Supporting Information for:
A Combined Spectroscopic and Theoretical Study of
Propofol·(H2O)3
By
Iker León,1 Emilio J. Cocinero,1 Judith Millán,2 Anouk M. Rijs,3,4 Imanol Usabiaga,1
Alberto Lesarri,5 Fernando Castaño1 and José A. Fernández*1
1
Dpto. de Química Física, Facultad de Ciencia y Tecnología, Universidad del País
Vasco-UPV/EHU, Bº Sarriena s/n, Leioa 48940, Spain.
2
Dpto. de Química, Facultad de Ciencias, Estudios Agroalimentarios e Informática,
Universidad de La Rioja, Madre de Dios, 51, Logroño 26006, Spain.
3
FOM Institute for Plasma Physics Rijnhuizen, Edisonbaan 14, 3439 MN Nieuwegein,
the Netherlands
4 Institute for Molecules and Materials, Radboud University Nijmegen, Toernooiveld 7,
6525 ED Nijmegen, the Netherlands
5
Dpto. de Química Física y Química Inorgánica, Facultad de Ciencias, Universidad de
Valladolid, Valladolid 47011, Spain.
*Corresponding author:
Dr. José A. Fernández
Departamento de Química-Física,
Facultad de Ciencia y Tecnología,
Universidad del País Vasco-UPV/EHU.
Bº Sarriena s/n, Leioa 48940. SPAIN
e-mail: josea.fernandez@ehu.es
Fax: ++ 34 94 601 35 00.
Phone ++ 34 94 601 5387
https://sites.google.com/site/gesemupv/
1
Figure S1. Conformations of propofol with their relative stability in kJ/mol, as
calculated at the M06-2X/6-311++G(d,p) level. Carbon atoms are depicted in yellow,
hydrogen atoms in blue and oxygen in red.
2
Figure S2. Conformations of propofol·(H2O)3 with their relative stability in kJ/mol, as
calculated at the M062X/6-311++G(d,p) level. Carbon atoms are depicted in yellow,
hydrogen atoms in blue and oxygen in red.
3
Table S1. Relative stability, dissociation energies and BSSE correction for the
propofol·(H2O)3 calculated structures in Fig. S2.
Structure
s1
s2
s3
s4
s5
s6
s7
s8
s9
s10
s11
s12
s13
s14
s15
s16
s17
s18
s19
s20
S21
s22
s23
s24
∆E (kJ/mol)
0.00
-0.05
0.01
2.08
4.88
4.29
4.97
4.36
3.10
6.07
6.07
5.75
7.91
9.21
10.65
12.62
12.83
12.67
16.32
16.66
16.07
17.39
18.64
18.46
∆EZPE (kJ/mol)
0.00
1.68
2.46
3.71
4.10
5.22
5.67
6.03
6.04
6.94
6.99
7.09
8.02
10.73
11.23
11.68
12.89
13.09
13.20
14.30
15.86
16.88
17.38
18.20
4
D0 (kJ/mol)
-95.19
-93.66
-93.83
-91.65
-94.87
-93.79
-93.76
-93.15
-89.31
-88.63
-88.58
-92.33
-87.44
-89.70
-85.46
-87.32
-91.61
-91.51
-82.45
-88.95
-80.42
-79.12
-86.64
-85.83
EBSSE (kJ/mol)
16.89
16.74
15.79
16.71
16.92
16.86
16.45
16.70
16.73
16.50
16.51
16.46
16.76
15.44
15.38
16.88
15.96
15.87
16.43
17.22
15.80
16.08
16.45
16.44
Figure S3. Experimental IDIRS for propofol·(H2O)3 together with the calculated
frequencies for each structure. A correction factor of 0.938 has been employed.
conformer 1
conformer1
conformer 2
conformer2
S13
S1
S14
S2
S15
S3
S16
S4
S17
S5
S18
S6
3100
S19
S8
S20
S9
S21
S10
S22
S11
S23
S12
3800
3500
Wavenumber / cm
S7
-1
5
S24
3100
3500
Wavenumber / cm
-1
3800
Figure S4. (OH) vibrations of the two assigned structures of propofol·(H2O)3.

6
Figure S5. (lower panel) Potential energy curve obtained using the calculated structure s3 as
starting point and rotating the isopropyl group on the right in 30º steps, while the rest of
the coordinates are relaxed. (upper panel) a more detailed scan around the global
minimum was performed, rotating the same isopropyl group in 10 degrees steps. Two
shallow minima separated by a very small barrier are found. Calculations performed at
B3LYP/6-311++G(d,p) level. Blue lines represent a spline fit added as an eye guide.
7
Figure S6. Lower panel: Potential energy curve obtained using the calculated structure s2 as
starting point and rotating propofol’s OH moiety in 30º steps, while the rest of the
coordinates are relaxed. Upper panel: a similar scan, but taking structure s3 as starting
point. Both curves present a common minimum at -30º. Calculations performed at
B3LYP/6-311++G(d,p) level. Blue lines represent a spline fit added as an eye guide.
8
Figure S7. Reaction path connecting structures s2 and s3, from the curves calculated in figure
7.
9