suppmat_1771. 1377KB Jun 05 2011 09:30:57 PM

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Table S1. Deprotonated hydrogen-bonded complexes

FH H2O NH3 HCl H2S PH3

FH F-(HF) F-(H2O) F-(NH3) Cl-(HF) SH-(HF) H2P-(HF)

H2O OH-(H2O)

OH-(H2O)2

OH-(NH3) Cl-(H2O) SH-(H2O) H2P-(H2O)

NH3 Cl-(NH3) SH-(NH3) H2P-(NH3)

HCl Cl-(HCl) Cl-(H2S) Cl-(PH3)

H2S SH-(H2S) SH-(PH3)

PH3 H2P-(PH3)

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Table S2. Intermolecular interaction energies (-∆En-1,n) of F-(HF) (kcal/mol)a

Basis set MP2 MP4 QCISD(T) CCSD(T)

aug-cc-pVDZ 43.4(41.2) 42.4(39.7) 43.6(41.1) 43.6(41.1) aug-cc-pVTZ 44.5(42.9) 43.6(41.8) 44.7(43.0) 44.8(43.1) aug-cc-pVQZ 44.2(43.1) 43.2(42.2) 44.4(43.5) 44.4(43.5) aug-cc-pV5Z 43.9(43.4) 42.9(42.5) 44.1(43.7) 44.2(43.8) CBS limit 43.5(43.4) 42.4(42.6) 43.7(43.8) 43.8(43.9) d-aug-cc-pVDZ 43.6(41.1) 42.5(39.6) 43.8(41.0) 43.9(41.1) d-aug-cc-pVTZ 44.9(42.9) 43.9(41.8) 45.1(43.0) 45.2(43.1) d-aug-cc-pVQZ 44.3(43.1) 43.2(42.2) 44.4(43.4) 44.5(43.5) CBS limit 43.2(43.0) 42.0(42.4) 43.2(43.6) 43.3(43.7)

a

Counterpoise-corrected values are in parentheses.

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Table S3. BSSE values for F-(HF) (kcal/mol)

aug-cc-pVDZ 2.2 2.7 2.5 2.5

aug-cc-pVTZ 1.6 1.8 1.7 1.7

aug-cc-pVQZ 1.1 1.0 0.9 0.9

aug-cc-pV5Z 0.5 0.4 0.4 0.4

CBS limit 0.1 -0.2 -0.1 -0.1

d-aug-cc-pVDZ 2.5 2.9 2.8 2.8 d-aug-cc-pVTZ 2.0 2.1 2.1 2.1 d-aug-cc-pVQZ 1.2 1.0 1.0 1.0

CBS limit 0.2 -0.4 -0.4 -0.4

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Table S4. Intermolecular interaction energies (-∆En-1,n) of F-(H2O) (kcal/mol)

aug-cc-pVDZ 26.8(25.3) 26.2(24.3) 27.0(25.2) 27.1(25.3) aug-cc-pVTZ 27.5(26.4) 27.0(25.8) 27.7(26.6) 27.8(26.7) aug-cc-pVQZ 27.4(26.7) 26.8(26.1) 27.6(27.0) 27.6(27.0) aug-cc-pV5Z 27.2(26.8) 26.6(26.3)

CBS limit 27.0(26.9) 26.3(26.3) 27.3(27.3) 27.2(27.2) d-aug-cc-pVDZ 27.0(25.3) 26.2(24.2) 27.2(25.3) 27.2(25.3) d-aug-cc-pVTZ 27.8(26.5) 27.1(25.8) 27.9(26.6) 28.0(26.7)

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Table S5. BSSE values for F-(H2O) (kcal/mol)

aug-cc-pVDZ 1.5 1.9 1.8 1.8

aug-cc-pVTZ 1.1 1.2 1.1 1.1

aug-cc-pVQZ 0.7 0.7 0.6 0.6

aug-cc-pV5Z 0.4 0.3

CBS limit 0.1 0.0 0.0 0.0

d-aug-cc-pVDZ 1.7 2.0 1.9 1.9 d-aug-cc-pVTZ 1.3 1.3 1.3 1.3

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Table S6. Intermolecular interaction energies (-∆En-1,n) of F-(NH3) (kcal/mol)

aug-cc-pVDZ 16.1(14.9) 16.1(14.6) 16.6(15.2) 16.6(15.2) aug-cc-pVTZ 16.4(15.6) 16.3(15.4) 16.8(16.0) 16.8(16.0) aug-cc-pVQZ 16.4(15.9) 16.2(15.7) 16.7(16.2) 16.7(16.2) aug-cc-pV5Z 16.2(15.9) 16.0(15.8)

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Table S7. BSSE values for F-(NH3) (kcal/mol)

aug-cc-pVDZ 1.2 1.5 1.4 1.4

aug-cc-pVTZ 0.8 0.9 0.8 0.8

aug-cc-pVQZ 0.5 0.5 0.5 0.5

aug-cc-pV5Z 0.3 0.2

CBS limit 0.1 -0.1 0.2 0.2

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Table S8. Intermolecular interaction energies (-∆En-1,n) of Cl-(HF) (kcal/mol)

aug-cc-pVDZ 23.1(22.0) 23.0(21.6) 22.8(21.5) 22.8(21.5) aug-cc-pVTZ 24.1(23.1) 24.0(23.0) 23.9(22.9) 23.8(22.8) aug-cc-pVQZ 23.9(23.3) 23.7(23.2) 23.6(23.1) 23.5(23.0) aug-cc-pV5Z 23.9(23.5) 23.7(23.4) 23.5(23.2) 23.5(23.2) CBS limit 23.7(23.6) 23.4(23.4) 23.2(23.2) 23.2(23.2)

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Table S9. BSSE values for Cl-(HF) (kcal/mol)

aug-cc-pVDZ 1.1 1.4 1.3 1.3

aug-cc-pVTZ 1.0 1.0 1.0 1.0

aug-cc-pVQZ 0.6 0.5 0.5 0.5

aug-cc-pV5Z 0.4 0.3 0.3 0.3

CBS limit 0.1 0.0 0.0 0.0

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[image:10.595.115.541.105.318.2]

Table S10. Intermolecular interaction energies (-∆En-1,n) of SH-(HF) (kcal/mol)

aug-cc-pVDZ 22.6(21.3) 22.6(21.0) 22.4(20.9) 22.4(20.9) aug-cc-pVTZ 23.3(22.3) 23.3(22.3) 23.0(22.0) 23.0(22.0) aug-cc-pVQZ 23.0(22.4) 22.9(22.5) 22.7(22.3) 22.7(22.3)

aug-cc-pV5Z 23.0(22.6)

CBS limit 22.7(22.6) 22.2(22.5) 22.2(22.5) 22.2(22.5)

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Table S11. BSSE values for SH-(HF) (kcal/mol)

aug-cc-pVDZ 1.3 1.6 1.5 1.5

aug-cc-pVTZ 1.0 1.0 1.0 1.0

aug-cc-pVQZ 0.6 0.4 0.4 0.4

aug-cc-pV5Z 0.4

CBS limit 0.1 -0.3 -0.3 -0.3

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Table S12. Intermolecular interaction energies (-∆En-1,n) of H2P-(HF) (kcal/mol).

aug-cc-pVDZ 23.2(21.7) 23.1(21.4) 22.7(21.1) 22.6(21.0) aug-cc-pVTZ 23.6(22.7) 23.5(22.7) 23.1(22.3) 23.0(22.2) aug-cc-pVQZ 23.4(22.8) 23.3(22.9)

aug-cc-pV5Z 23.4(23.0)

CBS limit 23.2(23.0) 23.0(23.0)

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Table S13. BSSE values for H2P-(HF) (kcal/mol)

aug-cc-pVDZ 1.5 1.7 1.6 1.6

aug-cc-pVTZ 0.9 0.8 0.8 0.8

aug-cc-pVQZ 0.6 0.4

aug-cc-pV5Z 0.4

CBS limit 0.2 0.0

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Table S14. Intermolecular interaction energies (-∆En-1,n) of OH-(H2O)n (n=1,2)

(kcal/mol)

n=1

aug-cc-pV5Z 26.7(26.3)

aug-cc-pV6Z 26.6(26.4)

n=2

aug-cc-pVDZ 22.0(20.3) 21.9(20.0) 22.2(20.4)

aug-cc-pVTZ 22.0(21.1)

aug-cc-pVQZ 21.9(21.4)

aug-cc-pV5Z 21.8(21.3)

CBS limit 21.7(21.4)

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[image:15.595.115.532.105.598.2]

Table S15. BSSE values for OH-(H2O)n (n = 1,2) (kcal/mol)

n=1

aug-cc-pVDZ 2.1 2.5 2.3 2.3

aug-cc-pVTZ 1.2 1.4 1.2 1.2

aug-cc-pVQZ 0.8 0.7 0.6 0.6

aug-cc-pV5Z 0.4

aug-cc-pV6Z 0.2

CBS limit 0.1 -0.1 0.2 0.0

n=2

aug-cc-pVDZ 1.7 1.9 1.8

aug-cc-pVTZ 0.9

aug-cc-pVQZ 0.5

aug-cc-pV5Z 0.5

CBS limit 0.3

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[image:16.595.113.540.109.374.2]

Table S16. Intermolecular interaction energies (-∆En-1,n) of OH-(NH3) (kcal/mol)

aug-cc-pV5Z 15.3(15.0)

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[image:17.595.115.538.114.374.2]

Table S17. BSSE values for OH-(NH3) (kcal/mol)

aug-cc-pVDZ 1.5 1.9 1.6 1.6

aug-cc-pVTZ 0.8 1.0 0.8 0.8

aug-cc-pVQZ 0.5 0.5 0.4 0.4

aug-cc-pV5Z 0.3

CBS limit 0.1 0.0 0.0 0.0

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[image:18.595.115.540.105.318.2]

Table S18. Intermolecular interaction energies (-∆En-1,n) of Cl-(H2O) (kcal/mol)

aug-cc-pV5Z 15.3(15.0)

CBS limit 15.2(15.1) 14.8(15.1) 14.7(15.0) 14.6(14.9)

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[image:19.595.113.539.113.317.2]

Table S19. BSSE values for Cl-(H2O) (kcal/mol)

aug-cc-pVDZ 1.0 1.1 1.1 1.1

aug-cc-pVTZ 0.8 0.8 0.8 0.8

aug-cc-pVQZ 0.5 0.3 0.3 0.3

aug-cc-pV5Z 0.3

CBS limit 0.1 -0.3 -0.3 -0.3

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[image:20.595.116.541.105.316.2]

Table S20. Intermolecular interaction energies (-∆En-1,n) of SH-(H2O) (kcal/mol)

aug-cc-pV5Z 15.2(14.9)

CBS limit 15.1(15.0) 14.8(15.1)

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[image:21.595.114.540.114.315.2]

Table S21. BSSE values for SH-(H2O) (kcal/mol)

aug-cc-pVDZ 1.2 1.4 1.4 1.4

aug-cc-pVTZ 0.8 0.8 0.8 0.8

aug-cc-pVQZ 0.5 0.3

aug-cc-pV5Z 0.3

CBS limit 0.1 -0.3

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Table S22. Intermolecular interaction energies (-∆En-1,n) of H2P-(H2O) (kcal/mol)

aug-cc-pV5Z 14.2(14.0)

CBS limit 14.1(14.1) 13.9(14.1)

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[image:23.595.114.540.113.315.2]

Table S23. BSSE values for H2P-(H2O) (kcal/mol)

aug-cc-pVDZ 1.2 1.3 1.3 1.3

aug-cc-pVTZ 0.7 0.6 0.6 0.6

aug-cc-pVQZ 0.4 0.2

aug-cc-pV5Z 0.2

CBS limit 0.0 -0.2

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[image:24.595.115.541.107.317.2]

Table S24. Intermolecular interaction energies (-∆En-1,n) of Cl-(NH3) (kcal/mol)

aug-cc-pV5Z 8.9(8.7)

CBS limit 8.8(8.8) 8.6(8.6)

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[image:25.595.115.540.114.316.2]

Table S25. BSSE values for Cl-(NH3) (kcal/mol)

aug-cc-pVDZ 0.8 1.0 1.0 1.0

aug-cc-pVTZ 0.6 0.6 0.6 0.6

aug-cc-pVQZ 0.3 0.3

aug-cc-pV5Z 0.2

CBS limit 0.0 0.0

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[image:26.595.115.541.106.316.2]

Table S26. Intermolecular interaction energies (-∆En-1,n) of SH-(NH3) (kcal/mol)

CBS limit 8.5(8.5) 8.2(8.4)

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[image:27.595.114.540.114.315.2]

Table S27. BSSE values for SH-(NH3) (kcal/mol)

aug-cc-pVDZ 1.0 1.2 1.2 1.2

aug-cc-pVTZ 0.6 0.6 0.6 0.6

aug-cc-pVQZ 0.3 0.2

aug-cc-pV5Z 0.2

CBS limit 0.0 -0.2

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[image:28.595.115.541.106.317.2]

Table S28. Intermolecular interaction energies (-∆En-1,n) of H2P-(NH3) (kcal/mol)

CBS limit 7.5(7.5) 7.3(7.4)

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[image:29.595.114.540.114.315.2]

Table S29. BSSE values for H2P-(NH3) (kcal/mol)

aug-cc-pVDZ 1.0 1.1 1.0 1.0

aug-cc-pVTZ 0.6 0.4 0.4 0.4

aug-cc-pVQZ 0.3 0.2

aug-cc-pV5Z 0.2

CBS limit 0.0 0.1

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[image:30.595.114.539.107.319.2]

Table S30. Intermolecular interaction energies (-∆En-1,n) of Cl-(HCl) (kcal/mol)

aug-cc-pV5Z 25.4(24.7)

CBS limit 25.5(25.2) 24.2(24.6) 23.7(24.0) 23.8(24.1)

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Table S31. BSSE values for Cl-(HCl) (kcal/mol)

aug-cc-pVDZ 2.1 2.5 2.5 2.5

aug-cc-pVTZ 1.7 1.8 1.7 1.7

aug-cc-pVQZ 1.1 0.8 0.8 0.8

aug-cc-pV5Z 0.7

CBS limit 0.3 -0.4 -0.3 -0.3

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[image:32.595.115.541.105.318.2]

Table S32. Intermolecular interaction energies (-∆En-1,n) of Cl-(H2S) (kcal/mol)

aug-cc-pVDZ 13.6(12.4) 12.9(11.4) 12.8(11.3) 12.8(11.3) aug-cc-pVTZ 14.2(13.3) 13.6(12.6) 13.4(12.5) 13.4(12.5)

aug-cc-pVQZ 14.1(13.5) 13.5(13.1) 13.2(12.8) 13.2(12.8)

aug-cc-pV5Z 14.1(13.7)

CBS limit 14.0(13.8) 13.2(13.5) 12.8(13.0) 12.8(13.0)

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[image:33.595.113.538.114.317.2]

Table S33. BSSE values for Cl-(H2S) (kcal/mol)

aug-cc-pVDZ 1.2 1.5 1.5 1.5

aug-cc-pVTZ 0.9 1.0 0.9 0.9

aug-cc-pVQZ 0.6 0.4 0.4 0.4

aug-cc-pV5Z 0.4

CBS limit 0.2 -0.3 -0.2 -0.2

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[image:34.595.115.541.106.317.2]

Table S34. Intermolecular interaction energies (-∆En-1,n) of Cl-(PH3) (kcal/mol)

CBS limit 6.8(6.7) 6.7(6.8)

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[image:35.595.114.540.114.315.2]

Table S35. BSSE values for Cl-(PH3) (kcal/mol)

aug-cc-pVDZ 0.9 1.1 1.1 1.1

aug-cc-pVTZ 0.5 0.5 0.6 0.6

aug-cc-pVQZ 0.3 0.2

aug-cc-pV5Z 0.2

CBS limit 0.1 -0.1

(36)

[image:36.595.116.540.105.317.2]

Table S36. Intermolecular interaction energies (-∆En-1,n) of SH-(H2S) (kcal/mol)

aug-cc-pVDZ 14.8(12.9) 13.7(11.5) 13.5(11.3) 13.5(11.3) aug-cc-pVTZ 15.1(13.9) 14.0(12.8) 13.7(12.5) 13.7(12.5)

aug-cc-pVQZ 15.0(14.3) 13.9(13.4)

aug-cc-pV5Z 15.0(14.5)

CBS limit 14.9(14.7) 13.7(14.0)

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Table S37. BSSE values for SH-(H2S) (kcal/mol)

aug-cc-pVDZ 1.9 2.2 2.2 2.2

aug-cc-pVTZ 1.2 1.2 1.2 1.2

aug-cc-pVQZ 0.7 0.5

aug-cc-pV5Z 0.5

CBS limit 0.2 -0.3

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[image:38.595.115.541.106.317.2]

Table S38. Intermolecular interaction energies (-∆En-1,n) of SH-(PH3) (kcal/mol)

CBS limit 6.5(6.5) 6.2(6.4)

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[image:39.595.114.540.114.315.2]

Table S39. BSSE values for SH-(PH3) (kcal/mol)

aug-cc-pVDZ 1.1 1.4 1.3 1.3

aug-cc-pVTZ 0.7 0.6 0.6 0.6

aug-cc-pVQZ 0.3 0.2

aug-cc-pV5Z 0.2

CBS limit 0.0 -0.2

(40)

[image:40.595.115.541.106.317.2]

Table S40. Intermolecular interaction energies (-∆En-1,n) of H2P-(PH3) (kcal/mol)

CBS limit 5.5(5.5) 5.2(5.3)

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[image:41.595.114.540.113.315.2]

Table S41. BSSE values for H2P-(PH3) (kcal/mol)

aug-cc-pVDZ 1.1 1.2 1.2 1.2

aug-cc-pVTZ 0.6 0.5 0.5 0.5

aug-cc-pVQZ 0.3 0.2

aug-cc-pV5Z 0.2

CBS limit 0.0 -0.1

(42)

M P 2

M P 2 (C P )

D T Q 5 C B S 35 36 37 38 39 40 41 42 43 44 45

M P 2

M P 2 (C P )

M P 2

M P 2 (C P )

D T Q 5 C B S 35 36 37 38 39 40 41 42 43 44 45

M P 4

M P 4 (C P )

M P 2

M P 2 (C P )

D T Q 5 C B S 35 36 37 38 39 40 41 42 43 44 45

Q C IS D (T)

Q C IS D (T) (C P )

M P 2

M P 2 (C P )

D T Q 5 C B S 35 36 37 38 39 40 41 42 43 44 45

C C S D (T)

[image:42.595.116.321.34.698.2]

C C S D (T) (C P )

Fig S1 Calculated intermolecular interaction energies of F-(HF) as a function of the correlation consistent basis set used. The counterpoise corrected values are denoted by CP.

(43)

M P 2

M P 2 (C P )

D T Q 5 C B S 35

36 37 38 39 40 41 42 43 44 45

M P 2

M P 2 (C P )

M P 2 (C P ), Q C ISD (T) (C P ), C C SD (T) (C P ) M P 4 (C P )

Fig S2 The counterpoise-uncorrected intermolecular interaction energies of F-(HF) evaluated using MP2/aug-cc-pVDZ level is close to the CBS limit at MP2, QCISD(T) and CCSD(T) levels.

(44)

M P 2

M P 2 (C P )

D T Q 5 C B S 20 21 22 23 24 25 26 27 28 29 30

M P 2

M P 2 (C P )

M P 2

M P 2 (C P )

D T Q 5 C B S 20 21 22 23 24 25 26 27 28 29 30

M P 4

M P 4 (C P )

M P 2

M P 2 (C P )

D T Q C B S

20 21 22 23 24 25 26 27 28 29 30

Q C ISD (T)

Q C ISD (T) (C P )

M P 2

M P 2 (C P )

D T Q C B S

20 21 22 23 24 25 26 27 28 29 30

C C S D (T)

[image:44.595.115.320.34.697.2]

C C SD (T) (C P )

Fig S3 Calculated intermolecular interaction energies of F-(H2O) as a function of the

correlation consistent basis set used. The counterpoise corrected values are denoted by CP.

(45)

M P 2

M P 2 (C P )

D T Q 5 C B S 20

21 22 23 24 25 26 27 28 29 30

M P 2

M P 2 (C P ) M P 4 (C P )

M P 2 (C P ), Q C IS D (T), C C S D (T)

Fig S4 The counterpoise-uncorrected intermolecular interaction energies of F-(H2O)

evaluated using MP2/aug-cc-pVDZ level is close to the CBS limit at MP2, QCISD(T) and CCSD(T) levels.

(46)

M P 2

M P 2 (C P )

D T Q 5 C B S 10 11 12 13 14 15 16 17 18 19 20

M P 2

M P 2 (C P )

M P 2

M P 2 (C P )

D T Q 5 C B S 10 11 12 13 14 15 16 17 18 19 20

M P 4

M P 4(C P )

M P 2

M P 2 (C P )

D T Q C B S

10 11 12 13 14 15 16 17 18 19 20

Q C ISD (T)

Q C ISD (T) (C P )

M P 2

M P 2 (C P )

D T Q C B S

10 11 12 13 14 15 16 17 18 19 20

C C S D (T)

[image:46.595.115.321.34.701.2]

C C S D (T) (C P )

Fig S5 Calculated intermolecular interaction energies of F-(NH3) as a function of the

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M P 2

M P 2 (C P )

D T Q 5 C B S 10

11 12 13 14 15 16 17 18 19 20

M P 2

M P 2 (C P )

M P 2 (C P ), M P 4 (C P ), Q C IS D (T) (C P ), C C S D (T) (C P )

Fig S6 The counterpoise-uncorrected intermolecular interaction energies of F-(NH3)

evaluated using MP2/aug-cc-pVDZ level is close to the CBS limit at MP2, MP4, QCISD(T) and CCSD(T) levels.

(48)

M P 2

M P 2 (C P )

D T Q 5 C B S 20 21 22 23 24 25 26 27 28 29 30

M P 2

M P 2 (C P )

M P 2

M P 2 (C P )

D T Q 5 C B S 20 21 22 23 24 25 26 27 28 29 30

M P 4

M P 4 (C P )

M P 2

M P 2 (C P )

D T Q 5 C B S 20 21 22 23 24 25 26 27 28 29 30

Q C IS D (T)

Q C IS D (T) (C P )

M P 2

M P 2 (C P )

D T Q 5 C B S 20 21 22 23 24 25 26 27 28 29 30

C C SD (T)

[image:48.595.116.321.33.694.2]

C C ISD (T) (C P )

Fig S7 Calculated intermolecular interaction energies of Cl-(HF) as a function of the correlation consistent basis set used. The counterpoise corrected values are denoted by CP.

(49)

M P 2

M P 2 (C P )

D T Q 5 C B S 20

21 22 23 24 25 26 27 28 29 30

M P 2

M P 2 (C P )

M P 2 (C P ), M P 4 (C P )

Q C ISD (T) (C P ), C C S D (T) (C P )

Fig S8 The counterpoise-uncorrected intermolecular interaction energies of Cl-(HF) evaluated using MP2/aug-cc-pVDZ level is close to the CBS limit at MP2, MP4, QCISD(T) and CCSD(T) levels.

(50)

M P 2

M P 2 (C P )

D T Q 5 C B S 20 21 22 23 24 25 26 27 28 29 30

M P 2

M P 2 (C P )

M P 2

M P 2 (C P )

D T Q C B S

20 21 22 23 24 25 26 27 28 29 30

M P 4

M P 4 (C P )

M P 2

M P 2 (C P )

D T Q C B S

20 21 22 23 24 25 26 27 28 29 30

Q C IS D (T)

Q C IS D (T) (C P )

M P 2

M P 2 (C P )

D T Q C B S

20 21 22 23 24 25 26 27 28 29 30

C C S D (T)

[image:50.595.115.320.32.699.2]

C C S D (T) (C P )

Fig S9 Calculated intermolecular interaction energies of SH-(HF) as a function of the correlation consistent basis set used. The counterpoise corrected values are denoted by CP.

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M P 2

M P 2 (C P )

D T Q 5 C B S 20

21 22 23 24 25 26 27 28 29 30

M P 2

M P 2 (C P )

M P 2 (C P ), M P 4 (C P ),

Q C IS D (T) (C P ), C C S D (T) (C P )

Fig S10 The counterpoise-uncorrected intermolecular interaction energies of SH-(HF) evaluated using MP2/aug-cc-pVDZ level is close to the CBS limit at MP2, MP4, QCISD(T) and CCSD(T) levels.

(52)

M P 2

M P 2 (C P )

D T Q 5 C B S 20 21 22 23 24 25 26 27 28 29 30

M P 2

M P 2 (C P )

M P 2

M P 2 (C P )

D T Q C B S

20 21 22 23 24 25 26 27 28 29 30

M P 4

M P 4 (C P )

Fig S11 Calculated intermolecular interaction energies of H2P-(HF) as a function of the

(53)

M P 2

M P 2 (C P )

D T Q 5 C B S 20

21 22 23 24 25 26 27 28 29 30

M P 2

M P 2 (C P )

M P 2 (C P ), M P 4 (C P )

Fig S12 The counterpoise-uncorrected intermolecular interaction energies of H2P-(HF) evaluated using MP2/aug-cc-pVDZ level is close to the CBS limit at MP2 and

MP4 levels.

(54)

M P 2

M P 2 (C P )

D T Q 5 6 C B S 20 21 22 23 24 25 26 27 28 29 30

M P 2

M P 2 (C P )

M P 2

M P 2 (C P )

D T Q C B S

20 21 22 23 24 25 26 27 28 29 30

M P 4

M P 4 (C P )

M P 2

M P 2 (C P )

D T Q C B S

20 21 22 23 24 25 26 27 28 29 30

Q C IS D (T)

Q C IS D (T) (C P )

M P 2

M P 2 (C P )

D T Q C B S

20 21 22 23 24 25 26 27 28 29 30

C C S D (T)

C C S D (T) (C P )

Fig S13 Calculated intermolecular interaction energies of OH-(H2O) as a function of the

(55)

M P 2

M P 2 (C P )

D T Q 5 6 C B S 20

21 22 23 24 25 26 27 28 29 30

M P 2

M P 2 (C P )

M P 2 (C P ), Q C IS D (T) (C P ), C C SD (T) (C P ) M P 4 (C P )

Fig S14 The counterpoise-uncorrected intermolecular interaction energies of OH-(H2O) evaluated using MP2/aug-cc-pVDZ level is close to the CBS limit at MP2,

QCISD(T) and CCSD(T) levels.

(56)

M P 2

M P 2 (C P )

D T Q 5 C B S 20

21 22 23 24 25 26 27 28 29 30

M P 2

M P 2 (C P )

Fig S15 Calculated intermolecular interaction energies of OH-(H2O)2 as a function of

the correlation consistent basis set used. The counterpoise corrected values are denoted by CP.

(57)

M P 2

M P 2 (C P )

D T Q 5 C B S 10 11 12 13 14 15 16 17 18 19 20

M P 2

M P 2 (C P )

M P 2

M P 2 (C P )

D T Q C B S

10 11 12 13 14 15 16 17 18 19 20

M P 4

M P 4 (C P )

M P 2

M P 2 (C P )

D T Q C B S

10 11 12 13 14 15 16 17 18 19 20

Q C IS D (T)

Q C IS D (T) (C P )

M P 2

M P 2 (C P )

D T Q C B S

10 11 12 13 14 15 16 17 18 19 20

C C S D (T)

C C S D (T) (C P )

Fig S16 Calculated intermolecular interaction energies of OH-(NH3) as a function of the

(58)

M P 2

M P 2 (C P )

D T Q 5 C B S 10

11 12 13 14 15 16 17 18 19 20

M P 2

M P 2 (C P )

M P 2 (C P ), M P 4 (C P ) Q C IS D (T) (C P ), C C S D (T)

Fig S17 The counterpoise-uncorrected intermolecular interaction energies of OH-(NH3) evaluated using MP2/aug-cc-pVDZ level is close to the CBS limit at

QCISD(T) and CCSD(T) levels.

(59)

M P 2

M P 2 (C P )

D T Q 5 C B S 10 11 12 13 14 15 16 17 18 19 20

M P 2

M P 2 (C P )

M P 2

M P 2 (C P )

D T Q C B S

10 11 12 13 14 15 16 17 18 19 20

M P 4

M P 4 (C P )

M P 2

M P 2 (C P )

D T Q C B S

10 11 12 13 14 15 16 17 18 19 20

Q C IS D (T)

Q C IS D (T) (C P )

M P 2

M P 2 (C P )

D T Q C B S

10 11 12 13 14 15 16 17 18 19 20

C C S D (T)

C C S D (T) (C P )

Fig S18 Calculated intermolecular interaction energies of Cl-(H2O) as a function of the

(60)

M P 2

M P 2 (C P )

D T Q 5 C B S 10

11 12 13 14 15 16 17 18 19 20

M P 2

M P 2 (C P )

M P 2 (C P ), M P 4 (C P ),

Q C ISD (T) (C P ), C C S D (T) (C P )

Fig S19 The counterpoise-uncorrected intermolecular interaction energies of Cl-(H2O) evaluated using MP2/aug-cc-pVDZ level is close to the CBS limit at MP2,

MP4, QCISD(T) and CCSD(T) levels.

(61)

M P 2

M P 2 (C P )

D T Q 5 C B S 10 11 12 13 14 15 16 17 18 19 20

M P 2

M P 2 (C P )

M P 2

M P 2 (C P )

D T Q C B S

10 11 12 13 14 15 16 17 18 19 20

M P 4

M P 4 (C P )

Fig S20 Calculated intermolecular interaction energies of SH-(H2O) as a function of the

(62)

M P 2

M P 2 (C P )

D T Q 5 C B S 10

11 12 13 14 15 16 17 18 19 20

M P 2

M P 2 (C P )

M P 2 (C P ), M P 4 (C P )

Fig S21 The counterpoise-uncorrected intermolecular interaction energies of SH-(H2O) evaluated using MP2/aug-cc-pVDZ level is close to the CBS limit at MP2

and MP4 levels.

(63)

M P 2

M P 2 (C P )

D T Q 5 C B S 10 11 12 13 14 15 16 17 18 19 20

M P 2

M P 2 (C P )

M P 2

M P 2 (C P )

D T Q C B S

10 11 12 13 14 15 16 17 18 19 20

M P 4

M P 4 (C P )

Fig S22 Calculated intermolecular interaction energies of H2P-(H2O) as a function of the

(64)

M P 2

M P 2 (C P )

D T Q 5 C B S 10

11 12 13 14 15 16 17 18 19 20

M P 2

M P 2 (C P )

M P 2 (C P ), M P 4 (C P )

Fig S23 The counterpoise-uncorrected intermolecular interaction energies of H2P-(H2O) evaluated using MP2/aug-cc-pVDZ level is close to the CBS limit at MP2

and MP4 levels.

(65)

M P 2

M P 2 (C P )

D T Q 5 C B S 0 1 2 3 4 5 6 7 8 9 10

M P 2

M P 2 (C P )

M P 2

M P 2 (C P )

D T Q C B S

0 1 2 3 4 5 6 7 8 9 10

M P 4

M P 4 (C P )

Fig S24 Calculated intermolecular interaction energies of Cl-(NH3) as a function of the

(66)

M P 2

M P 2 (C P )

D T Q 5 C B S 0

1 2 3 4 5 6 7 8 9 10

M P 2

M P 2 (C P )

M P 2 (C P ), M P 4 (C P )

Fig S25 The counterpoise-uncorrected intermolecular interaction energies of Cl-(NH3) evaluated using MP2/aug-cc-pVDZ level is close to the CBS limit at MP2 and

MP4 levels.

(67)

M P 2

M P 2 (C P )

D T Q 5 C B S 0 1 2 3 4 5 6 7 8 9 10

M P 2

M P 2 (C P )

M P 2

M P 2 (C P )

D T Q C B S

0 1 2 3 4 5 6 7 8 9 10

M P 4

M P 4 (C P )

Fig S26 Calculated intermolecular interaction energies of SH-(NH3) as a function of the

(68)

M P 2

M P 2 (C P )

D T Q 5 C B S 0

1 2 3 4 5 6 7 8 9 10

M P 2

M P 2 (C P )

M P 2 (C P ), M P 4 (C P )

Fig S27 The counterpoise-uncorrected intermolecular interaction energies of SH-(NH3) evaluated using MP2/aug-cc-pVDZ level is close to the CBS limit at MP2

and MP4 levels.

(69)

M P 2

M P 2 (C P )

D T Q 5 C B S 0 1 2 3 4 5 6 7 8 9 10

M P 2

M P 2 (C P )

M P 2

M P 2 (C P )

D T Q C B S

0 1 2 3 4 5 6 7 8 9 10

M P 4

M P 4 (C P )

Fig S28 Calculated intermolecular interaction energies of H2P-(NH3) as a function of the

(70)

M P 2

M P 2 (C P )

D T Q 5 C B S 0

1 2 3 4 5 6 7 8 9 10

M P 2

M P 2 (C P )

M P 2 (C P ), M P 4 (C P )

Fig S29 The counterpoise-uncorrected intermolecular interaction energies of H2P-(NH3) evaluated using MP2/aug-cc-pVDZ level is close to the CBS limit at MP2

and MP4 levels.

(71)

M P 2

M P 2 (C P )

D T Q 5 C B S 20 21 22 23 24 25 26 27 28 29 30

M P 2

M P 2 (C P )

M P 2

M P 2 (C P )

D T Q C B S

20 21 22 23 24 25 26 27 28 29 30

M P 4

M P 4 (C P )

M P 2

M P 2 (C P )

D T Q C B S

20 21 22 23 24 25 26 27 28 29 30

Q C ISD (T)

Q C ISD (T) (C P )

M P 2

M P 2 (C P )

D T Q C B S

20 21 22 23 24 25 26 27 28 29 30

C C SD (T)

C C SD (T) (C P )

Fig S30 Calculated intermolecular interaction energies of Cl-(HCl) as a function of the correlation consistent basis set used. The counterpoise corrected values are denoted by CP.

(72)

M P 2

M P 2 (C P )

D T Q 5 C B S 20

21 22 23 24 25 26 27 28 29 30

M P 2

M P 2 (C P )

M P 2 (C P ) M P 4 (C P )

Q C ISD (T) (C P ), C C S D (T) (C P )

Fig S31 The counterpoise-uncorrected intermolecular interaction energies of Cl-(HCl) evaluated using MP2/aug-cc-pVDZ level is close to the CBS limit at MP2 and MP4 levels.

(73)

M P 2

M P 2 (C P )

D T Q 5 C B S 10 11 12 13 14 15 16 17 18 19 20

M P 2

M P 2 (C P )

M P 2

M P 2 (C P )

D T Q C B S

10 11 12 13 14 15 16 17 18 19 20

M P 4

M P 4 (C P )

M P 2

M P 2 (C P )

D T Q C B S

10 11 12 13 14 15 16 17 18 19 20

Q C IS D (T)

Q C IS D (T) (C P )

M P 2

M P 2 (C P )

D T Q C B S

10 11 12 13

Fig S32 Calculated intermolecular interaction energies of Cl-(H2S) as a function of the

(74)

M P 2

M P 2 (C P )

D T Q 5 C B S 10

11 12 13 14 15 16 17 18 19 20

M P 2

M P 2 (C P )

M P 2 (C P ), M P 4 (C P )

Q C IS D (T) (C P ), C C S D (T) (C P )

Fig S33 The counterpoise-uncorrected intermolecular interaction energies of Cl-(H2S) evaluated using MP2/aug-cc-pVDZ level is close to the CBS limit at MP2 and

MP4 levels.

(75)

M P 2

M P 2 (C P )

D T Q 5 C B S 0 1 2 3 4 5 6 7 8 9 10

M P 2

M P 2 (C P )

M P 2

M P 2 (C P )

D T Q C B S

0 1 2 3 4 5 6 7 8 9 10

M P 4

M P 4 (C P )

Fig S34 Calculated intermolecular interaction energies of Cl-(PH3) as a function of the

(76)

M P 2

M P 2 (C P )

D T Q 5 C B S 0

1 2 3 4 5 6 7 8 9 10

M P 2

M P 2 (C P )

M P 2 (C P ), M P 4 (C P )

Fig S35 The counterpoise-uncorrected intermolecular interaction energies of Cl-(PH3) evaluated using MP2/aug-cc-pVDZ level is close to the CBS limit at MP2 and

MP4 levels.

(77)

M P 2

M P 2 (C P )

D T Q 5 C B S 10 11 12 13 14 15 16 17 18 19 20

M P 2

M P 2 (C P )

M P 2

M P 2 (C P )

D T Q C B S

10 11 12 13 14 15 16 17 18 19 20

M P 4

M P 4 (C P )

Fig S36 Calculated intermolecular interaction energies of SH-(H2S) as a function of the

(78)

M P 2

M P 2 (C P )

D T Q 5 C B S 10

11 12 13 14 15 16 17 18 19 20

M P 2

M P 2 (C P )

M P 2 (C P ) M P 4 (C P )

Fig S37 The counterpoise-uncorrected intermolecular interaction energies of SH-(H2S) evaluated using MP2/aug-cc-pVDZ level is close to the CBS limit at MP2

level.

(79)

M P 2

M P 2 (C P )

D T Q 5 C B S 0 1 2 3 4 5 6 7 8 9 10

M P 2

M P 2 (C P )

M P 2

M P 2 (C P )

D T Q C B S

0 1 2 3 4 5 6 7 8 9 10

M P 4

M P 4 (C P )

Fig S38 Calculated intermolecular interaction energies of SH-(PH3) as a function of the

(80)

M P 2

M P 2 (C P )

D T Q 5 C B S 0

1 2 3 4 5 6 7 8 9 10

M P 2

M P 2 (C P )

M P 2 (C P ), M P 4 (C P )

Fig S39 The counterpoise-uncorrected intermolecular interaction energies of SH-(PH3) evaluated using MP2/aug-cc-pVDZ level is close to the CBS limit at MP2 and

MP4 levels.

(81)

M P 2

M P 2 (C P )

D T Q 5 C B S 0 1 2 3 4 5 6 7 8 9 10

M P 2

M P 2 (C P )

M P 2

M P 2 (C P )

D T Q C B S

0 1 2 3 4 5 6 7 8 9 10

M P 4

M P 4 (C P )

Fig S40 Calculated intermolecular interaction energies of H2P-(PH3) as a function of the

(82)

M P 2

M P 2 (C P )

D T Q 5 C B S 0

1 2 3 4 5 6 7 8 9 10

M P 2

M P 2 (C P )

M P 2 (C P ), M P 4 (C P )

Fig S41 The counterpoise-uncorrected intermolecular interaction energies of H2P-(PH3) evaluated using MP2/aug-cc-pVDZ level is close to the CBS limit at MP2

and MP4 levels.