SUPPLEMENTARY MATERIAL
Theoretical Study on the Hydrophobic and Hydrophilic Hydration on Large
Solutes: The Case of Phthalocyanines in water
Elisa I. Martı́n, José M. Martı́nez and Enrique Sánchez Marcos
Departamento de Quimica Fisica. Universidad de Sevilla. 41012-Sevilla, Spain
Figure S1: O-OW and O-HW RDFs for the [CuPc(SO3 )4 ]4− in water.
uµ
z
θ
θ
ɸ
x
y
Figure S2: Definition of the θ and φ polar coordinates for the dipole vector ~uµ of a
water molecule.
Figure S3: Bulk-relative orientational distribution functions for the θ polar component of the ~uµ , ~uHH and ~u⊥ vectors of the water molecules belonging to axial
(left side) and peripheral regions (right side) for the H2 Pc (black), CuPc (red) and
[CuPc(SO3 )4 ]4− (green) systems. The magenta lines on the right side correspond to
the sulphonate orientation distribution functions of the [CuPc(SO3 )4 ]4− system.
Figure S4: Mean square displacement, MSD (Å2 ), for the first and second solvation
shells of CuPc in aqueous solution as a function of time.
Figure S5: Reorientational times, τl,i , (l = 1 or 2) for the unit vectors (~uHH , ~u⊥ ) of
the water molecules belonging to the first and second shells and bulk water obtained
from the simulations of CuPc (red circle), H2 Pc (green square) and [CuPc(SO3 )4 ]4−
(blue triangle) complexes in aqueous solution. The picture includes the values for
1-Order (black dotted line) and 2-Order (red dotted line) calculated from the pure
water simulation.
rOO
α
Figure S6: Spatial parameters used to define the hydrogen bond formed between
two water molecules.
Figure S7: Distribution functions of the geometrical parameters, rOO and αH−O···O ,
for the water molecules belonging to the first shell (red line), second shell (green
line) and bulk water (black line) obtained from simulations of CuPc, H2 Pc and
[CuPc(SO3 )4 ]4− complexes in aqueous solution. The black circles describe the distribution function computed from pure water simulation.
Figure S8:Distribution functions of the geometrical parameters, rOO and αH−O···O ,
for the water molecules belonging to the first shell (red line), second shell (green
line), sulphonate regions (pink line) and bulk water (black line) obtained from the
simulation of [CuPc(SO3 )4 ]4− complex in aqueous solution. The black circles describe
the distribution function computed from a pure water simulation.
Figure S9: Autocorrelation functions, C(t), for hydrogen bonds formed between two water molecules belonging to 1st shell-1st shell (red line), 1st shell-2nd shell (orange line), 2nd shell-2nd shell (green
line), 2nd shell-bulk (blue line) and bulk-bulk (pink line) calculated from simulation of CuPc complex in aqueous solution. The black line describe the autocorrelation functions computed from pure
water simulation.
Table S1: Mean residence times (ps) of water molecules belonging to the first and
second solvation shells and axial sub-region obtained from the MD simulations of
the CuPc, H2 Pc and [CuPc(SO3 )4 ]4− in aqueous solution. Values into parentheses
indicate the standard deviation of the results.
First shell
System
Second shell
Axial region
τ (t*=0 ps) τ (t*=2 ps) τ (t*=0 ps) τ (t*=2 ps) τ (t*=2 ps)
CuPc
10.2 (0.4) 29.4 (0.4)
3.4 (0.1)
14.2 (0.1)
19.9 (0.6)
H2 Pc
9.1 (0.2)
28.0 (0.6)
3.4 (0.1)
14.0 (0.1)
13.3 (0.6)
[CuPc(SO3 )4 ]4− 11.6 (0.1) 31.5 (0.1)
4.6 (0.1)
16.7 (0.1)
22.5 (0.6)
Table S2: Reorientational times, τl,i , of l-Order (l = 1 or 2) for the unit vectors
(~uµ , ~uHH , ~u⊥ ) of the water molecules belonging to the axial, peripheral and sulphonated regions inside the first shell obtained from the simulations of CuPc, H2 Pc
and [CuPc(SO3 )4 ]4− complexes in aqueous solution. The standard deviation was less
that 0.5 ps for all cases.
a
Value obtained for the equivalent sulphonate groups.
b
Value obtained for the non-equivalent sulphonate group.
Axial region
System
Peripheral region
Sulphonated region
τ1,d τ1,HH τ1,⊥ τ2,d τ2,HH τ2,⊥ τ1,d τ1,HH τ1,⊥ τ2,d τ2,HH τ2,⊥ τ1,d τ1,HH τ1,⊥ τ2,d τ2,HH τ2,⊥
CuPc
15.1 11.5 9.7 5.0
5.5
5.6 7.6
6.7
4.6 2.6
3.2
2.3
H2 Pc
9.9
5.8 3.2
3.5
3.2 7.6
6.8
4.6 2.7
3.3
2.4
[CuPc(SO3 )4 ]4− 16.8 12.5 11.3 5.7
6.2
7.0 8.6
7.2
5.1 2.9
3.5
2.6
7.5
9.9a 11.1a 5.9a 3.2a 5.1a 2.6a
14.4b 15.8b 8.2b 4.7b 7.7b 4.8b