We applied first principles molecular dynamics (MD) technique to study structure, dynamics, and magnetic interactions of the Gd3+ aqua ion dissolved in liquid water, a prototypical system for Gd-based complexes used as contrast agents for magnetic resonance imaging. The first coordination sphere contains eight water molecules with an average Gd-O distance of 2.37Å and an average geometric arrangement close to a square antiprism. The mean tilt angle of the electric dipole vector of these water molecules is θ=145°. In our picosecond time scale simulation we observe no exchange event from the first coordination sphere but only fast “wagging” motions. The second coordination sphere is well pronounced though water molecules in this sphere are subjected to large amplitude dynamic motions. The isotropic hyperfine coupling constants for the inner sphere water molecules [Aiso(O17I)=0.65±0.03MHz,Aiso(H1I)=0.085±0.005MHz] are in good agreement with experimental data and with an earlier study using classical MD. Second sphere Fermi contact hyperfine coupling constants calculated are more than one order of magnitude smaller and of opposite sign as those of the first coordination sphere. The effect of spin polarization induced by the paramagnetic Gd3+ ion on the dipolar hyperfine interaction was found to be sizable only for the O17 nuclei of inner sphere water molecules and has a screening character.

1.
E.
Tóth
,
L.
Helm
, and
A. E.
Merbach
, in
The Chemistry of Contrast Agents in Medical Magnetic Resonance Imaging
, 1st ed., edited by
A. E.
Merbach
and
E.
Tóth
(
Wiley
,
New York
,
2001
), pp.
45
119
.
2.
E.
Tóth
,
L.
Helm
, and
A. E.
Merbach
, in
In Comprehensive Coordination Chemistry II
, edited by
J.
Meyer
and
T.
McCleverty
(
Elsevier
,
Oxford
,
2004
), Vol.
9
, pp.
841
881
.
3.
E.
Tóth
,
L.
Helm
, and
A. E.
Merbach
, in
Topics in Current Chemistry
, edited by
W.
Krause
(
Spinger
,
Berlin
,
2002
), Vol.
221
, pp.
62
101
.
4.
L.
Helm
,
E.
Tóth
, and
A. E.
Merbach
,
Lanthanide Ions as Magnetic Resonance Imaging Agents. Nuclear and Electronic Relaxation Properties. Applications
,
Metal Ions in Biological Systems Vol. 40
(
Marcel Dekker
,
New York
,
2003
).
5.
P.
Caravan
,
J. J.
Ellison
,
T. J.
McMurry
, and
R. B.
Lauffer
,
Chem. Rev.
99
,
2293
(
1999
).
6.
O. V.
Yazyev
and
L.
Helm
,
J. Chem. Phys.
125
,
054503
(
2006
).
7.
O. V.
Yazyev
,
L.
Helm
,
V. G.
Malkin
, and
O. L.
Malkina
,
J. Phys. Chem. A
109
,
10997
(
2005
).
8.
A.
Borel
,
L.
Helm
, and
A. E.
Merbach
,
Chem. Eur. J.
7
,
600
(
2001
).
9.
C.
Clavaguéra
,
F.
Calvo
, and
J. -P.
Dognon
,
J. Chem. Phys.
124
,
074505
(
2006
).
10.
C.
Clavaguéra
,
E.
Sansot
,
F.
Calvo
, and
J. P.
Dognon
,
J. Phys. Chem. B
110
,
12848
(
2006
).
11.
F.
Yerly
,
A.
Borel
,
L.
Helm
, and
A. E.
Merbach
,
Chem. Eur. J.
9
,
5468
(
2003
).
12.
F.
Yerly
,
K. I.
Hardcastle
,
L.
Helm
,
S.
Aime
,
M.
Botta
, and
A. E.
Merbach
,
Chem. Eur. J.
8
,
1031
(
2002
).
13.
R.
Car
and
M.
Parrinello
,
Phys. Rev. Lett.
55
,
2471
(
1985
).
14.
T.
Ikeda
,
M.
Boero
, and
K.
Terakura
,
J. Chem. Phys.
126
,
034501
(
2007
).
15.
D.
Marx
,
M. E.
Tuckerman
,
J.
Hutter
, and
M.
Parrinello
,
Nature (London)
397
,
601
(
1999
).
16.
A.
Pasquarello
,
I.
Petri
,
P. S.
Salmon
,
O.
Parisel
,
R.
Car
,
E.
Tóth
,
D. H.
Powell
,
H. E.
Fischer
,
L.
Helm
, and
A. E.
Merbach
,
Science
291
,
856
(
2001
).
17.
M. E.
Tuckerman
,
D.
Marx
, and
M.
Parrinello
,
Nature (London)
417
,
925
(
2002
).
18.
R.
Pollet
and
D.
Marx
,
J. Chem. Phys.
126
,
181102
(
2007
).
19.
J. A.
Weil
,
J. R.
Bolton
, and
J. E.
Wertz
,
Electron Paramagnetic Resonance: Elementary Theory and Practical Applications
(
Wiley
,
New York
,
1994
).
20.
Calculation of NMR and EPR Parameters: Theory and Applications
, edited by
M.
Kaupp
,
M.
Buehl
, and
V. G.
Malkin
(
Wiley-VCH
,
Weinheim
,
2004
).
21.
F. H.
Spedding
,
P. F.
Cullen
, and
A.
Habenschuss
,
J. Phys. Chem.
78
,
1106
(
1974
).
22.
D.
Marx
,
J.
Hutter
, and
M.
Parrinello
,
Chem. Phys. Lett.
241
,
457
(
1995
).
23.
S.
Nosé
,
J. Chem. Phys.
81
,
511
(
1984
).
24.
S.
Nosé
,
Mol. Phys.
52
,
255
(
1984
).
25.
W. G.
Hoover
,
Phys. Rev. A
31
,
1695
(
1985
).
26.
A. D.
Becke
,
Phys. Rev. A
38
,
3098
(
1988
).
27.
C.
Lee
,
W.
Yang
, and
R. G.
Parr
,
Phys. Rev. B
37
,
785
(
1988
).
28.
M.
Sprik
,
J.
Hutter
, and
M.
Parrinello
,
J. Chem. Phys.
105
,
1142
(
1996
).
29.
D.
Vanderbilt
,
Phys. Rev. B
41
,
7892
(
1990
).
30.
A.
Borel
,
L.
Helm
, and
C. A. E.
Daul
,
Chem. Phys. Lett.
383
,
584
(
2004
).
31.
R.
Pollet
,
C.
Clavaguéra
, and
J. -P.
Dognon
,
J. Chem. Phys.
124
,
164103
(
2006
).
32.
CPMD version 3.9.1, Copyright IBM Corp 1990–2004, Copyright MPI für Festkörperforschung Stuttgart 1997–2001, http://www.cpmd.org.
33.
O. V.
Yazyev
,
I.
Tavernelli
,
L.
Helm
, and
U.
Röthlisberger
,
Phys. Rev. B
71
,
115110
(
2005
).
34.
O. V.
Yazyev
and
L.
Helm
,
Theor. Chim. Acc.
115
,
190
(
2006
).
35.
N.
Troullier
and
J.
Martins
,
Phys. Rev. B
43
,
1993
(
1991
).
36.
S. G.
Louie
,
S.
Froyen
, and
M. L.
Cohen
,
Phys. Rev. B
26
,
1738
(
1982
).
37.
C. G.
Van de Walle
and
P. E.
Blöchl
,
Phys. Rev. B
47
,
4244
(
1993
).
38.
R.
Declerck
,
E.
Pauwels
,
V.
Van Speybroeck
, and
M.
Waroquier
,
Phys. Rev. B
74
,
245103
(
2006
).
39.
D.
Marx
and
J.
Hutter
, in
Modern Methods and Algorithms of Quantum Chemistry
, edited by
J.
Grotendorst
(
NIC
,
Julich
,
2000
), pp.
301
449
.
40.
G.
Arfken
,
Mathematical Methods for Physicists
, 3rd ed. (
Academic
,
Orlando, FL
,
1985
).
41.
O. V.
Yazyev
,
I.
Tavernelli
,
L.
Helm
, and
U.
Rothlisberger
(unpublished).
42.
H.
Ohtaki
and
T.
Radnai
,
Chem. Rev.
93
,
1157
(
1993
).
43.
A. V.
Astashkin
,
A. M.
Raitsimring
, and
P.
Caravan
,
J. Phys. Chem. A
108
,
1990
(
2004
).
44.
A. M.
Raitsimring
,
A. V.
Astashkin
,
D.
Baute
,
D.
Goldfarb
, and
P.
Caravan
,
J. Phys. Chem. A
108
,
7318
(
2004
).
45.
T.
Ikeda
,
M.
Hirata
, and
T.
Kimura
,
J. Chem. Phys.
122
,
024510
(
2005
).
46.
T.
Ikeda
,
M.
Hirata
, and
T.
Kimura
,
J. Chem. Phys.
122
,
244507
(
2005
).
47.
R. D.
Shannon
,
Acta Crystallogr. A
32
,
751
(
1976
).
48.
C.
Cossy
,
L.
Helm
,
D. H.
Powell
, and
A. E.
Merbach
,
N. J. Chem.
19
,
27
(
1995
).
49.
D. L.
Kepert
,
Inorganic Stereochemistry
,
Inorganic Chemistry Concepts Vol. 6
(
Springer
,
Berlin
,
1982
).
50.
F. A.
Dunand
,
A.
Borel
, and
A. E.
Merbach
,
J. Am. Chem. Soc.
124
,
710
(
2002
).
51.
D. H.
Powell
,
O. M. N.
Dhubhghaill
,
D.
Pubanz
,
L.
Helm
,
Y. S.
Lebedev
,
W.
Schlaepfer
, and
A. E.
Merbach
,
J. Am. Chem. Soc.
118
,
9333
(
1996
).
52.
J.
Reuben
and
D.
Fiat
,
J. Chem. Phys.
51
,
4909
(
1969
).
53.
J.
Kowalewski
,
A.
Laaksonen
,
L.
Nordenskiöld
, and
M.
Blomberg
,
J. Chem. Phys.
74
,
2927
(
1981
).
54.
L.
Nordenskiöld
,
A.
Laaksonen
, and
J.
Kowalewski
,
J. Am. Chem. Soc.
104
,
379
(
1982
).
55.
J.
Kowalewski
,
L.
Nordenskiöld
,
N.
Benetis
, and
P. -O.
Westlund
,
Prog. Nucl. Magn. Reson. Spectrosc.
17
,
141
(
1985
).
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