supplementary material for: formation pathways of msea from dms-oh in the presence of o 2 : a...
DESCRIPTION
SP12 SP41 SP34 SP23 Figure S2. Geometries of the MPW1K/MG3S saddle points which connect two conformations of the radical CH 3 S(O 2 )(OH)CH 3. Distances are given in Å. Dihedrals are given in degrees.TRANSCRIPT
Supplementary material for:
Formation Pathways of MSEA from DMS-OH in the Presence of O2: A Theoretical Study
JUAN M. RAMÍREZ-ANGUITA, ÀNGELS GONZÁLEZ-LAFONT*,JOSÉ M. LLUCH
Departament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra, Barcelona, Spain
C1
C2
C3
C4
Figure S1. Geometries of the MPW1K/MG3S minima corresponding to the different conformations for the radical CH3S(O2)(OH)CH3. Distances are given in Å. Angles are given in degrees.
SP12
SP41SP34
SP23
Figure S2. Geometries of the MPW1K/MG3S saddle points which connect two conformations of the radical CH3S(O2)(OH)CH3. Distances are given in Å. Dihedrals are given in degrees.
-5.0
-4.0
-3.0
-2.0
-1.0
0.0
1.0
2.0
C1
-1.3
C2
-1.3
C3
-4.4
C4
-4.2
SP12
1.6SP23
0.6
SP34
-1.5
SP41
-0.3
C1
-1.3
DMSOH + O2
0.0
C1V C1
Ga )(V ‡
SP12V ‡ SP12
Ga )(V C2V C2
Ga )(V ‡
SP23V ‡ SP23
Ga )(V
MPW1K/MG3S -9.8 -6.3 -8.1 -4.8 -10.0 -6.6 -8.0 -4.9
M05-2X/MG3S -15.3 -13.2 -13.2 -10.2 -15.8 -13.9 -13.9 -11.0 CCSD(T)/MG3S // MPW1K/MG3S -14.2 -10.7 -11.8 -8.5 -14.2 -10.7 -12.2 -9.0
C3V C3
Ga )(V ‡
SP34V ‡ SP34
Ga )(V C4V C4
Ga )(V ‡
SP41V ‡ SP41
Ga )(V
MPW1K/MG3S -13.1 -9.5 -10.5 -7.2 -12.9 -9.3 -7.7 -4.7 M05-2X/MG3S -18.8 -15.7 -15.7 -12.8 -18.4 -13.6 -13.6 -10.9 CCSD(T)/MG3S // MPW1K/MG3S -17.3 -13.8 -14.5 -11.2 -17.3 -13.7 -13.0 -10.0
Figure S3. Gibbs free energy profile at the CCSD(T)/MG3S//MPW1K/MG3S level for the stationary points of the exchange process of the different CH3S(O2)(OH)CH3 conformations. Energies are given in kcal/mol.
Table S1. Energies of the stationary points for the exchange process of the CH3S(O2)(OH)CH3 conformations at different levels of calculation. V and _ stand for the classical potential energies and the adiabatic potential energies, respectively. All energies (in kcal/mol) are relative to DMS-OH + O2.
GaV
SP4-1a
Figure S4. Geometries of the MPW1K/MG3S stationary points located for the reaction R4. Distances are given in Å. Dihedrals are given in degrees.
SP4-1b
Min4-1
SPMin4
Min4-2
SP4-2
PC4-1
SP4-3
PC1/PC4-2
-30
-20
-10
0
10
20
30
40
Min2a
8.2
Min2b
6.9
SP4-1a
26.4
SP4-1b
24.5
Min4-2
-5.4Min4-1
-7.4
SPMin4
2.5
PC4-2
-16.8
SP4-3
29.1
SP4-2
14.8
PC4-1
-3.8
MSEA + CH2OOH
-5.8
MSEA + CH3OO -
18.8
O2 + DMSOH 0.0
Figure S5. CCSD(T)/MG3S/MPW1K/MG3S Gibbs free energy (kcal/mol) profile at 298 K for the reaction R4
Table S2. Energies of the stationary points for the reaction R4 at different levels of calculation. V and stand for the classical potential energies and the adiabatic potential energies, respectively. All energies (in kcal/mol) are relative to reactants.
GaV
SP5
Figure S6. Geometries of the MPW1K/MG3S stationary points located for the reaction R5. Distances are given in Å. Dihedrals are given in degrees.
PC5