The tunneling spectra of the ordered monolayer films of decamolybdodicobaltate (DMDC) compounds deposited from aqueous solutions on HOPG were measured by scanning tunnel microscopy in air. The DMDC spectra, as well as the tunneling spectra of other polyoxometalates (POMs), exhibit well-defined negative differential resistances (NDRs). The mechanism of formation of these spectral features was established from the collection of revealed NDR dependences on the external varying parameters and found to be common to all systems exhibiting Wannier–Stark localization. A model of biresonance tunneling was developed to provide an explanation for the totality of experimental data, both the literature and original, on the tunneling POM probing. A variant of the tunneling electron-vibrational POM spectroscopy was proposed allowing the determination of the three basic energy parameters—energy gaps between the occupied and unoccupied states, frequencies of the vibrational transitions accompanying biresonance electron-tunneling processes, and electron-vibrational interaction constants on the monomolecular level.

1.
M. T.
Pope
,
Heteropoly and Isopoly Oxometalates
(
Springer-Verlag
,
Berlin
,
1983
).
2.
I. V.
Kozhevnilov
,
Catal. Rev.: Sci. Eng.
37
,
311
(
1995
).
3.
Chemical Reviews, special issue January/February, all chapters, 1998.
4.
D.-L.
Long
,
E.
Burkholder
, and
L.
Cronin
,
Chem. Soc. Rev.
36
,
105
(
2007
).
5.
G. I. T.
Cooper
,
P. I.
Kitson
,
R.
Winter
,
M.
Zagnoni
,
D.-L.
Long
, and
L.
Cronin
,
Angew. Chem., Int. Ed.
50
,
10373
(
2011
).
6.
R. I.
Hamers
, in
Scanning Tunneling Microscopy and Spectroscopy
, edited by
D. A.
Donnell
(
VCH
,
New York
,
1993
), Chap. 4.
7.
F. I.
Dalidchik
and
B. R.
Shub
,
Nanotechnol. Russ.
1-2
,
82
(
2006
).
8.
M.
Ruben
,
I.-M.
Lehn
, and
P.
Muller
,
Chem. Soc. Rev.
35
,
1056
(
2006
).
9.
I. K.
Song
and
M. A.
Barteau
,
Langmuir
20
,
1850
(
2004
).
10.
I. K.
Song
,
M. S.
Kaba
, and
M. A.
Barteau
,
J. Phys. Chem.
100
,
17528
(
1996
).
11.
I. K.
Song
,
M. S.
Kaba
, and
M. A.
Barteau
,
J. Phys. Chem.
100
,
19577
(
1996
).
12.
I. K.
Song
,
R. B.
Shnitser
,
J. J.
Cowan
,
G. L.
Hill
, and
M. A.
Barteau
,
Inorg. Chem.
41
(
5
),
1292
(
2002
).
13.
M.
Kinne
and
M. A.
Barteau
,
Surf. Sci.
447
,
105
(
2000
).
14.
I. K.
Song
,
I. E.
Lyons
, and
M. A.
Barteau
,
Catal. Today
81
,
137
(
2003
).
15.
A. M.
Dykhne
,
S. Yu.
Vasil’ev
,
O. A.
Petrii
,
G. A.
Tsirlina
, and
A. G.
Rudavets
,
Dokl. Phys.
44
(
10
),
653
(
1999
).
16.
I.
Kovacs
,
J. Phys.: Conf. Ser.
61
,
623
(
2007
).
17.
F. I.
Dalidchik
,
E. M.
Balashov
,
B. A.
Budanov
 et al,
Russ. J. Phys. Chem. B
4
(
6
),
896
(
2010
).
18.
F. I.
Dalidchik
,
B. A.
Budanov
,
N. N.
Kolchenko
,
E. M.
Balashov
, and
S. A.
Kovalevskii
,
J. Exp. Theor. Phys.
115
(
6
),
1068
(
2012
).
19.
E. M.
Balashov
,
B. A.
Budanov
,
F. I.
Dalidchik
, and
S. A.
Kovalevskiy
,
JETP Lett.
101
(
9
),
643
(
2015
).
20.
C. I.
Cabello
,
M.
Franco
,
F. M.
Cabrerizo
,
A.
Alvarez
, and
H. I.
Thomas
,
J. Mol. Catal. A: Chem.
186
,
89
(
2002
).
21.
C.
Martin
,
C.
Lamonier
,
M.
Fournier
,
M.
Olivier
,
V.
Harlé
,
D.
Guillaume
, and
E.
Payen
,
Chem. Mater.
17
,
4438
(
2005
).
22.
F. I.
Dalidchik
,
S. A.
Kovalevskii
, and
B. A.
Budanov
,
Nanotechnol. Russ.
7
(
11-12
),
635
(
2012
).
23.
I. K.
Song
, private communication (
2009
).
24.
I.
Freund
,
I.
Halbritter
, and
I. K. H.
Horberi
,
Microsc. Res. Tech.
44
,
327
(
1999
).
25.
S. Yu.
Vasil’ev
and
A. V.
Denisov
,
Tech. Phys.
45
(
1
),
99
(
2000
).
26.
M.
Asada
,
S.
Suzuki
, and
N.
Kishimoto
,
Jpn. J. Appl. Phys., Part 1
47
,
4375
(
2008
).
27.
F. I.
Dalidchik
and
V. Z.
Slonim
,
J. Exp. Theor. Phys.
43
,
25
(
1976
).
28.
I.-W.
Lyo
and
P.
Avouris
,
Science
245
(
4924
),
1369
(
1989
).
29.
G. H.
Wannier
,
Rev. Mod. Phys.
34
,
645
(
1962
).
30.
Z.
Sun
,
I.
Swart
,
C.
Delerue
,
D.
Vanmaekelbergh
, and
P.
LilIeroth
,
Phys. Rev. Lett.
102
,
196401
(
2009
).
31.
S.
Sapmaz
,
P.
Iarillo-Herrero
,
Ya. M.
Blanter
,
C.
Dekker
, and
H. S. I.
van der Zant
,
Phys. Rev. Lett.
96
,
026801
(
2006
).
32.
G. V.
Nazin
,
X. H.
Qiu
, and
W.
Ho
,
J. Chem. Phys.
122
,
181105
(
2005
).
33.
F. I.
Dalidchik
,
J. Exp. Theor. Phys.
60
(
4
),
795
(
1984
).
34.
35.
T.
Ozaki
and
H.
Kino
,
Phys. Rev. B
69
,
195113
(
2004
).
36.
I.
Morrison
,
D. M.
Bylander
, and
L.
Kleinman
,
Phys. Rev. B
47
,
6728
(
1993
).
37.
I. P.
Perdew
,
K.
Burke
, and
M.
Ernzerhof
,
Phys. Rev. Lett.
77
,
3865
(
1996
).
You do not currently have access to this content.