Starting from the structure of the (TTM-TTP)I3 molecular-based material, we examine the characteristics of frontier molecular orbitals using ab initio (CASSCF/CASPT2) configurations interaction calculations. It is shown that the singly occupied and second-highest-occupied molecular orbitals are close to each other, i.e., this compound should be regarded as a two-orbital system. By dividing virtually the [TTM-TTP] molecule into three fragments, an effective model is constructed to rationalize the origin of this picture. In order to investigate the low-temperature, symmetry breaking experimentally observed in the crystal, the electronic distribution in a pair of [TTM-TTP] molecules is analyzed from CASPT2 calculations. Our inspection supports and explains the speculated intramolecular charge ordering which is likely to give rise to low-energy magnetic properties.

1.
D.
Jérome
and
H. J.
Schulz
,
Adv. Phys.
31
,
299
(
1982
).
2.
H.
Seo
,
C.
Hotta
, and
H.
Fukuyama
,
Chem. Rev. (Washington, D.C.)
104
,
5005
(
2004
).
3.
W. P.
Su
,
J. R.
Shrieffer
, and
A. J.
Heeger
,
Phys. Rev. Lett.
42
,
1698
(
1979
).
4.
R.
Peierls
,
Quantum Theory of Solids
(
Clarendon
,
Oxford
,
1955
).
5.
S. A.
Borshch
,
K.
Prassides
,
V.
Robert
, and
A. O.
Solonenko
,
J. Chem. Phys.
109
,
4562
(
1998
).
6.
V.
Robert
,
S.
Petit
, and
S. A.
Borshch
,
Inorg. Chem.
38
,
1573
(
1999
).
7.
V.
Robert
,
J. Chem. Phys.
121
,
4297
(
2004
).
8.
J. -P.
Malrieu
and
V.
Robert
,
J. Chem. Phys.
120
,
7374
(
2004
).
9.
H.
Tanaka
,
Y.
Okano
,
H.
Kobayashi
,
W.
Suzuki
, and
A.
Kobayashi
,
Science
291
,
285
(
2001
).
10.
C.
Rovira
,
J. J.
Novoa
,
J. -L.
Mozos
,
P.
Ordejón
, and
E.
Canadell
,
Phys. Rev. B
65
,
081104
(
2002
).
11.
S.
Ishibashi
,
H.
Tanaka
,
M.
Kohyama
,
M.
Tokumoto
,
A.
Kobayashi
,
H.
Kobayashi
, and
K.
Terakura
,
J. Phys. Soc. Jpn.
74
,
843
(
2005
).
12.
S.
Ishibashi
,
K.
Terakura
, and
A.
Kobayashi
,
J. Phys. Soc. Jpn.
77
,
024702
(
2008
).
13.
H.
Seo
,
S.
Ishibashi
,
Y.
Okano
,
H.
Kobayashi
,
A.
Kobayashi
,
H.
Fukuyama
, and
K.
Terakura
,
J. Phys. Soc. Jpn.
77
,
023714
(
2008
).
14.
For a review, see
T.
Mori
,
Chem. Rev. (Washington, D.C.)
104
,
4947
(
2004
).
15.
T.
Mori
,
H.
Inokuchi
,
Y.
Misaki
,
T.
Yamabe
,
H.
Mori
, and
S.
Tanaka
,
Bull. Chem. Soc. Jpn.
67
,
661
(
1994
).
16.
T.
Mori
,
T.
Kawamoto
,
J.
Yamaura
,
T.
Enoki
,
Y.
Misaki
,
T.
Yamabe
,
H.
Mori
, and
S.
Tanaka
,
Phys. Rev. Lett.
79
,
1702
(
1997
).
17.
M.
Maesato
,
Y.
Sasou
,
S.
Kagoshima
,
T.
Mori
,
T.
Kawamoto
,
Y.
Misaki
, and
T.
Yamabe
,
Synth. Met.
103
,
2109
(
1999
).
18.
N.
Fujimura
,
A.
Namba
,
T.
Kambe
,
Y.
Nogami
,
K.
Oshima
,
T.
Mori
,
T.
Kawamoto
,
Y.
Misaki
, and
T.
Yamabe
,
Synth. Met.
103
,
2111
(
1999
).
19.
M.
Onuki
,
K.
Hiraki
,
T.
Takahashi
,
D.
Jinno
,
T.
Kawamoto
,
T.
Mori
,
T.
Takano
, and
Y.
Misaki
,
Synth. Met.
120
,
921
(
2001
).
20.
M.
Onuki
,
K.
Hiraki
,
T.
Takahashi
,
D.
Jinno
,
T.
Kawamoto
,
T.
Mori
,
K.
Tanaka
, and
Y.
Misaki
,
J. Phys. Chem. Solids
62
,
405
(
2001
).
21.
K.
Yakushi
,
R.
Świetlik
,
K.
Yamamoto
,
T.
Kawamoto
,
T.
Mori
,
Y.
Misaki
, and
K.
Tanaka
,
Synth. Met.
135–136
,
583
(
2003
).
22.
R.
Świetlik
,
K.
Yakushi
,
K.
Yamamoto
,
T.
Kawamoto
, and
T.
Mori
,
J. Phys. IV
114
,
87
(
2004
).
23.
R.
Świetlik
,
K.
Yakushi
,
K.
Yamamoto
,
T.
Kawamoto
, and
T.
Mori
,
Synth. Met.
150
,
83
(
2005
).
24.
Y.
Nogami
,
T.
Kambe
,
N.
Fujimura
,
K.
Oshima
,
T.
Mori
, and
T.
Kawamoto
,
Synth. Met.
135–136
,
637
(
2003
).
25.
J. -B.
Rota
,
L.
Norel
,
C.
Train
,
N.
Ben Amor
,
D.
Maynau
, and
V.
Robert
,
J. Am. Chem. Soc.
130
,
10380
(
2008
).
26.
S.
Messaoudi
,
V.
Robert
,
N.
Guihery
, and
D.
Maynau
,
Inorg. Chem.
45
,
3212
(
2006
).
27.
M.
Kepenekian
,
B.
Le Guennic
,
K.
Awaga
, and
V.
Robert
,
Phys. Chem. Chem. Phys.
11
,
6066
(
2009
).
28.
J. -B.
Rota
,
B.
Le Guennic
, and
V.
Robert
,
Inorg. Chem.
49
,
1230
(
2010
).
29.
G.
Ghigo
,
B. O.
Roos
, and
P.
Malmqvist
,
Chem. Phys. Lett.
396
,
142
(
2004
).
30.
M.
Kepenekian
,
V.
Robert
, and
B.
Le Guennic
,
J. Chem. Phys.
131
,
114702
(
2009
).
31.
G.
Karlström
,
R.
Lindh
,
P. -Å.
Malmqvist
,
B. O.
Roos
,
U.
Ryde
,
V.
Veryazov
,
P. -O.
Widmark
,
M.
Cossi
,
B.
Schimmelpfennig
,
P.
Neogrady
, and
L.
Seijo
,
Comput. Mater. Sci.
28
,
222
(
2003
).
32.
T.
Mori
,
A.
Kobayashi
,
Y.
Sasaki
,
H.
Kobayashi
,
G.
Saito
, and
H.
Inokuchi
,
Bull. Chem. Soc. Jpn.
57
,
627
(
1984
).
33.
T.
Mori
, Ph.D. thesis,
University of Tokyo
,
1985
.
34.
M. J.
Frisch
,
G. W.
Trucks
,
H. B.
Schlegel
 et al, GAUSSIAN 03, Gaussian, Inc., Pittsburgh PA,
2003
, we have used a BLYP functional and a triple zeta basis set.
You do not currently have access to this content.