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Austrian-Indonesian Centre (AIC) for Computational Chemistry, Gadjah Mada University, Sekip Utara, Yogyakarta 55281, Indonesia
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Gadjah Mada University, Sekip Utara, Yogyakarta 55281, Indonesia
Theoretical Chemistry Division, Institute of General, Inorganic and Theoretical Chemistry, University of Innsbruck, Innrain 80-82,
A-6020 Innsbruck, Austria
b
c
a r t i c l e
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Article history:
Received 7 November 2014
In nal form 28 November 2014
Available online 4 December 2014
a b s t r a c t
The solvation of Li(I) in liquid ammonia has been investigated by an ab initio quantum mechanical chargeeld molecular dynamics (QMCF-MD) simulation. Being the rst simulation of a metal cation in liquid
ammonia employing this methodology, the work yields a wide range of accurate structural and dynamical
data. Li(I) is tetrahedrally coordinated by four ammonia molecules in the rst solvation shell at a distance
Two ligand exchange attempts have been observed within 12 ps of simulation time. The second
of 2.075 A.
solvation shell shows a more labile structure with numerous successful exchanges. The results are in
excellent agreement with experiments.
2014 Elsevier B.V. All rights reserved.
1. Introduction
Lithium is a metal of high interest in industry because of its
applications in modern technologies such as lithium batteries,
which are an essential part of mobile electronic devices [1]. In
academia, lithium is often used as a starting point to assess new
theoretical methods in computational chemistry because of its simplicity.
The solvation of lithium in liquid ammonia has been subject
of standard computational chemistry methods such as ab initio
HartreeFock [2] and MllerPlesset-2 (MP2) [3], ab initio self
consistent eld for molecular interactions (SCF-MI) [4] and density functional theory (DFT) calculations [5] Various simulation
methods such as molecular dynamics simulations [3,6], a quantum
mechanical molecular mechanical molecular dynamics (QM/MMMD) simulation [7] and a Monte Carlo simulation using a three
body potential [8] have previously been reported. Experimentally,
neutron diffraction [9,10] and X-ray diffraction [11], infrared spectroscopy [12] and inelastic X-ray scattering [13] have been used to
investigate the solvation properties of lithium in liquid ammonia.
Ab initio calculations in gas phase cannot yield any information
about dynamical properties and solvent inuence of the system
at hand. Both the pair potential approach and the Monte Carlo
2. Method
Corresponding author at: Austrian-Indonesian Centre (AIC) for Computational
Chemistry, Gadjah Mada University, Sekip Utara, Yogyakarta 55281, Indonesia.
E-mail address: ria.armunanto@ugm.ac.id (R. Armunanto).
http://dx.doi.org/10.1016/j.cplett.2014.11.066
0009-2614/ 2014 Elsevier B.V. All rights reserved.
The QMCF-MD methodology [25] is an enhancement of conventional QM/MM approaches [2629], which does not require
any potential functions for any species in the system investigated
FJ
M
qMM
qQM
I
J
qMM
qQM
I
J
N1 +N2
rIJ2
I=1
1+2
rIJ2
I=1
N2
+ 1 rIJ 3
2 1
FIJnC
rc
+ FIJnC
(2)
(3)
I=1
/ J
I=
where FJcore corresponds to the quantum mechanical forces acting
layer
FJsmooth = S(r)(FJ
= FJMM ) + FJMM
(4)
tsimulation Nav
0.5
Nex
(5)
0.5
Nex
(6)
0.0
Nex
Nt N
C(t) =
Nt N
Table 1
Characteristic values of LiN and LiH radial distribution functions obtained from
QMCF-MD simulation.a
Atom pair
N
Li
Li
H
rM1
rm1
N(m1)
rM2
rm2
N(m2)
2.075
2.625
3.08
3.28
4.05
12.82
4.82
4.88
6.60
6.40
25
75
a
rMi and rmi are the distances in of the ith maxima and minima observed in the
corresponding RDF. N(mi) is the average coordination number of the ith shell.
(1)
= FJQM +
FJMM =
159
Nt
J
(7)
mechanical core zone and layer zone were set to 3.4 and 6.6 A,
respectively. A smoothing zone of 0.2 A was applied at the border of the QM and the MM region. All atoms in the QM region
(core zone and layer zone) were treated at the HartreeFock level
of theory using the well established DZP Dunning [36] basis sets. To
integrate the equation of motion, a second-order Adams-Bashforth
predictor-corrector algorithm was used with a time step of 0.2 fs.
the
To correct the cutoff of the long-range interaction above 10.3 A,
reaction eld approach was used [37]. The system was heated to
700 K for 2 ps and then re-equilibrated at 235.15 K for 2 ps. Sampling was done every fth step during a simulation time of 12 ps.
All QM calculations within the simulation were executed with the
TURBOMOLE 5.9 package [38,39]. The popular VMD package was
employed to visually analyze the trajectory [40].
3. Result and discussion
The Li+ N and Li+ H RDFs are displayed in Figure 1a and structural characteristics are listed in Table 1. There are two solvation
shells, the rst one ranging from 1.78 to 3.08 A with an average
coordination number of 4.05. This coordination number is in excellent agreement with data from experiments employing neutron
diffraction [9,10] and X-ray diffraction [11]. The rst LiN RDF
peak located at 2.075 A is also in excellent agreement with experimental values of 2.01 and 2.06 A from X-ray [11] and neutron
diffraction measurements [9,10], respectively (see Table 2). In the
work at hand, the hydrogen bonds between rst and second shell
are described by quantum mechanics, whereas an earlier QM/MM
simulation only included the rst solvation shell in the QM treatment [7], resulting in a slightly enlarged ion-ammonia distance.
Earlier Monte Carlo and pair potential simulations not including
three-body potentials report a wrong coordination number of six
[6,8].
the maximum LiN
The second shell ranges from 3.08 to 6.60 A,
This shell contains approxprobability being located at 4.82 A.
imately 25 ammonia molecules. This value is larger than the
coordination number of the second hydration shell of lithium(I)
in water [1]. Hayama et al. [11] reported a value of 30 for the coordination number and a second shell LiN RDF maximum at 5.50 A
employing X-ray measurements. The weakly pronounced non-zero
valley of the Li+ N RDF between the rst and second shell indicates
few ligand exchange events between these shells. The non-zero
Li+ N RDF value after 6.5 A indicates that the second solvation
160
Figure 1. (a) LiN (solid line) and LiH (dashed line) radial distribution functions including the corresponding integration information, and (b) angular distribution function
NLiN in the rst solvation shell of the Li+ ion.
Table 2
Structural properties of rst solvation shell of Li+ : Li+ N distance (d) in and coordination number (CN).
Method
CN
Geometry
System
QMCF-MD simulation
2.075
Tetrahedral
QM/MM simulation
2.15
Tetrahedral
Octahedral
2.29
Octahedral
2.105
2.15
2.01
2.06
4
4
4
4
4
4
Tetrahedral
Tetrahedral
Tetrahedral
Tetrahedral
Tetrahedral
Tetrahedral
Refs.
ion; 235.15 K;
This work
ion; 235 K;
[7]
ion; 277 K;
[8]
ion; 235 K;
[6]
[4]
[3]
[2]
[11]
[9]
[10]
161
Figure 2. (a) Coordination number distribution of the rst and second solvation shell, and (b) evolution of the root-mean-square-deviation of the rst shell coordination
geometry from an ideal tetrahedral arrangement. Marks tA1 and tA2 indicate the two observed ligand exchange attempts during the simulation time of 12 ps.
Figure 4. Power spectrum of Li+ in liquid ammonia obtained via Fourier transformed
velocity auto-correlation functions from the QMCF-MD simulation. For comparison,
experimentally obtained values are depicted as single.
Figure 3. (a) Evolution of selected Li(I)N distances during the simulation. The bor Marks tA1 and tA2 indicate
derline of the rst and second shell is shown at 3 08 A.
the two observed ligand exchange attempts during the simulation time of 12 ps. A
detailed plot is given for the rst exchange attempt. Snapshots obtained from the
QMCF-MD simulation depicting, (b) an ideal tetrahedral rst shell arrangement, and
(c) a trigonal bipyramidal coordination geometry observed at the exchange attempt
at tA1 .
strength. The RMSD plot shows a second peak located at 9.8 ps,
which corresponds to a strongly squeezed tetrahedral coordination.
The power spectrum of lithium(I) in liquid ammonia is displayed
in Figure 4. The maximum is located at 358 cm1 and a smaller
peak is found at 550 cm1 . This corresponds to force constants of
35 Nm1 and 82.8 Nm1 , respectively. These values are in very
good agreement with the experimentally observed frequencies of
361 and 561 cm1 (35.6 and 86.0 Nm1 ) for the Li(I)N vibrational stretching of [Li(NH3 )n ]+ species in liquid ammonia [43], and
162
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