Chemiluminescence of 1,2-Dioxetanone studied by a closedshell DFT approach
Luís Pinto da Silva, Joaquim C.G. Esteves da Silva*
Centro de Investigação em Química, Departamento de Quimica e Bioquímica,
Faculdade de Ciencias da Universidade do Porto
R. Campo Alegre 687 4169-007 Porto, Portugal
*Corresponding author: Joaquim C.G. Esteves da Silva
e-mail: jcsilva@fc.up.pt; Tel: 351 226082869; Fax: 351 226082959
Supplementary Data:
Table S1. S2 before and after spin annihilation, at the open-shell O3LYP/cc-pVDZ level of
theory.
Table S2. S2 before and after spin annihilation, at the open-shell B3LYP/cc-pVDZ level of
theory.
Table S3. S2 before and after spin annihilation, at the open-shell MPWB1K/cc-pVDZ level of
theory.
Table S4. S2 before and after spin annihilation, at the open-shell O3LYP/aug-cc-pVDZ level of
theory.
Table S5. S2 before and after spin annihilation, at the open-shell B3LYP/aug-cc-pVDZ level of
theory.
Table S6. S2 before and after spin annihilation, at the open-shell MPWB1K/aug-cc-pVDZ level
of theory.
Table S7. Cartesian coordinates of the S0 transition state, at the O3LYP/cc-pVDZ level of
theory.
Table S8. Cartesian coordinates of the S0 transition state, at the B3LYP/cc-pVDZ level of
theory.
Table S9. Cartesian coordinates of the S0 transition state, at the MPWB1K/cc-pVDZ level of
theory.
Table S10. Cartesian coordinates of the S0 transition state, at the O3LYP/aug-cc-pVDZ level of
theory.
Table S11. Cartesian coordinates of the S0 transition state, at the B3LYP/aug-cc-pVDZ level of
theory.
Table S12. Cartesian coordinates of the S0 transition state, at the MPWB1K/aug-cc-pVDZ level
of theory.
Figure S1. IRC paths for stables closed- and open-shell S0 and S1 states, with the cc-pVDZ basis
set.
Figure S2. Bond lengths of O5-O3, C2-C1, O5-C2 and O3-C1 bonds, with the cc-pVDZ basis set.
Figure S3. Variation of the O5-C2-C2 and O3-C1-C2 angles, with the cc-pVDZ basis set.
Figure S4. NBO charges of the CH2O and CO2 moieties of simple 1,2-dioxetanone, with the ccpVDZ basis set.
Figure S5. Atomic NBO charges of O5, O3 and O4, with the cc-pVDZ basis set.
Table S1. S2 before and after spin annihilation, at the open-shell O3LYP/cc-pVDZ level of
theory.
Intrinsic
Reaction Before
After
Coordinates
0.1
0.1425
0.0006
0.0
0.2858
0.0025
-0.1
0.3281
0.0039
-0.2
0.2823
0.0029
-0.3
0.1650
0.0008
-0.4
0.0107
0.0000
Table S2. S2 before and after spin annihilation, at the open-shell B3LYP/cc-pVDZ level of
theory.
Intrinsic
Reaction Before
After
Coordinates
0.2
0.0734
0.0002
0.1
0.2521
0.0025
0.0
0.3670
0.0044
-0.1
0.4540
0.0080
0.2
0.4227
0.0067
-0.3
0.3270
0.0036
-0.4
0.1822
0.0010
Table S3. S2 before and after spin annihilation, at the open-shell MPWB1K/cc-pVDZ level of
theory.
Intrinsic
Reaction Before
After
Coordinates
0.2
0.0620
0.0002
0.1
0.2693
0.0037
0.0
0.3833
0.0060
-0.1
0.4924
0.0114
-0.2
0.4465
0.0086
-0.3
0.3373
0.0043
Table S4. S2 before and after spin annihilation, at the open-shell O3LYP/aug-cc-pVDZ level of
theory.
Intrinsic
Reaction Before
After
Coordinates
0.1
0.1675
0.0009
0.0
0.3103
0.0033
-0.1
0.3547
0.0051
-0.2
0.3094
0.0040
-0.3
0.1979
0.0014
-0.4
0.0320
0.0000
Table S5. S2 before and after spin annihilation, at the open-shell B3LYP/aug-cc-pVDZ level of
theory.
Intrinsic
Reaction Before
After
Coordinates
0.2
0.1095
0.0005
0.1
0.2877
0.0037
0.0
0.4894
0.0105
-0.1
0.4556
0.0089
-0.2
0.3620
0.0051
-0.3
0.2224
0.0017
Table S6. S2 before and after spin annihilation, at the open-shell MPWB1K/aug-cc-pVDZ level
of theory.
Intrinsic
Reaction Before
After
Coordinates
0.2
0.0867
0.0004
0.1
0.2952
0.0048
0.0
0.4104
0.0074
-0.1
0.5177
0.0140
-0.2
0.4685
0.0107
-0.3
0.3600
0.0055
-0.4
0.2023
0.0015
Table S7. Cartesian coordinates of the S0 transition state, at the O3LYP/ccpVDZ level of theory.
O
C
C
O
O
H
H
1.50937400
0.82788200
-0.58587800
-0.23763900
-1.66615400
0.82539500
0.82539500
0.24126500
-0.88141800
0.02359900
1.24379400
-0.48869000
-1.47283100
-1.47283500
0.00000000
0.00000200
0.00000000
-0.00000300
0.00000200
0.93549400
-0.93548700
Table S8. Cartesian coordinates of the S0 transition state, at the B3LYP/ccpVDZ level of theory.
O
C
C
O
O
H
H
1.50280400
0.83432000
-0.60602000
-0.22168100
-1.68495100
0.83695100
0.83695100
0.24590600
-0.88734000
0.02286900
1.23659400
-0.47882400
-1.47315800
-1.47316200
0.00000000
0.00000200
0.00000000
-0.00000300
0.00000200
0.93758600
-0.93757900
Table S9. Cartesian coordinates of the S0 transition state, at the
MPWB1K/cc-pVDZ level of theory.
O
C
C
O
O
H
H
1.47620000
0.83007300
-0.59971300
-0.20245500
-1.66717900
0.83072400
0.83072400
0.24667100
-0.88538400
0.01959800
1.21985600
-0.48211300
-1.46286900
-1.46287400
0.00000000
0.00000200
0.00000000
-0.00000200
0.00000200
0.93645400
-0.93644700
Table S10. Cartesian coordinates of the S0 transition state, at the
O3LYP/aug-cc-pVDZ level of theory.
O
O
C
C
O
H
H
-1.51594300
0.23051900
-0.82119600
0.58462400
1.66764400
-0.81881600
-0.81951400
0.23247000
1.25242700
-0.88535300
0.03161900
-0.47744400
-1.46932200
-1.46790400
-0.00066700
0.00036600
0.00046200
0.00010700
-0.00035300
-0.93562200
0.93744300
Table S11. Cartesian coordinates of the S0 transition state, at the
B3LYP/aug-cc-pVDZ level of theory.
O
O
C
C
O
H
H
-1.53381500
0.18028500
-0.82835700
0.56177800
1.66297200
-0.86850500
-0.86861500
0.21291100
1.19904100
-0.92361300
-0.04005200
-0.49875500
-1.50988700
-1.50907400
-0.00016600
-0.00052400
0.00037200
0.00005000
0.00029500
-0.93154500
0.93279300
Table S12. Cartesian coordinates of the S0 transition state, at the
MPWB1K/aug-cc-pVDZ level of theory.
O
C
C
O
O
H
H
-1.48630000
-0.81334000
0.59605000
0.17834000
1.67248000
-0.80614000
-0.80630000
0.22320000
-0.89555000
0.03772000
1.23333000
-0.44658000
-1.46633000
-1.46623000
-0.00014000
-0.00002000
0.00003000
0.00015000
-0.00002000
-0.93721000
0.93723000
Figure S1. IRC paths for stables closed- and open-shell S0 and S1 states, with the cc-pVDZ basis
set.
Figure S2. Bond lengths of O5-O3, C2-C1, O5-C2 and O3-C1 bonds, with the cc-pVDZ basis set.
Figure S3. Variation of the O5-C2-C2 and O3-C1-C2 angles, with the cc-pVDZ basis set.
Figure S4. NBO charges of the CH2O and CO2 moieties of simple 1,2-dioxetanone, with the ccpVDZ basis set.
Figure S5. Atomic NBO charges of O5, O3 and O4, with the cc-pVDZ basis set.