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B3LYP OPT

B3LYP OPT. CCSD(T)/aptz//B3LYP/6-31+G(d,p) unit: kcal/mol. TS 2. 40.5 [44.4]. TS 1. 28.6 [28.8]. 0. -4.4 [-6.3]. CH 2 O+NH 3. -12 .6 [-13.8]. CH 2 NH+H 2 O. Int 1. 40.5. TS 2. TS 2. 28.6. 25.2. 28.6. TS 1. TS 1. 22.5. 14.1. 21.1. 11.8. 11.7. 8.7. 3.8. 0.

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B3LYP OPT

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  1. B3LYP OPT

  2. CCSD(T)/aptz//B3LYP/6-31+G(d,p) unit: kcal/mol TS 2 40.5 [44.4] TS 1 28.6 [28.8] 0 -4.4 [-6.3] CH2O+NH3 -12.6 [-13.8] CH2NH+H2O Int 1

  3. 40.5 TS 2 TS 2 28.6 25.2 28.6 TS 1 TS 1 22.5 14.1 21.1 11.8 11.7 8.7 3.8 0 0 CH2O+NH3 CH2O+NH3 -4.4 -7.1 -4.4 -7.3 -6.9 CH2NH+H2O -12.6 Int 1 -7.6 Int 1 -12.6 -16.0 CH2NH+H2O -16.5 -14.4 -16.8 40.5 B3LYP/6-31+G(d,p) unit: kcal/mol Black: reaction without any solvent molecule Blue: reaction with one water molecule Green: reaction with one ammonia molecule B3LYP/6-31+G(d,p) unit: kcal/mol Black: reaction without any solvent molecule Blue: reaction with two water molecules Green: reaction with two ammonia molecules

  4. 14.1 TS 2 13.6 10.2 3.8 TS 1 0 -1.0 CH2O+NH3 -5.6 -5.6 -7.1 -7.5 CH2NH+H2O -14.7 -16.0 Int 1 -17.7 B3LYP/6-31+G(d,p) unit: kcal/mol Black: reaction with two water molecules in gas phase Purple: reaction with two water molecule in PCM Red: reaction with two water molecule in SMD

  5. 40.4 [40.6] TS_D1 28.8 [31.3] TS_D2 -2.4 [-1.2] 0 Int 2 Int_D -19.7 [-20.2] Direct pathway CCSD(T)/aptz//B3LYP/6-31+G(d,p) unit: kcal/mol CH2NH2CN

  6. 39.1 [39.7] 32.5 [31.9] TS_In2 TS_In1 9.3 [10.8] 0 Int_In Int 2 -19.7 [-20.2] Indirect pathway CCSD(T)/aptz//B3LYP/6-31+G(d,p) unit: kcal/mol CH2NH2CN

  7. Direct pathway TS_D1 TS_D1 40.4 40.4 TS_D2 TS_D2 26.2 28.8 28.8 24.8 23.7 24.8 22.6 19.4 22.5 19.0 0.9 0 0 -0.2 -2.3 -2.4 Int 2 Int 2 -2.4 -2.7 Int_D Int_D -17.0 -18.3 -19.7 -19.7 -19.9 -20.5 CH2NH2CN CH2NH2CN B3LYP/6-31+G(d,p) unit: kcal/mol Black: reaction without any solvent molecule Blue: reaction with one water molecule Green: reaction with one ammonia molecule B3LYP/6-31+G(d,p) unit: kcal/mol Black: reaction without any solvent molecule Blue: reaction with two water molecules Green: reaction with two ammonia molecules

  8. TS_In2 Indirect pathway TS_In2 39.1 39.1 TS_In1 TS_In1 32.5 32.5 26.4 29.0 25.8 25.3 23.5 19.9 19.6 22.1 Int_In Int_In 9.3 9.3 9.1 9.2 7.4 7.9 0 0 Int 2 Int 2 -18.3 -17.0 -19.7 -19.7 -20.5 -19.9 CH2NH2CN CH2NH2CN B3LYP/6-31+G(d,p) unit: kcal/mol Black: reaction without any solvent molecule Blue: reaction with two water molecules Green: reaction with two ammonia molecules B3LYP/6-31+G(d,p) unit: kcal/mol Black: reaction without any solvent molecule Blue: reaction with one water molecule Green: reaction with one ammonia molecule

  9. Direct pathway TS_D1 TS_D1 40.4 40.4 TS_D2 TS_D2 28.8 28.8 18.4 15.8 11.9 10.8 8.9 7.9 6.8 4.6 0.6 0 0 -2.4 -2.4 Int 2 Int 2 -2.5 -4.2 Int_D -6.9 Int_D -18.2 -19.7 -19.7 -21.0 -24.2 -26.7 CH2NH2CN CH2NH2CN B3LYP/6-31+G(d,p) unit: kcal/mol Black: reaction with two water molecules in gas phase Purple: reaction with two water molecule in PCM Red: reaction with two water molecule in SMD B3LYP/6-31+G(d,p) unit: kcal/mol Black: reaction with two ammonia molecules in gas phase Purple: reaction with two ammonia molecule in PCM Red: reaction with two ammonia molecule in SMD

  10. Indirect pathway TS_In2 TS_In2 39.1 39.1 TS_In1 TS_In1 32.5 32.5 20.8 15.0 18.2 Int_In 13.0 13.5 10.0 9.3 8.8 9.3 7.1 Int_In 8.6 5.0 6.3 0 1.2 0 Int 2 Int 2 -18.2 -19.7 -19.7 -24.2 -21.0 CH2NH2CN -26.7 CH2NH2CN B3LYP/6-31+G(d,p) unit: kcal/mol Black: reaction with two water molecules in gas phase Purple: reaction with two water molecule in PCM Red: reaction with two water molecule in SMD B3LYP/6-31+G(d,p) unit: kcal/mol Black: reaction with two ammonia molecules in gas phase Purple: reaction with two ammonia molecule in PCM Red: reaction with two ammonia molecule in SMD

  11. 56.4 [61.2] TS 3 26.5 [32.2] 20.7 [25.6] 21.7 [27.9] 4.5 [6.9] TS 6 0.1 [2.4] TS 7 TS 4 -3.6 [-0.4] -4.3 [-0.6] 0 TS 5 Int 4 CH2NH2CN+H2O Int 3 Int 5 -23.8 [-18.7] -26.7 [-20.4] Int 6 Glycine+NH3 CCSD(T)/aptz//B3LYP/6-31+G(d,p) unit: kcal/mol

  12. TS 3 56.4 39.2 38.9 TS 4 26.6 TS 6 TS 7 22.4 23.0 26.5 21.7 20.7 17.5 TS 5 10.5 Int 4 7.9 3.8 3.3 3.8 5.7 1.3 0 -2.9 Int 5 2.0 0.1 CH2NH2CN+H2O -4.3 -3.6 -7.0 -7.8 Int 3 -19.3 Int 6 -20.9 -21.8 -22.8 -26.6 B3LYP/6-31+G(d,p) unit: kcal/mol Black: reaction without any solvent molecule Blue: reaction with one water molecule Green: reaction with one ammonia molecule -23.8 Glycine+NH3

  13. TS 3 56.4 39.3 TS 6 TS 4 29.7 36.0 25.3 TS 7 23.9 21.7 26.5 20.2 TS 5 20.7 20.6 Int 4 8.1 6.3 5.7 Int 5 5.3 0 0.1 -0.7 3.3 5.0 -4.3 CH2NH2CN+H2O -0.3 -3.6 -8.6 Int 6 Int 3 -8.7 -18.4 B3LYP/6-31+G(d,p) unit: kcal/mol Black: reaction without any solvent molecule Blue: reaction with two water molecules Green: reaction with two ammonia molecules -20.6 -23.8 -26.6 -27.6 Glycine+NH3 -29.4

  14. TS 3 39.3 38.7 37.9 TS 4 25.3 TS 7 22.5 24.7 22.2 22.3 20.2 Int 3 TS 5 8.1 Int 4 5.3 7.2 6.3 2.1 4.2 TS 6 -0.7 0 -0.7 -1.3 -0.9 CH2NH2CN+H2O -1.4 -4.7 Int 5 -8.7 -9.0 -11.7 -9.5 -15.6 B3LYP/6-31+G(d,p) unit: kcal/mol Black: reaction with two water molecules in gas phase Purple: reaction with two water molecule in PCM Red: reaction with two water molecule in SMD Int 6 -19.2 -20.6 -20.3 Glycine+NH3 -21.3

  15. MP2 OPT

  16. CCSD(T)/aptz//MP2/6-31+G(d,p) unit: kcal/mol TS 2 44.6 [44.3] TS 1 29.9 [28.6] 0 -5.7 [-6.5] CH2O+NH3 -13.0 [-14.0] CH2NH+H2O Int 1

  17. 44.6 44.6 TS 2 TS 2 29.9 28.1 29.9 TS 1 TS 1 25.0 17.1 23.6 13.6 13.6 9.8 4.6 0 0 CH2O+NH3 CH2O+NH3 -5.7 -8.0 -5.7 -8.5 -8.5 CH2NH+H2O -13.0 Int 1 -9.3 Int 1 -13.0 -16.6 CH2NH+H2O -17.2 -15.6 -18.0 MP2/6-31+G(d,p) unit: kcal/mol Black: reaction without any solvent molecule Blue: reaction with one water molecule Green: reaction with one ammonia molecule MP2/6-31+G(d,p) unit: kcal/mol Black: reaction without any solvent molecule Blue: reaction with two water molecules Green: reaction with two ammonia molecules

  18. 17.7 TS 2 15.6 11.4 4.6 TS 1 0 -1.5 CH2O ＋ NH3 ＋2H2O -7.0 -7.0 -8.5 -9.2 CH2NH+3H2O -15.7 -16.6 Int 1 -19.0 MP2/6-31+G(d,p) unit: kcal/mol Black: reaction with two water molecules in gas phase Purple: reaction with two water molecules in PCM Red: reaction with two water molecules in SMD

  19. 43.4 [40.7] TS_D1 34.2 [31.0] TS_D2 0.9 [-1.4] 0 Int 2 Int_D -18.2 [-18.5] Direct pathway CCSD(T)/aptz//MP2/6-31+G(d,p) unit: kcal/mol CH2NH2CN

  20. 42.7 [40.0] 34.3 [31.8] TS_In2 TS_In1 13.5 [10.5] 0 Int_In Int 2 -18.2 [-18.5] Indirect pathway CCSD(T)/aptz//MP2/6-31+G(d,p) unit: kcal/mol CH2NH2CN

  21. Direct pathway TS_D1 43.4 TS_D1 43.4 TS_D2 TS_D2 34.2 28.3 34.2 29.7 28.1 23.9 24.8 28.8 27.5 23.2 0 1.9 2.7 0.9 0 0.9 Int 2 -0.5 0.5 Int_D Int_D Int 2 -18.2 -18.2 -19.4 -18.3 -21.5 CH2NH2CN -20.3 CH2NH2CN MP2/6-31+G(d,p) unit: kcal/mol Black: reaction without any solvent molecule Blue: reaction with one water molecule Green: reaction with one ammonia molecule MP2/6-31+G(d,p) unit: kcal/mol Black: reaction without any solvent molecule Blue: reaction with two water molecules Green: reaction with two ammonia molecules

  22. Indirect pathway TS_In2 42.7 TS_In2 TS_In1 42.7 34.3 TS_In1 30.2 34.3 28.6 31.3 29.3 28.2 28.2 23.1 18.1 Int_In 13.5 Int_In 13.5 13.2 13.3 11.4 11.7 0 0 Int 2 Int 2 -18.2 -19.4 -21.5 -18.2 CH2NH2CN -18.3 -20.3 CH2NH2CN MP2/6-31+G(d,p) unit: kcal/mol Black: reaction without any solvent molecule Blue: reaction with one water molecule Green: reaction with one ammonia molecule MP2/6-31+G(d,p) unit: kcal/mol Black: reaction without any solvent molecule Blue: reaction with two water molecules Green: reaction with two ammonia molecules

  23. Direct pathway Indirect pathway TS_D1 TS_D2 TS_In2 24.8 23.2 23.1 TS_In1 16.2 18.1 Int_In 13.2 12.6 12.0 11.4 10.8 8.4 8.1 10.0 6.5 3.3 0 -0.5 0 Int 2 Int 2 -1.0 -5.6 Int_D -21.5 -21.5 -22.3 -22.3 -28.2 -28.2 CH2NH2CN CH2NH2CN MP2/6-31+G(d,p) unit: kcal/mol Black: reaction with two ammonia molecules in gas phase Purple: reaction with two ammonia molecules in PCM Red: reaction with two ammonia molecules in SMD

  24. 63.9 [60.7] TS 3 22.0 [31.8] 31.1 [25.2] 28.7 [27.4] 12.6 [6.4] TS 6 8.4 [2.0] TS 7 TS 4 4.3 [-0.8] 1.0 [-4.0] 0 TS 5 Int 4 CH2NH2CN+H2O Int 3 Int 5 -17.2 [-19.1] -19.2 [-22.0] Int 6 Glycine+NH3 CCSD(T)/aptz//MP2/6-31+G(d,p) unit: kcal/mol

  25. TS 3 63.9 46.7 TS 4 44.6 36.1 TS 7 32.8 28.7 31.1 28.6 TS 6 24.2 TS 5 17.3 22.0 11.7 14.5 12.7 10.2 12.5 9.0 12.5 4.4 8.4 0 1.0 4.3 Int 4 0.7 Int 3 Int 5 CH2NH2CN+H2O 0.3 -12.6 Int 6 -14.8 -14.8 -16.4 -19.2 -17.2 Glycine+NH3 MP2/6-31+G(d,p) unit: kcal/mol Black: reaction without any solvent molecule Blue: reaction with one water molecule Green: reaction with one ammonia molecule

  26. TS 3 63.9 47.1 TS 4 33.9 38.9 TS 7 32.2 28.7 TS 6 31.1 22.0 25.0 TS 5 20.5 14.5 13.1 11.7 12.5 Int 4 8.4 10.7 11.1 8.1 9.3 0 6.2 1.0 4.3 -0.5 Int 3 CH2NH2CN+H2O Int 5 -1.2 -12.6 -14.6 -17.2 MP2/6-31+G(d,p) unit: kcal/mol Black: reaction without any solvent molecule Blue: reaction with two water molecules Green: reaction with two ammonia molecules -19.2 -20.0 Glycine+NH3 -21.4 Int 6

  27. TS 3 47.1 45.8 44.6 TS 4 33.9 33.0 30.4 23.3 TS 7 22.1 20.5 Int 3 11.7 TS 6 10.7 9.3 TS 5 Int 4 8.1 9.9 8.1 7.7 7.2 9.2 5.3 4.6 0 4.5 -0.5 -1.3 -5.9 CH2NH2CN+H2O Int 5 -2.2 -9.7 -14.6 Int 6 -17.5 Glycine+NH3 -18.9 -21.4 MP2/6-31+G(d,p) unit: kcal/mol Black: reaction with two water molecules in gas phase Purple: reaction with two water molecules in PCM Red: reaction with two water molecules in SMD

  28. TS 3 38.9 35.5 TS 7 TS 4 32.2 31.6 31.6 32.8 29.2 25.0 19.8 TS 6 Int 3 TS 5 14.5 13.1 11.1 13.6 Int 4 8.7 7.3 10.3 6.2 2.8 5.6 0 4.3 Int 5 -1.1 -3.5 0.1 CH2NH2CN+H2O -1.2 -6.7 -2.1 -12.6 -16.6 Glycine+NH3 -17.5 -20.0 Int 6 MP2/6-31+G(d,p) unit: kcal/mol Black: reaction with two ammonia molecules in gas phase Purple: reaction with two ammonia molecules in PCM Red: reaction with two ammonia molecules in SMD

  29. CH2O + NH3 → CH2NH + HCN → CH2NH2CN + 2H2O → Glycine + NH3 TS 2 unit：kcal/mol 44.6 TS_D1 TS_In2 [44.3] 37.9 37.2 [34.0] [33.4] TS 3 TS 1 30.8 29.9 TS_In1 TS_D2 [27.0] [28.6] 28.8 28.7 [25.2] [24.3] Int_In 8.0 TS 6 Int 2 [3.8] 0 -11.1 TS 4 1.7 CH2O+NH3 [-1.8] TS 7 [0.2] -2.0 -4.3 Int_D [-8.4] [-6.2] -4.6 Int 1 [-8.0] TS 5 -13.0 -20.5 [-14.0] [-27.2] Int 4 CH2NH2CN+2H2O -23.7 Int 3 -24.6 [-25.1] [-31.7] -28.7 [-34.4] Dash-line：direct pathway Solid-line：indirect pathway Int 5 Int 6 -52.2 -32.1 -50.2 [-55.6] [-37.6] [-52.7] Without parentheses；MP2/6-31+G(d,p) With parentheses：CCSD(T)/aptz//MP2/6-31+G(d,p) Glycine+NH3

  30. Comparison in Gas Phase and in Solvation Model (PCM,SMD) TS 2 44.6 TS_D1 TS_In2 [40.3] (32.8) 37.9 37.2 [19.3] [19.3] TS 3 TS 1 (9.5) (9.6) 30.8 29.9 TS_In1 TS_D2 [34.3] [22.7] 28.8 28.7 (24.4) (14.9) [12.5] [24.8] (5.5) (17.0) Int_In 8.0 TS 5 Int 2 [7.5] 0 2.2 TS 4 (5.7) 1.7 TS 6 [7.5] [-0.2] CH2O+NH3 -2.0 (-1.7) (-5.4) -4.3 Int_D [1.5] [0.1] -4.6 (-8.4) Int 1 (-7.3) [-2.3] -13.0 (-9.5) [-10.8] (-16.1) Int 4 CH2NH2CN+2H2O -23.7 Int 3 -24.6 [-24.6] [-24.5] -28.7 MP2/6-31+G(d,p) unit: kcal/mol Black: gas phase Blue: PCM Green: SMD (-33.5) (-35.6) [-24.9] -43.7 (-35.2) [-42.8] -44.9 [-41.9] (-45.3) (-50.8) Int 5 Glycine+NH3

  31. Comparison in Microsolvation Model with One Water Molecule TS 2 44.6 TS_D1 TS_In2 [23.6] 37.9 37.2 [22.8] [23.4] TS 3 TS 1 30.8 29.9 TS_In1 TS_D2 [10.1] [9.8] 28.8 28.7 [21.8] [21.2] Int_In 8.0 TS 5 Int 2 [6.5] 0 TS 4 2.2 1.7 TS 6 [-24.1] [9.5] CH2O+NH3 -2.0 -4.3 Int_D [-0.6] [-8.6] -4.6 Int 1 [-4.2] -13.0 [-15.6] CH2NH2CN+2H2O Int 4 -24.6 -23.7 Int 3 [-24.9] [-4.2] -28.7 [-26.4] -43.7 [-35.9] MP2/6-31+G(d,p) unit: kcal/mol Int 5 Glycine +NH3 -44.9 [-46.2]

  32. Calculating the Microsolvation System in Solvation Model (PCM,SMD) TS_In2 TS_D1 23.4 22.8 [11.4] [12.4] TS 2 (5.2) (5.8) 23.6 TS_In1 [25.7] TS_D2 21.8 21.2 (22.0) [11.3] [17.2] (5.2) TS 1 (9.6) Int 2 TS 3 Int_In 9.8 9.5 10.1 [6.1] [6.0] [16.7] 6.5 (0.8) (-0.3) (9.1) [9.0] 0 (7.6) TS 4 CH2O+NH3 +H2O -0.6 Int_D [3.4] TS 6 -4.2 (-6.5) [-1.2] -8.6 (-8.8) [0.3] Int 1 (-5.7) -15.6 [-11.5] (-14.8) TS 5 Int 4 Int 3 CH2NH2CN+3H2O -24.1 -24.9 -25.2 [17.4] -26.4 -35.9 [-22.4] [-24.0] (-24.3) [-21.7] [-33.5] MP2/6-31+G(d,p) unit: kcal/mol Black: gas phase Blue: PCM Green: SMD (-31.4) (-34.7) (-31.5) (-37.6) Glycine +NH3+H2O -46.2 [-40.5] (-48.1) Int 5

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