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