Supplementary Data for
Theoretical Study on the Reaction Mechanism of NO and CO Catalyzed by Rh Atom
Qian-Qian Xua, Hua-Qing Yangb*,Chao Gaob, Chang-Wei Hu,a,*
a Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, Sichuan, 610064, P.R. China
b College of Chemical Engineering, Sichuan University, Chengdu, Sichuan, 610065, P.R. China
Struct. Chem.
*Correspondence to: H.-Q. Yang; e-mail: ;
C.-W.Hu; e-mail: (or)
Fax: 028-85411105
Telephone: 028-85411105
- Table S1: Zero-point energies (ZPE) (hartree), total energies (Ec) (hartree) corrected by ZPE, and relative energies (Er) (kJ mol1) with respect to reactants [Rh(4F) + 2NO+CO] of the species plus NO for the reaction (2)Rh + NO + CO → RhN + CO2 calculated at the B3LYP/6-311+G(2d), SDD and CCSD(T)//B3LYP/6-311+G(2d), SDDlevels……..…………………………………….…....……………P3
- Table S2: Zero-point energies (ZPE) (hartree), total energies (Ec) (hartree) corrected by ZPE, and relative energies (Er) (kJ mol1) with respect to reactants [Rh(4F) + 2NO+CO] of the species plus CO2for the reaction (3)RhN + NO → Rh + N2O calculated at the B3LYP/6-311+G(2d), SDD and CCSD(T)// B3LYP/6-311+G(2d), SDDlevels…………………………………….………..….………………………P4
- Table S3: Zero-point energies (ZPE) (hartree), total energies (Ec) (hartree) corrected by ZPE, and relative energies (Er) (kJ mol1) with respect to reactants [Rh(4F) + 2NO] of the species for the reaction (4)Rh + 2NO → RhO + N2O calculated at the B3LYP/6-311+G(2d), SDD and CCSD(T)//B3LYP/6-311+G(2d), SDDlevels…………………….……………………….…………………………………………..…..…..P5
- Table S4: Zero-point energies (ZPE) (hartree), total energies (Ec) (hartree) corrected by ZPE, and relative energies (Er) (kJ mol1) with respect to reactants [Rh(4F) + N2O + CO] of the species plus CO for the reaction (5)Rh + N2O → RhO + N2 calculated at the B3LYP/6-311+G(2d), SDD and CCSD(T)//B3LYP/6-311+G(2d), SDDlevels……….……………………………….….….….….…..…..P6
- Table S5: Zero-point energies (ZPE) (hartree), total energies (Ec) (hartree) corrected by ZPE, and relative energies (Er) (kJ mol1) with respect to reactants [Rh(4F) + N2O + CO] of the species plus N2 for the reaction (6)RhO + CO → Rh + CO2 calculated at the B3LYP/6-311+G(2d), SDD and CCSD(T)//B3LYP/6-311+G(2d), SDDlevels……………………...... ….….……….....P6
- Table S6: Zero-point energies (ZPE) (hartree), total energies (Ec) (hartree) corrected by ZPE, and relative energies (Er) (kJ mol1) with respect to reactants [RhN(1Σ)+CO] of the species for the formation of the NCO and CN side products in the reaction of NO and CO catalyzed by rhodium atomcalculated at the B3LYP/6-311+G(2d), SDD and CCSD(T)//B3LYP/6-311+G(2d), SDDlevels…………………………...P7
- Table S7: Standard orientation of the species in the reaction of NO and CO catalyzed by rhodium atomcalculated at the B3LYP/6-311+G(2d), SDD level…………………………….….….….….….…….....…P8
- Table S8: Vibration frequencies (cm-1) scaled by 0.963/IR intensities (Debye2 amu-1Å-2) of some typical species in the reaction of NO and CO catalyzed by rhodium atom calculated at the B3LYP/6-311+G(2d), SDD level…………………………………………………...... ….….….…..…….…P14
Table S1: Zero-point energies (ZPE) (hartree), total energies (Ec) (hartree) corrected by ZPE, and relative energies (Er) (kJ mol1) with respect to reactants [Rh(4F) +2NO+CO] of the species plus NO for the reaction (2)Rh + NO + CO → RhN + CO2calculated at the B3LYP/6-311+G(2d), SDD and CCSD(T)//B3LYP/6-311+G(2d), SDDlevels
Species / B3LYP / CCSD(T)ZPE / Ec / Er / Ec / Er
Rh(2D) +NO+CO / 0.01394 / -483.69658 / 32.0 / -482.27862 / 9.1
1RhNO+CO / 0.01540 / -483.79194 / -218.4 / -482.37031 / -231.7
2RhCO+NO / 0.01629 / -483.77689 / -178.8 / -482.34009 / -152.3
1OCRhNO / 0.01936 / -483.86023 / -397.7 / -482.44000 / -414.6
1TS1 / 0.01815 / -483.73448 / -67.5 / -482.31932 / -97.8
1TS1, <S2>=0.437 / 0.01794 / -483.73546 / -70.1 / -482.31804 / -94.4
1NRhCO2 / 0.01868 / -483.78484 / -199.7 / -482.37141 / -234.6
1NRhCO2, <S2>=0.704 / 0.01811 / -483.78673 / -204.7 / -482.36392 / -214.9
RhN(1Σ) +CO2 / 0.01848 / -483.77071 / -162.6 / -482.35466 / -190.6
Rh(4F) +NO+CO / 0.01394 / -483.70877 / 0.0 / -482.28207 / 0.0
3RhNO+CO / 0.01526 / -483.76707 / -153.1 / -482.33666 / -143.3
4RhCO+NO / 0.01489 / -483.72883 / -52.7 / -482.30490 / -59.9
3OCRhNO / 0.01795 / -483.82420 / -303.1 / -482.39138 / -287.0
3TS1 / 0.01708 / -483.74062 / -83.6 / -482.31004 / -73.4
3cyc-NRhCO2 / 0.01884 / -483.74660 / -99.3 / -482.31633 / -89.9
3TS2 / 0.01752 / -483.73499 / -68.8 / -482.30287 / -54.6
3NRhCO2 / 0.01831 / -483.78972 / -212.5 / -482.36113 / -207.6
RhN(3Σ)+CO2 / 0.01834 / -483.78460 / -199.1 / -482.35361 / -187.8
Table S2: Zero-point energies (ZPE) (hartree), total energies (Ec) (hartree) corrected by ZPE, and relative energies (Er) (kJ mol1) with respect to reactants [Rh(4F) +2NO+CO] of the species plus CO2for the reaction (3)RhN + NO → Rh + N2O calculated at the B3LYP/6-311+G(2d), SDD and CCSD(T)// B3LYP/6-311+G(2d), SDDlevels
Species / B3LYP / CCSD(T)ZPE / Ec / Er / Ec / Er
RhN(1Σ)+NO / 0.01849 / -483.77071 / -162.6 / -482.35466 / -190.6
2NRhON / 0.01923 / -483.79857 / -235.8 / -482.34845 / -174.3
2TS3 / 0.01945 / -483.78114 / -190.0 / -482.35570 / -193.3
2RhON2 / 0.02055 / -483.86260 / -403.9 / -482.43162 / -392.6
Rh(2D) +N2O / 0.02272 / -483.84220 / -350.3 / -482.40607 / -325.6
RhN(3Σ)+NO / 0.01835 / -483.78460 / -199.1 / -482.35361 / -187.8
4NRhON / 0.01940 / -483.80940 / -264.2 / -482.36882 / -227.7
4TS3 / 0.01848 / -483.76861 / -157.1 / -482.33284 / -133.3
4RhON2 / 0.02006 / -483.84336 / -353.4 / -482.39843 / -305.5
Rh(4F) +N2O / 0.02272 / -483.85440 / -382.3 / -482.40952 / -334.6
2NRhNO / 0.02015 / -483.83799 / -339.3 / -482.40119 / -312.7
2TS4 / 0.01918 / -483.79702 / -231.7 / -482.36386 / -214.7
2RhNNO / 0.02237 / -483.86862 / -419.7 / -482.42503 / -375.3
4NRhNO / 0.02041 / -483.84639 / -361.3 / -482.41045 / -337.1
4TS4 / 0.01897 / -483.79217 / -219.0 / -482.34836 / -174.0
4RhNNO / 0.02279 / -483.85442 / -382.4 / -482.41065 / -337.6
Table S3: Zero-point energies (ZPE) (hartree), total energies (Ec) (hartree) corrected by ZPE, and relative energies (Er) (kJ mol1) with respect to reactants [Rh(4F) +2NO] of the species for the reaction (4)Rh + 2NO → RhO + N2Ocalculated at the B3LYP/6-311+G(2d), SDD and CCSD(T)//B3LYP/6-311+G(2d), SDDlevels
Species / B3LYP / CCSD(T)ZPE / Ec / Er / Ec / Er
Rh(2D) +2NO / 0.00891 / -370.34960 / 32.0 / -369.16434 / 9.1
1RhNO+NO / 0.01037 / -370.44497 / -218.4 / -369.25604 / -231.7
2ONRhON / 0.01071 / -370.44486 / -218.1 / -369.25782 / -236.4
2TS5 / 0.01118 / -370.41080 / -128.7 / -369.20774 / -104.9
2RhONNO / 0.01377 / -370.41159 / -130.7 / -369.20298 / -92.4
2TS6 / 0.01174 / -370.38187 / -52.7 / -369.19249 / -64.9
2ORhON2 / 0.01384 / -370.44904 / -229.0 / -369.24751 / -209.3
RhO(2Σ)+N2O / 0.01296 / -370.43548 / -193.4 / -369.23049 / -164.6
Rh(4F) +2NO / 0.00891 / -370.36180 / 0.0 / -369.16779 / 0.0
3RhNO+NO / 0.01022 / -370.42009 / -153.1 / -369.22239 / -143.4
4ONRhON / 0.01279 / -370.44858 / -227.8 / -369.23729 / -182.5
4TS5 / 0.01125 / -370.40757 / -120.2 / -369.18787 / -52.7
4RhONNO / 0.01377 / -370.41811 / -147.8 / -369.21398 / -121.3
4TS6 / 0.01116 / -370.37089 / -23.9 / -369.15870 / 23.9
4ORhON2 / 0.01338 / -370.44838 / -227.3 / -369.25024 / -216.5
RhO(4Σ)+N2O / 0.01293 / -370.44694 / -223.5 / -369.24462 / -201.7
Table S4: Zero-point energies (ZPE) (hartree), total energies (Ec) (hartree) corrected by ZPE, and relative energies (Er) (kJ mol1) with respect to reactants [Rh(4F)+ N2O + CO] of the species plus CO for the reaction (5)Rh + N2O → RhO + N2calculated at the B3LYP/6-311+G(2d), SDD and CCSD(T)//B3LYP/6-311+G(2d), SDDlevels
Species / B3LYP / CCSD(T)ZPE / Ec / Er / Ec / Er
Rh(2D) +N2O / 0.01610 / -408.55020 / 32.0 / -407.27077 / 9.1
2RhONN / 0.01470 / -408.55928 / 8.2 / -407.26962 / 12.1
2TS7 / 0.01367 / -408.55697 / 14.3 / -407.27573 / -4.0
2ORhN2 / 0.01455 / -408.64477 / -216.3 / -407.37386 / -261.6
RhO(2Σ)+N2 / 0.01249 / -408.62715 / -170.0 / -407.34819 / -194.2
Rh(4F) +N2O / 0.01610 / -408.56240 / 0.0 / -407.27422 / 0.0
4RhON2 / 0.01344 / -408.55136 / 29.0 / -407.26313 / 29.1
4TS7 / 0.01260 / -408.54290 / 51.2 / -407.25997 / 37.4
4ORhN2 / 0.01423 / -408.66089 / -258.6 / -407.38291 / -285.4
RhO(4Σ)+N2 / 0.01246 / -408.63681 / -200.1 / -407.36232 / -231.3
Table S5: Zero-point energies (ZPE) (hartree), total energies (Ec) (hartree) corrected by ZPE, and relative energies (Er) (kJ mol1) with respect to reactants [Rh(4F)+ N2O + CO] of the species plus N2for the reaction (6)RhO + CO → Rh + CO2calculated at the B3LYP/6-311+G(2d), SDD and CCSD(T)//B3LYP/6-311+G(2d), SDDlevels
Species / B3LYP / CCSD(T)ZPE / Ec / Er / Ec / Er
RhO(2Σ)+CO / 0.01249 / -408.62715 / -170.0 / -407.34819 / -194.2
2ORhCO / 0.01551 / -408.68704 / -327.2 / -407.41676 / -374.2
2TS8 / 0.01474 / -408.65916 / -254.0 / -407.39187 / -308.9
2RhCO2 / 0.01672 / -408.70699 / -379.6 / -407.42383 / -392.8
Rh(2D) +CO2 / 0.01721 / -408.68690 / -326.9 / -407.40950 / -355.2
RhO(4Σ)+CO / 0.01246 / -408.63861 / -200.1 / -407.36232 / -231.3
4ORhCO / 0.01494 / -408.68663 / -326.2 / -407.41152 / -360.5
4TS8 / 0.01370 / -408.61870 / -147.8 / -407.35007 / -199.1
4RhCO2 / 0.01725 / -408.69896 / -358.5 / -407.41355 / -365.8
Rh(4F) +CO2 / 0.01721 / -408.69910 / -358.9 / -407.41295 / -364.2
Table S6: Zero-point energies (ZPE) (hartree), total energies (Ec) (hartree) corrected by ZPE, and relative energies (Er) (kJ mol1) with respect to reactants [RhN(1Σ)+CO] of the species for the formation of the NCO and CN side products in the reaction of NO and CO catalyzed by rhodium atomcalculated at the B3LYP/6-311+G(2d), SDD and CCSD(T)//B3LYP/6-311+G(2d), SDDlevels
Species / B3LYP / CCSD(T)ZPE / Ec / Er / Ec / Er
RhN(1Σ)+ CO / 0.00741 / -278.54889 / 0.0 / -277.55095 / 0.0
1NRhCO / 0.01020 / -278.60358 / -143.6 / -277.60253 / -135.4
1NRhCO, <S2>=0.926 / 0.00972 / -278.61155 / -164.5 / -277.60087 / -131.1
1TS9 / 0.00913 / -278.57583 / -70.7 / -277.57511 / -63.4
1TS9, <S2>=0.745 / 0.00906 / -278.58423 / -92.8 / -277.57492 / -62.9
1RhNCO / 0.01068 / -278.60776 / -154.6 / -277.59127 / -105.9
1RhNCO, <S2>=0.898 / 0.01220 / -278.65123 / -268.7 / -277.62616 / -197.5
Rh(2D) +NCO / 0.00880 / -278.53905 / 25.8 / -277.51023 / 106.9
1TS10 / 0.01074 / -278.59735 / -127.2 / -277.57353 / -59.3
1TS10, <S2>=0.858 / 0.01079 / -278.61337 / -169.3 / -277.59327 / -111.1
RhN(3Σ) +NO / 0.00727 / -278.56279 / -36.5 / -277.54990 / 2.8
3NRhCO / 0.00963 / -278.62156 / -190.8 / -277.60707 / -147.3
3TS9 / 0.00899 / -278.58691 / -99.8 / -277.57174 / -54.6
3RhNCO / 0.01215 / -278.66105 / -294.5 / -277.63392 / -217.8
Rh(4F) +NCO / 0.00880 / -278.55124 / -6.2 / -277.51368 / 97.9
3TS10 / 0.01092 / -278.62347 / -195.8 / -277.60150 / -132.7
1RhOCN / 0.01162 / -278.60172 / -138.7 / -277.57781 / -70.5
1RhOCN, <S2>=0.861 / 0.01155 / -278.61706 / -179.0 / -277.59381 / -112.5
1TS11 / 0.00867 / -278.51339 / 93.2 / -277.51172 / 103.0
1TS11, <S2>=1.040 / 0.00828 / -278.54134 / 19.8 / -277.51368 / 97.9
1ORhCN / 0.00985 / -278.57465 / -67.6 / -277.57587 / -65.4
1ORhCN, <S2>=0.249 / 0.00972 / -278.59357 / -117.3 / -277.58096 / -78.8
RhO(2Σ) +CN / 0.00679 / -278.45835 / 237.7 / -277.43301 / 309.6
3RhOCN / 0.01148 / -278.62594 / -202.3 / -277.60156 / -132.9
3TS11 / 0.00834 / -278.54775 / 3.0 / -277.53120 / 51.8
3ORhCN / 0.00968 / -278.60303 / -142.1 / -277.59082 / -104.7
RhO(4Σ) +CN / 0.00676 / -278.46981 / 207.6 / -277.44715 / 272.5
Table S7: Standard orientation of the species in the reaction of NO and CO catalyzed by rhodium atomcalculated at the B3LYP/6-311+G(2d), SDD level
1
Rh(4F):
Rh 0.000000 0.000000 0.000000
Rh(2D):
Rh 0.000000 0.000000 0.000000
NO:
N 1.683105 -1.397849 0.000000
O 0.535665 -1.397849 0.000000
CO：
O 0.000000 0.000000 -0.482433
C 0.000000 0.000000 0.643244
CO2:
O -0.962254 1.038397 0.001182
C -2.121975 1.075082 -0.003160
O -3.281697 1.111768 -0.007502
1RhNO：
Rh -0.000117 0.577837 0.000000
N 0.139927 -1.132242 0.000000
O -0.122348 -2.260859 0.000000
2RhCO:
Rh -0.491801 1.025098 0.000000
O 2.462597 0.760117 0.000000
C 1.316240 0.862934 0.000000
1OCRhNO:
Rh 0.044852 -0.574838 -0.000049
C -1.569381 0.401640 -0.000126
O -2.429789 1.154281 0.000140
O 2.016187 1.438915 -0.000377
N 1.530428 0.387759 0.000724
1TS1:
Rh 0.173748 1.007383 0.089529
C 0.506449 -1.047690 -0.049637
O 1.597878 -1.534525 -0.124690
O -0.695083 -1.464149 -0.024030
N -1.345319 0.297224 0.109533
1NRhCO2:
Rh 0.613755 -0.180403 -0.000050
N 1.472675 1.229674 0.000028
O -2.301239 0.979469 0.000000
O -1.280556 -1.116808 0.000040
C -1.529273 0.100937 0.000036
RhN(1Σ):
Rh 0.000000 0.000000 -0.218127
N 0.000000 0.000000 1.402244
1TS1, <S2>=0.437:
Rh -0.741401 -0.235239 -0.000127
C 1.331297 -0.084385 -0.000114
O 2.057227 -1.036113 0.000617
O 1.460732 1.181355 -0.000869
N -0.395486 1.418593 0.001201
1NRhCO2, <S2>=0.704:
Rh -0.604831 -0.162566 -0.063050
N -1.674822 1.066482 0.236560
O 2.342993 0.995228 -0.067193
O 1.323810 -1.087183 0.196242
C 1.601121 0.097623 0.024822
3RhNO:
Rh 0.000000 0.576222 0.000000
N 0.387687 -1.237775 0.000000
O -0.339226 -2.158197 0.000000
4RhCO:
Rh 0.000000 0.619216 0.000000
O -0.193898 -2.440415 0.000000
C 0.258530 -1.390234 0.000000
3OCRhNO:
Rh -0.028460 -0.312114 -0.000029
C -1.845090 0.263310 -0.000611
O -2.903897 0.690388 0.000329
O 2.856684 0.712430 -0.000385
N 1.818826 0.178159 0.000763
3TS1:
Rh 0.202646 1.028497 0.001003
C 0.672078 -0.818403 0.000355
O 1.431020 -1.700049 -0.000266
O -0.947443 -1.207180 -0.000628
N -1.427796 0.026172 -0.000464
3cyc-NRhCO2:
Rh -0.000303 0.793008 0.000000
N -1.466705 -0.384817 0.000000
O -0.707428 -1.616783 0.000000
O 1.573059 -1.697652 0.000000
C 0.557566 -1.081495 0.000000
3TS2:
Rh -0.100180 -0.657375 -0.778373
N -1.476607 0.432239 -0.827455
O -0.660176 1.648466 0.346695
O 1.433635 0.964087 1.006813
C 0.377419 0.931356 0.441870
3NRhCO2:
Rh -0.598146 -0.134859 -0.152291
N -1.627496 0.972076 0.565161
O 2.340840 0.925172 -0.142097
O 1.258512 -1.060150 0.441830
C 1.578385 0.062884 0.072632
RhN(3Σ):
Rh 0.000000 0.000000 0.148642
N 0.000000 0.000000 1.801358
N2O:
N 0.000000 0.000000 0.000000
N 0.000000 0.000000 1.121794
O 0.000000 0.000000 2.309045
2NRhON:
Rh -0.425142 -0.141019 -0.000001
N -1.882407 0.634627 -0.000009
N 2.702166 0.388980 0.000010
O 1.639370 -0.120772 0.000005
RhO(2Σ):
Rh 0.000000 0.000000 0.264481
O 0.000000 0.000000 -1.487707
2TS3:
Rh -0.535085 -0.127004 0.000009
N 0.753593 -1.266875 0.000008
N 2.164797 0.467324 -0.000002
O 1.194916 1.114962 -0.000007
2RhON2:
Rh -0.620467 -0.025882 0.000058
N 1.076018 -1.039124 -0.000083
N 1.824989 -0.106780 0.000099
O 0.943727 1.137118 -0.000067
2NRhNO：
N 1.521430 1.063253 0.000000
O -2.442519 0.442041 0.000000
Rh 0.421608 -0.220793 0.000000
N -1.440317 -0.149060 0.000000
2TS4：
Rh -0.450655 -0.064382 0.022190
N -1.837677 1.031813 0.119241
N -0.152750 1.856641 -0.351817
O 0.520417 2.620317 0.210386
2RhNNO：
Rh -0.009037 0.775685 0.000000
N 1.073356 -0.962676 0.000000
N -0.076077 -1.300962 0.000000
O -0.866082 -2.227076 0.000000
4NRhON：
Rh -0.400853 -0.068514 -0.000035
N -2.010115 0.305539 0.000092
N 2.751791 0.203834 -0.000122
O 1.588054 -0.066102 0.000235
4TS3：
Rh 0.598085 -0.067311 -0.000001
N -0.543279 1.298241 0.000008
N -1.871953 0.190938 -0.000011
O -1.250899 -0.924408 0.000008
RhO(4Σ)：
Rh 0.000000 0.000000 0.262369
O 0.000000 0.000000 -1.468155
4RhON2：
Rh 0.000000 0.826586 0.000000
N 1.104119 -2.092524 0.000000
N -0.054176 -2.050135 0.000000
O -0.918701 -1.024720 0.000000
4NRhNO：
N -1.583764 -1.142390 0.000000
O 0.108412 2.549675 0.000000
Rh -0.075782 -0.346422 0.000000
N 0.456133 1.440433 0.000000
4TS4：
Rh -0.488387 -0.184641 0.040382
N -1.674660 1.133730 0.144747
N -0.155472 1.889730 -0.464823
O 0.397854 2.605570 0.279694
4RhNNO：
Rh 0.073099 1.734342 0.000000
N 0.724085 -0.915673 0.000000
N 0.037500 -1.807504 0.000000
O -0.712525 -2.726194 0.000000
2ONRhON：
Rh -1.734659 -0.022923 0.147311
N -0.725388 1.352705 -0.048618
N 3.677207 -0.331653 0.229917
O 0.249411 1.980096 -0.099148
O 2.909303 -1.063590 -0.207339
2TS5：
Rh -0.950347 -0.075173 0.000241
N 0.872869 0.651457 0.061786
N 2.024911 -0.460874 0.059326
O 1.271593 1.786168 -0.052897
O 1.538551 -1.530083 -0.054434
2RhONNO：
Rh 0.000000 0.834262 0.000000
N 0.560685 -1.030828 0.000000
N -0.653123 -1.641786 0.000000
O 1.582667 -1.695253 0.000000
O -1.501784 -0.658935 0.000000
2TS6：
Rh -0.070449 0.735781 0.000000
N 0.484591 -1.214362 0.000000
N -0.548062 -1.842836 0.000000
O 1.707429 -1.468412 0.000000
O -1.618214 -0.151391 0.000000
2ORhON2：
Rh -0.544753 0.523717 -0.000004
N 2.457955 -0.448112 0.000002
O 1.320544 -0.838535 -0.000063
N 3.525657 -0.125567 0.000060
O -1.929821 1.566820 0.000005
4ONRhON：
Rh 0.819610 0.441602 0.006204
N -0.354788 1.758314 0.076048
N 2.922346 -1.907092 -0.114504
O -1.124496 2.625103 0.122409
O 2.113201 -1.003292 -0.068035
4TS5：
Rh -0.406962 0.000463 -0.027269
N 0.130867 0.000086 1.836874
N 1.858255 -0.000004 2.294407
O -0.654410 -0.000857 2.732382
O 2.557263 0.000312 1.357976
4RhONNO：
Rh 0.035186 0.990775 0.000000
N 0.575069 -1.035623 0.000000
N -0.662330 -1.632074 0.000000
O 1.565508 -1.754335 0.000000
O -1.525995 -0.709348 0.000000
4TS6：
Rh -0.581733 1.433817 0.000000
N 0.638233 -1.487941 0.000000
N -0.521901 -1.695099 0.000000
O 1.769364 -1.928265 0.000000
O -1.348668 -0.263733 0.000000
4ORhON2：
Rh -0.005490 0.044962 0.045934
N -0.012716 0.007209 3.815568
N 0.960893 0.079556 4.363929
O -1.047090 -0.070447 3.231581
O 1.419568 -0.108281 1.022902
N2:
N 0.161090 -0.322581 0.000000
N -0.930509 -0.322581 0.000000
2RhONN:
N 2.281526 -0.702126 0.000000
N 1.348270 -0.034141 0.000000
O 0.903572 1.212940 0.000000
Rh -0.738188 -0.119141 0.000000
2TS7:
N -0.282317 0.000002 0.354747
N 0.021914 -0.000002 1.442178
O 1.322735 0.000000 2.271537
Rh -0.280911 0.000001 3.449801
2ORhN2:
Rh 0.069722 0.434084 0.000000
N -0.913368 -1.233057 0.000000
N -1.373603 -2.235924 0.000000
O 1.769064 0.038582 0.000000
4TS7：
Rh 0.024520 0.724787 0.000000
N -1.101134 -1.101100 0.000000
N -0.190945 -1.848262 0.000000
O 1.109374 -0.991740 0.000000
4ORhN2：
Rh 0.176683 0.306167 0.000000
N -1.119500 -1.352924 0.000000
N -1.724167 -2.268891 0.000000
O 1.494365 1.446898 0.000000
2ORhCO：
Rh 0.437599 -0.247242 0.000000
O 0.998580 1.414883 0.000000
C -1.394921 -0.049628 0.000000
O -2.511199 0.182484 0.000000
2TS8：
Rh 0.119967 -0.002335 -0.127637
O -0.335497 -0.002687 1.649213
C 1.467135 0.009636 1.169119
O 2.372807 0.016879 1.868347
2RhCO2：
Rh 0.729071 -0.096679 0.000000
O -0.933456 1.235950 0.000000
C -1.292039 0.042373 0.000000
O -2.198439 -0.723886 0.000000
4ORhCO：
Rh 0.331956 0.065848 0.000001
O 1.605584 1.287066 0.000001
C -1.633185 -0.138091 0.000001
O -2.754548 0.047029 0.000000
4TS8：
Rh 0.007858 -0.004554 -0.230602
O -0.193578 0.001083 1.696838
C 1.470390 0.008724 1.170125
O 2.339745 0.016241 1.922681
4RhCO2：
Rh 0.000000 1.425773 0.000000
O 1.045405 -2.412483 0.000000
C -0.000189 -2.916401 0.000000
O -1.045263 -3.420192 0.000000
NCO:
N -0.000002 0.000000 0.001864
C 0.000003 0.000000 1.213384
O 0.000216 0.000000 2.381065
1NRhCO：
Rh 1.166050 0.000000 0.494710
N 0.048916 0.000000 1.757972
C 2.883572 0.000000 1.268164
O 3.791483 0.000000 1.957344
1NRhCO, <S2>=0.926:
Rh 1.166971 0.000000 0.489311
N 0.033137 0.000000 1.756781
C 2.881514 0.000000 1.285240
O 3.808398 0.000000 1.946859
1TS9:
Rh 0.351062 0.000000 0.187805
N -0.353129 0.000000 1.776352
C 1.645269 0.000000 1.594211
O 2.512651 0.000000 2.336740
1TS9, <S2>=0.745:
Rh 0.345590 0.000127 0.149745
N -0.251399 -0.000051 1.807963
C 1.595802 -0.000263 1.594523
O 2.465861 0.000187 2.342877
1RhNCO:
Rh 0.274808 0.000000 0.019277
N 0.056389 0.000000 1.853195
C 1.374116 0.000000 1.769815
O 2.450540 0.000000 2.252820
1RhNCO, <S2>=0.898:
Rh -0.294202 0.000000 -0.319910
N 0.423923 0.000000 1.518827
C 1.505481 0.000000 2.046396
O 2.520651 0.000000 2.649795
1TS10:
Rh 0.004548 0.000000 0.013415
N -0.034655 0.000000 2.492284
C 0.989376 0.000000 1.885345
O 1.883228 0.000000 1.029410
1TS10, <S2>=0.858:
Rh -0.005112 0.000000 -0.080878
N -0.007112 0.000000 2.563367
C 0.970109 0.000000 1.889695
O 1.884612 0.000000 1.048271
3NRhCO:
Rh 1.170800 0.000000 0.472448
N 0.039574 0.000000 1.766341
C 2.872107 0.000000 1.295066
O 3.807540 0.000000 1.944335
3TS9:
Rh 0.340143 -0.000234 0.122439
N -0.185898 0.000348 1.828831
C 1.564842 -0.000169 1.595805
O 2.436766 0.000055 2.348033
3RhNCO:
Rh -0.296527 0.000000 -0.335808
N 0.425605 0.000000 1.522529
C 1.504673 0.000000 2.053727
O 2.522102 0.000000 2.654659
3TS10:
Rh 0.053093 0.000000 -0.237964
N 0.046975 0.000000 2.703432
C 0.935633 0.000000 1.927725
O 1.806796 0.000000 1.027261
CN:
N 0.000000 0.000000 -0.070357
C 0.000000 0.000000 1.281877
1RhOCN：
Rh -0.229247 0.000000 0.206864
N -0.233213 0.000000 3.737090
C 0.403334 0.000000 2.757968
O 1.075580 0.000000 1.690709
1RhOCN, <S2>=0.861:
Rh -0.190688 0.000000 0.099951
N -0.186053 0.000000 3.808623
C 0.383406 0.000000 2.791012
O 1.009789 0.000000 1.693045
1TS11:
Rh -0.015726 0.000001 -0.114126
N 0.206503 0.000001 2.995052
C 0.391704 -0.000003 1.840928
O 1.602850 0.000001 0.687394
1TS11, <S2>=1.040:
Rh -0.000172 -0.000001 -0.129305
N 0.233951 -0.000002 3.014976
C 0.331384 0.000003 1.852185
O 1.620168 0.000000 0.671391
1ORhCN:
Rh -0.377404 -0.269516 0.000000
N 2.661262 0.271437 0.000000
C 1.507804 0.147098 0.000000
O -1.235252 1.196172 0.000000
1ORhCN, <S2>=0.249:
Rh -0.377895 -0.237719 0.000000
N 2.689743 0.265302 0.000000
C 1.539035 0.124523 0.000000
O -1.294473 1.193086 0.000000
3RhOCN:
Rh -0.155192 0.000000 -0.001197
N -0.140280 0.000000 3.871828
C 0.368157 0.000000 2.823046
O 0.943769 0.000000 1.698954
3TS11:
Rh 0.001078 0.000000 -0.123556
N 0.266254 -0.000001 3.006104
C 0.291399 0.000001 1.833084
O 1.626600 0.000000 0.693616
3ORhCN:
Rh -0.379441 -0.236271 0.000000
N 2.692795 0.266115 0.000000
C 1.542662 0.121324 0.000000
O -1.299606 1.194024 0.000000
1
Table S8: Vibration frequencies (cm-1) scaled by 0.963/IR intensities (Debye2 amu-1Å-2) of some typical species in the reaction of NO and CO catalyzed by rhodium atomcalculated at the B3LYP/6-311+G(2d), SDD level
NO: 1883/43.5
CO: 2129 /81.7
CO2:651/29.1,651/29.1,1314/0.0,2312/678.4
1RhNO：103/16.2, 609/0.2, 1787/797.2
2RhCO:331/6.1, 331/6.1, 494/9.1, 1968/713.8
1OCRhNO:74/1.5, 231/2.2, 288/2.4, 340/4.9, 449/34.7, 493/1.2, 661/10.4, 1754/1195.3, 2012/769.0
1TS1:i395/13.8, 168/4.5, 225/0.7, 425/3.7, 560/0.8, 699/202.0, 891/21.0, 1075/159.7, 1746/539.8
1NRhCO2:97/0.0, 115/3.4, 249/42.3, 324/14.8, 522/2.2, 609/533.6, 1002/36.2, 1116/214.7, 1983/698.5
RhN(1Σ):1005/170.1
1TS1, <S2>=0.437:i415/14.5, 159/3.9, 226/1.1, 414/3.8, 558/1.4, 699/203.2, 827/32.3, 1069/152.7, 1747/523.6
1NRhCO2, <S2>=0.704:51/4.0, 90/2.1, 178/64.1, 257/25.9, 530/9.7, 566/551.8, 948/46.5, 1136/189.1, 2017/611.7
3RhNO:242/4.8, 545/6.9, 1650/885.9
4RhCO:230/49.2, 347/11.4, 1954/1223.8
3OCRhNO:48/1.4, 87/0.1, 258/3.0, 310/0.7, 376/5.2, 426/45.3, 448/4.0, 1737/1152.2, 2015/893.8
3TS1:i575/20.3, 150/1.7, 307/4.8, 403/0.1, 420/0.6, 513/3.8, 597/1.7, 1072/157.5, 1878/470.2
3cyc-NRhCO2:198/5.1, 286/7.9, 456/0.5, 492/1.0, 517/2.0, 660/2.8, 732/26.7, 971/118.4, 1771/494.0
3TS2:i445/13.9, 118/4.7, 232/0.6, 368/2.3, 545/4.3, 681/191.1, 746/16.0, 1095/153.1, 1741/446.5
3NRhCO2:96/13.0, 106/5.6, 190/28.8, 282/33.4, 560/108.6, 576/347.4, 883/23.1, 1147/160.2, 2017/559.9
RhN(3Σ):946/72.1
N2O:588/5.0, 588/5.0, 1266/69.6, 2233/388.5
2NRhON: 62/4.9, 181/1.1, 257/0.4, 260/27.2, 938/249.1, 1504/1063.0
2TS3:i305/17.8, 194/4.6, 203/7.7, 498/16.9, 775/4.6, 1623/464.4
2RhON2:104/42.1, 351/2.2, 438/0.8, 537/41.0, 749/3.0, 1580/108.7
2NRhNO: 62/6.9, 267/1.9, 279/4.1, 432/6.3, 814/47.6, 1736/901.2
2TS4:i390/32.2, 193/2.4, 221/2.2, 389/1.4, 712/9.2, 1661/836.2
2RhNNO: 176/3.6, 396/21.3, 469/1.1, 628/138.8, 1149/238.6,1709/328.4
4NRhON: 33/4.1, 272/0.5, 275/0.3, 360/4.5, 904/164.1, 1427/550.2
4TS3:i416/106.5, 155/0.0, 334/5.5, 484/10.9, 765/2.0, 1146/125.6
4RhON2:92/2.1, 282/7.2, 312/61.9, 434/143.5, 711/92.4, 1720/444.8
4NRhNO:90/6.5, 320/0.1, 355/1.6, 459/0.8, 741/27.4, 1734/874.8
4TS4:i296/50.1, 140/6.4, 275/9.6, 390/2.0, 717/22.8, 1567/831.7
4RhNNO: 41/0.8, 65/2.4, 554/16.1, 581/4.9, 1252/182.5, 2209/404.9
2ONRhON:10/0.8, 15/0.1, 23/1.1, 29/0.4, 49/22.1,132/12.4, 615/0.3, 1774/768.8, 1882/43.0
2TS5:i552/1161.5, 98/6.3, 171/4.8, 210/2.2, 268/7.0, 410/28.1, 607/102.5, 1421/616.4, 1540/707.0
2RhONNO:146/0.8, 219/4.6, 271/1.7, 365/1.1, 577/8.8, 675/0.3, 986/0.2, 1126/91.3,1455/264.5
2TS6:i485/11.1, 154/5.6, 215/3.9, 375/0.6, 480/0.4, 489/93.2, 691/27.2, 1115/177.4, 1442/215.7
2ORhON2: 62/4.5, 88/5.2, 115/3.8, 201/2.0, 543/4.8, 566/6.6, 810/53.7, 1215/107.2, 2249/443.2
RhO(2Σ):804/68.6
4ONRhON:56/2.6, 199/1.3, 211/0.5, 385/19.1, 434/1.9, 436/1.7, 517/82.6, 1373/607.0, 1793/1222.5
4TS5: i355/67.6, 94/0.2, 153/0.2, 189/0.0, 268/0.3, 403/1.1, 603/22.2, 1434/1125.2, 1610/1027.2
4RhONNO:157/1.1, 250/6.5, 265/1.4, 366/0.6, 538/10.1, 664/2.6, 948/0.8, 1225/177.0, 1408/248.9
4TS6:i741/9.3, 39/3.7,79/4.0, 298/1.5, 377/4.7, 481/19.2, 571/28.7, 1143/78.6, 1729/365.1
4ORhON2:32/6.7, 38/7.5, 63/4.8, 82/10.8, 578/6.3, 585/4.2, 782/72.7, 1258/72.9,2239/313.6
RhO(4Σ):789/84.6
2RhONN: 166/1.6, 274/7.1, 410/1.2, 590/219.9, 794/55.9, 1849/378.0
2TS7: i425/50.5, 199/1.9, 448/474.6, 466/21.0, 589/63.9, 1946/312.1
2ORhN2: 105/13.0, 273/9.2, 274/0.1, 374/14.7, 788/44.1, 2205/374.1
N2:2345/0.0
4TS7:i604/41.3, 250/7.3, 256/2.9, 409/22.9, 665/8.0, 1616/255.7
4ORhN2: 58/10.9, 259/0.0, 264/8.6, 270/12.6, 783/28.1, 2250/282.4
2ORhCO:136/9.1, 360/0.1, 419/5.3, 485/18.1, 778/34.7, 2033/794.9
2TS8: i416/50.5, 331/0.6, 353/0.0, 480/13.4, 717/40.4, 2002/612.4
2RhCO2:211/2.9, 332/4.8,527/7.6, 655/269.4,1125/159.9, 1873/551.0
4ORhCO:96/13.1, 338/0.0, 357/2.7, 398/23.9, 739/21.7, 2040/815.7
4TS8:i702/82.6, 240/7.5, 245/0.0, 425/19.9, 607/45.5, 1930/569.8
4RhCO2:9/0.1, 20/0.2, 647/37.6, 649/24.0, 1313/0.0, 2309/637.3
NCO:454/37.1, 1283/9.3, 1982/75.1
1NRhCO：154/9.3, 340/0.9, 405/2.3, 460/24.3, 924/50.4, 2028/953.3
1NRhCO, <S2>=0.926:135/11.0, 320/2.8, 330/0.0, 435/24.0, 853/28.0, 2035/842.8
1TS9:i372/109.5, 288/2.3, 303/1.4, 413/17.4, 845/45.7, 2009/746.8
1TS9, <S2>=0.745:i448/54.5, 310/0.1, 322/0.3, 444/16.8, 789/22.1, 1965/709.4
1RhNCO:206/2.5, 361/18.0, 371/24.8, 720/77.3, 1003/8.8, 1854/684.9
1RhNCO, <S2>=0.898:96/10.8, 402/29.7, 571/20.1, 643/9.1, 1309/3.4, 2136/1874.0
1TS10:i190/9.2, 318/11.1, 512/8.9, 538/26.4, 1167/30.1, 2005/141.9
1TS10, <S2>=0.858:i128/5.6, 299/26.1, 544/7.0, 549/20.0, 1148/39.1, 2021/205.5
3NRhCO:138/10.9, 325/5.3, 331/0.2, 443/24.8, 800/26.3, 2034/815.1
3TS9:i508/33.5, 301/1.1, 347/0.0, 458/15.6, 756/10.2, 1936/663.3
3RhNCO:91/10.2, 389/38.4, 582/13.8, 634/7.9, 1307/3.5, 2133/2013.6
3TS10:i89/7.5, 341/25.4, 548/11.1, 550/5.1, 1126/44.4, 2049/189.6
CN:2067/19.9
1RhOCN：81/10.2, 447/6.5, 536/7.3,604/18.9, 1113/40.6, 2132/81.4
1RhOCN, <S2>=0.861:85/9.9, 409/21.5, 538/8.8, 593/19.7, 1116/58.8, 2143/117.4
1TS11:i794/215.4, 242/3.9, 304/0.5, 431/2.7, 711/21.6, 1978/27.7
1TS11, <S2>=1.040:i602/91.5, 262/3.4, 299/0.0, 396/7.4, 655/27.0, 1890/68.5
1ORhCN:122/19.5, 262/0.0, 327/4.0, 467/19.5, 865/60.4, 2121/14.4
1ORhCN, <S2>=0.249:117/14.7, 265/0.2, 289/0.9, 448/21.9, 862/56.8, 2130/13.1
3RhOCN:83/8.8, 378/29.3, 542/5.1, 584/16.5, 1119/68.6, 2146/144.1
3TS11:i640/106.7, 262/3.3, 304/0.0, 386/6.0, 676/22.5, 1897/63.4
3ORhCN:116/15.7, 266/0.3, 285/2.0, 442/22.9, 852/51.5, 2131/10.9
1