Volume 917 of Lecture Notes in Physics, edited by P. R.
Lang
and Y.
Liu
(Springer
, Cham, Switzerland
, 2016
), pp. 459
–490
.66.
H. R.
Zelsmann
, J. Mol. Struct.
350
, 95
(1995
).67.
R.
Khatib
, T.
Hasegawa
, M.
Sulpizi
, E. H. G.
Backus
, M.
Bonn
, and Y.
Nagata
, J. Phys. Chem. C
120
, 18665
(2016
).68.
Y.
Maréchal
, J. Mol. Struct.
1004
, 146
(2011
).69.
70.
M.
Falk
and T. A.
Ford
, Can. J. Chem.
44
, 1699
(1966
).71.
M.
Schubert
, Phys. Rev. B
53
, 4265
(1996
).72.
M.
Reithmeier
and A.
Erbe
, Phys. Chem. Chem. Phys.
12
, 14798
(2010
).73.
D. B.
Asay
and S. H.
Kim
, J. Phys. Chem. B
109
, 16760
(2005
).74.
M.
Foster
, M.
Furse
, and D.
Passno
, Surf. Sci.
502-503
, 102
(2002
).75.
M.
Foster
, M.
D’Agostino
, and D.
Passno
, Surf. Sci.
590
, 31
(2005
).76.
P. B.
Miranda
, L.
Xu
, Y. R.
Shen
, and M.
Salmeron
, Phys. Rev. Lett.
81
, 5876
(1998
).77.
M. S.
Bergren
, D.
Schuh
, M. G.
Sceats
, and S. A.
Rice
, J. Chem. Phys.
69
, 3477
(1978
).78.
J.
Janecěk
and R. R.
Netz
, Langmuir
23
, 8417
(2007
).79.
Q.
Du
, R.
Superfine
, E.
Freysz
, and Y. R.
Shen
, Phys. Rev. Lett.
70
, 2313
(1993
).80.
A.
Yamakata
, E.
Soeta
, T.
Ishiyama
, M.
Osawa
, and A.
Morita
, J. Am. Chem. Soc.
135
, 15033
(2013
).81.
L. F.
Scatena
and G. L.
Richmond
, J. Phys. Chem. B
105
, 11240
(2001
).82.
M. G.
Brown
, D. S.
Walker
, E. A.
Raymond
, and G. L.
Richmond
, J. Phys. Chem. B
107
, 237
(2003
).83.
S.
Devineau
, K. I.
Inoue
, R.
Kusaka
, S. H.
Urashima
, S.
Nihonyanagi
, D.
Baigl
, A.
Tsuneshige
, and T.
Tahara
, Phys. Chem. Chem. Phys.
19
, 10292
(2017
).84.
M. A.
Sánchez
, T.
Kling
, T.
Ishiyama
, M.-J.
van Zadel
, P. J.
Bisson
, M.
Mezger
, M. N.
Jochum
, J. D.
Cyran
, W. J.
Smit
, H. J.
Bakker
, M. J.
Shultz
, A.
Morita
, D.
Donadio
, Y.
Nagata
, M.
Bonn
, and E. H. G.
Backus
, Proc. Natl. Acad. Sci. U. S. A.
114
, 227
(2017
).© 2018 Author(s).
2018
Author(s)
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