Impact of Medium, Substituents and Specific Interactions with Water on Hydration of Carbonyl

Impact of Medium, Substituents and Specific Interactions with Water on Hydration of Carbonyl Compounds

Damanjit Kaur • Rajinder Kaur • Shweta Khanna

Department of Chemistry, Guru Nanak Dev University, Amritsar 143005, India

E-mail: ,

Table S1: Optimized parameters for HCHO and CH2(OH)2 at B3LYP/6-31++G(d,p) and MP2/6-31++G(d,p) theoretical levels.

Parameters / HCHO / Parameters / CH2(OH)2
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.210 / 1.224 / C2-O1 / 1.396 / 1.400
H3-C2 / 1.108 / 1.098 / O3-C2 / 1.423 / 1.424
H4-C2 / 1.108 / 1.098 / H4-C2 / 1.095 / 1.088
H3-C2-O1 / 121.9 / 121.7 / H5-O1 / 0.968 / 0.967
H4-C2-O1 / 121.9 / 121.7 / H6-O3 / 0.966 / 0.965
H4-C2-O1-H3 / 180.00 / 180.0 / H7-C2 / 1.102 / 1.095
O3-C2-O1 / 109.2 / 109.1
H4-C2-O1 / 105.6 / 105.4
H5-O1-C2 / 108.3 / 107.6
H6-O3-C2 / 109.5 / 108.9
H7-C2-O1 / 111.7 / 111.7
H4-C2-O1-O3 / 119.3 / 119.0
H5-O1-C2-O3 / 53.8 / 53.0
H6-O3-C2-H4 / 95.2 / 100.9
H7-C2-O1-H4 / 119.3 / 119.8

Table S2: Optimized parameters for CH3CHO and CH3CH(OH)2 at B3LYP/6-31++G (d,p)and MP2/6-31++G(d,p) theoretical levels.

Parameters / CH3CHO / Parameters / CH3CH(OH)2
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.213 / 1.227 / C2-O1 / 1.401 / 1.403
C3-C2 / 1.505 / 1.500 / O3-C2 / 1.431 / 1.431
H4-C2 / 1.113 / 1.104 / C4-C2 / 1.518 / 1.509
H5-C3 / 1.092 / 1.087 / H5-O1 / 0.968 / 0.968
H6-C3 / 1.097 / 1.091 / H6-O3 / 0.966 / 0.967
H7-C3 / 1.097 / 1.091 / H7-C4 / 1.094 / 1.089
C3-C2-O1 / 124.7 / 124.4 / H8-C4 / 1.095 / 1.090
H4-C2-O1 / 119.9 / 119.8 / H9-C4 / 1.093 / 1.088
H5-C3-C2 / 110.9 / 110.4 / H10-C2 / 1.104 / 1.098
H6-C3-C2 / 109.5 / 109.4 / O3-C2-O1 / 106.9 / 106.6
H7-C3-C2 / 109.5 / 109.4 / C4-C2-O1 / 108.0 / 107.6
H4-C2-O1-C3 / 180.0 / 180.0 / H5-O1-C2 / 107.8 / 107.2
H5-C3-C2-O1 / 0.001 / 0.001 / H6-O3-C2 / 109.3 / 108.7
H6-C3-C2-O1 / 121.7 / 121.4 / H7-C4-C2 / 110.2 / 110.0
H7-C3-C2-O1 / 238.3 / 238.6 / H8-C4-C2 / 110.4 / 110.3
H9-C4-C2 / 109.3 / 108.7
H10-C2-O1 / 110.4 / 110.5
C4-C2-O1-O3 / 121.2 / 120.6
H5-O1-C2-O3 / 47.7 / 47.7
H6-O3-C2-C4 / 81.0 / 81.2
H7-C4-C2-O1 / 59.5 / 59.4
H8-C4-C2-O1 / 179.5 / 179.6
H9-C4-C2-O1 / 299.5 / 299.5
H10-C2-O1-C4 / 121.1 / 121.6

Table S3: Optimized parameters for ClCH2CHO and ClCH2CH(OH)2at B3LYP/6-31++G (d,p)and MP2/6-31++G(d,p) theoretical levels.

Parameters / ClCH2CHO / Parameters / ClCH2CH(OH)2
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.210 / 1.223 / C2-O1 / 1.393 / 1.397
C3-C2 / 1.520 / 1.513 / O3-C2 / 1.427 / 1.427
H4-C2 / 1.108 / 1.101 / C4-C2 / 1.525 / 1.515
H5-C3 / 1.091 / 1.087 / Cl5-C4 / 1.810 / 1.779
H6-C3 / 1.094 / 1.090 / H6-O1 / 0.967 / 0.967
Cl7-C3 / 1.805 / 1.778 / H7-O3 / 0.967 / 0.967
C3-C2-O1 / 121.7 / 121.9 / H8-C4 / 1.090 / 1.087
H4-C2-O1 / 122.1 / 121.8 / H9-C4 / 1.090 / 1.087
H5-C3-C2 / 110.1 / 109.5 / H10-C2 / 1.102 / 1.097
H6-C3-C2 / 109.1 / 108.9 / O3-C2-O1 / 108.1 / 108.1
Cl7-C3-C2 / 111.6 / 111.0 / C4-C2-O1 / 108.0 / 107.5
H4-C2-O1-C3 / 178.6 / 178.3 / Cl5-C4-C2 / 112.1 / 111.6
H5-C3-C2-O1 / -36.1 / -31.1 / H6-O1-C2 / 108.5 / 107.7
H6-C3-C2-O1 / 83.8 / 88.6 / H7-O3-C2 / 109.6 / 108.9
Cl7-C3-C2-O1 / 202.6 / 207.7 / H8-C4-C2 / 110.0 / 109.5
H9-C4-C2 / 109.5 / 108.4
H10-C2-O1 / 111.5 / 111.5
C4-C2-O1-O3 / 117.9 / 117.6
Cl5-C4-C2-O1 / 71.5 / 68.1
H6-O1-C2-C4 / 174.1 / 170.7
H7-O3-C2-O1 / 209.2 / 213.9
H8-C4-C2-O1 / 190.3 / 187.6
H9-C4-C2-O1 / 311.6 / 308.0
H10-C2-O1-C4 / 121.5 / 121.7

Table S4: Optimized parameters for FCH2CHO and FCH2CH(OH)2at B3LYP/6-31++G (d,p)and MP2/6-31++G(d,p) theoretical levels.

Parameters / FCH2CHO / Parameters / FCH2CH(OH)2
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.211 / 1.224 / C2-O1 / 1.394 / 1.399
C3-C2 / 1.517 / 1.512 / O3-C2 / 1.427 / 1.427
H4-C2 / 1.110 / 1.102 / C4-C2 / 1.523 / 1.512
H5-C3 / 1.096 / 1.090 / F5-C4 / 1.399 / 1.403
H6-C3 / 1.096 / 1.090 / H6-O1 / 0.967 / 0.967
F7-C3 / 1.396 / 1.402 / H7-O3 / 0.966 / 0.966
C3-C2-O1 / 122.3 / 121.8 / H8-C4 / 1.094 / 1.089
H4-C2-O1 / 122.4 / 122.4 / H9-C4 / 1.094 / 1.088
H5-C3-C2 / 110.1 / 110.3 / H10-C2 / 1.102 / 1.096
H6-C3-C2 / 110.1 / 110.3 / O3-C2-O1 / 108.7 / 109.5
F7-C3-C2 / 109.8 / 109.3 / C4-C2-O1 / 107.7 / 107.1
H4-C2-O1-C3 / 180.0 / 180.0 / F5-C4-C2 / 110.1 / 109.7
H5-C3-C2-O1 / -60.4 / -60.8 / H6-O1-C2 / 108.8 / 108.2
H6-C3-C2-O1 / 60.3 / 60.8 / H7-O3-C2 / 109.6 / 109.1
F7-C3-C2-O1 / 179.9 / 180.0 / H8-C4-C2 / 110.1 / 110.1
H9-C4-C2 / 109.8 / 109.5
H10-C2-O1 / 111.4 / 111.4
C4-C2-O1-O3 / 118.3 / 117.0
F5-C4-C2-O1 / 70.9 / 67.5
H6-O1-C2-C4 / 177.0 / 175.0
H7-O3-C2-O1 / 213.5 / 226.2
H8-C4-C2-O1 / 189.5 / 186.1
H9-C4-C2-O1 / 311.4 / 308.4
H10-C2-O1-C4 / 120.6 / 121.0

Table S5: Optimized parameters for CH3COCH3 and (CH3)2C(OH)2at B3LYP/6-31++G (d,p)and MP2/6-31++G(d,p) theoretical levels.

Parameters / CH3COCH3 / Parameters / (CH3)2C(OH)2
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.219 / 1.231 / C2-O1 / 1.410 / 1.411
C3-C2 / 1.518 / 1.511 / O3-C2 / 1.438 / 1.437
C4-C2 / 1.518 / 1.511 / C4-C2 / 1.526 / 1.516
H5-C3 / 1.091 / 1.086 / C5-C2 / 1.534 / 1.523
H6-C3 / 1.096 / 1.091 / H6-O1 / 0.968 / 0.969
H7-C3 / 1.097 / 1.091 / H7-O3 / 0.966 / 0.967
H8-C4 / 1.091 / 1.086 / H8-C4 / 1.092 / 1.088
H9-C4 / 1.096 / 1.091 / H9-C4 / 1.095 / 1.090
H10-C4 / 1.097 / 1.091 / H10-C4 / 1.094 / 1.089
C3-C2-O1 / 121.6 / 121.7 / H11-C5 / 1.095 / 1.090
C4-C2-O1 / 121.6 / 121.7 / H12-C5 / 1.093 / 1.089
H5-C3-C2 / 110.1 / 109.8 / H13-C5 / 1.096 / 1.092
H6-C3-C2 / 110.8 / 110.0 / O3-C2-O1 / 105.5 / 105.3
H7-C3-C2 / 109.7 / 109.9 / C4-C2-O3 / 110.7 / 110.9
H8-C4-C2 / 110.1 / 109.8 / C5-C2-C4 / 112.8 / 113.0
H9-C4-C2 / 110.8 / 110.0 / H6-O1-C2 / 107.5 / 106.8
H10-C4-C2 / 109.8 / 109.9 / H7-O3-C2 / 109.4 / 108.7
C4-C2-O1-C3 / 180.0 / 180.0 / H8-C4-C2 / 109.1 / 108.7
H5-C3-C2-O1 / 5.9 / 0.3 / H9-C4-C2 / 110.5 / 110.3
H6-C3-C2-O1 / 127.7 / 121.3 / H10-C4-C2 / 110.5 / 110.1
H7-C3-C2-O1 / 245.5 / 239.2 / H11-C5-C2 / 110.1 / 109.7
H8-C4-C2-O1 / 5.8 / 0.2 / H12-C5-C2 / 110.0 / 109.7
H9-C4-C2-O1 / 127.6 / 121.3 / H13-C5-C2 / 111.4 / 111.0
H10-C4-C2-O1 / 245.4 / 239.2 / C4-C2-O3-O1 / 115.0 / 114.6
C5-C2-C4-O1 / 122.1 / 122.0
H6-O1-C2-C4 / 196.4 / 196.0
H7-O3-C2-O1 / 164.7 / 163.5
H8-C4-C2-O1 / 59.5 / 59.4
H9-C4-C2-O1 / 179.4 / 179.3
H10-C4-C2-O1 / 299.7 / 299.6
H11-C5-C2-O1 / -60.0 / -59.9
H12-C5-C2-O1 / 59.7 / 59.8
H13-C5-C2-O1 / 179.6 / 179.8

Table S6: Optimized parameters for ClCH2COCH3 and (ClCH2)(CH3)C(OH)2at B3LYP/6-31++G (d,p)and MP2/6-31++G(d,p) theoretical levels.

Parameters / ClCH2COCH3 / Parameters / (ClCH2)(CH3)C(OH)2
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.211 / 1.224 / C2-O1 / 1.413 / 1.414
C3-C2 / 1.530 / 1.523 / O3-C2 / 1.427 / 1.426
C4-C2 / 1.519 / 1.511 / C4-C2 / 1.536 / 1.524
Cl5-C3 / 1.790 / 1.765 / C5-C2 / 1.523 / 1.513
H6-C3 / 1.094 / 1.091 / H6-O1 / 0.968 / 0.968
H7-C3 / 1.094 / 1.090 / H7-O3 / 0.969 / 0.970
H8-C4 / 1.097 / 1.092 / H8-C4 / 1.092 / 1.089
H9-C4 / 1.091 / 1.087 / H9-C4 / 1.089 / 1.087
H10-C4 / 1.095 / 1.090 / Cl10-C4 / 1.810 / 1.779
C3-C2-O1 / 123.3 / 123.2 / H11-C5 / 1.095 / 1.090
C4-C2-O1 / 122.6 / 122.7 / H12-C5 / 1.091 / 1.087
Cl5-C3-C2 / 114.2 / 113.7 / H13-C5 / 1.093 / 1.089
H6-C3-C2 / 108.8 / 108.2 / O3-C2-O1 / 110.1 / 110.3
H7-C3-C2 / 109.7 / 109.0 / C4-C2-O3 / 106.9 / 107.5
H8-C4-C2 / 109.1 / 109.0 / C5-C2-C4 / 114.2 / 114.3
H9-C4-C2 / 109.4 / 109.3 / H6-O1-C2 / 108.6 / 107.8
H10-C4-C2 / 112.0 / 111.4 / H7-O3-C2 / 107.6 / 106.9
C4-C2-O1-C3 / 179.6 / 179.5 / H8-C4-C2 / 109.3 / 108.6
Cl5-C3-C2-O1 / 6.7 / 7.7 / H9-C4-C2 / 109.3 / 108.7
H6-C3-C2-O1 / -114.0 / -113.3 / Cl10-C4-C2 / 114.4 / 113.5
H7-C3-C2-O1 / 128.4 / 129.5 / H11-C5-C2 / 109.3 / 108.9
H8-C4-C2-O1 / -101.3 / -102.2 / H12-C5-C2 / 110.3 / 110.3
H9-C4-C2-O1 / 17.4 / 17.0 / H13-C5-C2 / 110.4 / 110.0
H10-C4-C2-O1 / 139.9 / 139.0 / C4-C2-O3-O1 / 115.2 / 115.1
C5-C2-C4-O1 / 125.0 / 124.7
H6-O1-C2-C4 / 171.9 / 173.6
H7-O3-C2-O1 / -45.4 / -46.8
H8-C4-C2-O1 / 52.4 / 54.4
H9-C4-C2-O1 / 172.9 / 174.0
Cl10-C4-C2-O1 / 293.0 / 294.6
H11-C5-C2-O1 / -61.0 / -62.3
H12-C5-C2-O1 / 59.5 / 58.1
H13-C5-C2-O1 / 180.4 / 179.1

Table S7: Optimized parameters for FCH2COCH3and (FCH2)(CH3)C(OH)2at B3LYP/6-31++G (d,p)and MP2/6-31++G(d,p) theoretical levels.

Parameters / FCH2COCH3 / Parameters / (FCH2)(CH3)C(OH)2
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.212 / 1.225 / C2-O1 / 1.414 / 1.415
C3-C2 / 1.526 / 1.520 / O3-C2 / 1.425 / 1.426
C4-C2 / 1.517 / 1.511 / C4-C2 / 1.532 / 1.520
F5-C3 / 1.382 / 1.389 / C5-C2 / 1.523 / 1.512
H6-C3 / 1.098 / 1.093 / H6-O1 / 0.968 / 0.968
H7-C3 / 1.098 / 1.093 / H7-O3 / 0.969 / 0.969
H8-C4 / 1.095 / 1.090 / H8-C4 / 1.095 / 1.090
H9-C4 / 1.091 / 1.087 / H9-C4 / 1.093 / 1.088
H10-C4 / 1.097 / 1.092 / F10-C4 / 1.399 / 1.403
C3-C2-O1 / 121.9 / 122.0 / H11-C5 / 1.095 / 1.090
C4-C2-O1 / 123.0 / 123.2 / H12-C5 / 1.092 / 1.087
F5-C3-C2 / 111.9 / 111.5 / H13-C5 / 1.093 / 1.088
H6-C3-C2 / 109.9 / 109.9 / O3-C2-O1 / 110.2 / 110.4
H7-C3-C2 / 109.2 / 109.5 / C4-C2-O3 / 107.8 / 108.0
H8-C4-C2 / 112.3 / 111.7 / C5-C2-C4 / 113.0 / 113.1
H9-C4-C2 / 109.5 / 109.3 / H6-O1-C2 / 108.8 / 108.1
H10-C4-C2 / 108.9 / 108.9 / H7-O3-C2 / 107.6 / 106.8
C4-C2-O1-C3 / -179.2 / -179.0 / H8-C4-C2 / 109.9 / 109.8
F5-C3-C2-O1 / -5.3 / -5.4 / H9-C4-C2 / 109.5 / 109.6
H6-C3-C2-O1 / -126.2 / -125.8 / F10-C4-C2 / 111.2 / 110.6
H7-C3-C2-O1 / 115.0 / 114.6 / H11-C5-C2 / 109.6 / 109.2
H8-C4-C2-O1 / -146.9 / -144.9 / H12-C5-C2 / 110.1 / 109.8
H9-C4-C2-O1 / -24.3 / -22.7 / H13-C5-C2 / 110.4 / 110.0
H10-C4-C2-O1 / 94.1 / 96.1 / C4-C2-O3-O1 / 115.4 / 115.2
C5-C2-C4-O1 / 123.8 / 123.8
H6-O1-C2-C4 / 168.9 / 169.3
H7-O3-C2-O1 / -43.6 / -43.6
H8-C4-C2-O1 / 50.8 / 51.2
H9-C4-C2-O1 / 172.3 / 173.2
F10-C4-C2-O1 / 291.6 / 292.2
H11-C5-C2-O1 / -59.4 / -60.3
H12-C5-C2-O1 / 61.2 / 60.2
H13-C5-C2-O1 / 181.9 / 180.9

Table S8: Optimized parameters for(CH3O)CHO and (CH3O)CH(OH)2at B3LYP/6-31++G (d,p)and MP2/6-31++G(d,p) theoretical levels.

Parameters / (CH3O)CHO / Parameters / (CH3O)CH(OH)2
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.209 / 1.219 / C2-O1 / 1.387 / 1.388
O3-C2 / 1.344 / 1.348 / O3-C2 / 1.388 / 1.389
C4-O3 / 1.446 / 1.446 / C4-O3 / 1.429 / 1.433
H5-C2 / 1.099 / 1.093 / O5-C2 / 1.416 / 1.416
H6-C4 / 1.090 / 1.087 / H6-O1 / 0.970 / 0.970
H7-C4 / 1.092 / 1.087 / H7-C2 / 1.101 / 1.096
H8-C4 / 1.092 / 1.084 / H8-C4 / 1.099 / 1.093
O3-C2-O1 / 126.7 / 125.6 / H9-C4 / 1.094 / 1.088
C4-O3-C2 / 118.0 / 114.5 / H10-C4 / 1.091 / 1.085
H5-C2-O1 / 124.6 / 125.1 / H11-O5 / 0.967 / 0.968
H6-C4-O3 / 110.6 / 110.0 / O3-C2-O1 / 108.8 / 108.7
H7-C4-O3 / 107.4 / 110.0 / C4-O3-C2 / 115.0 / 113.5
H8-C4-O3 / 107.4 / 105.0 / O5-C2-O3 / 107.5 / 107.1
C4-O3-C2-O1 / 0.003 / 0.001 / H6-O1-C2 / 107.3 / 106.4
H5-C2-O1-O3 / 180.0 / 180.0 / H7-C2-O1 / 106.3 / 106.3
H6-C4-O3-C2 / -60.4 / -60.4 / H8-C4-O3 / 110.7 / 110.4
H7-C4-O3-C2 / 60.4 / 60.4 / H9-C4-O3 / 111.2 / 111.0
H8-C4-O3-C2 / 180.0 / 180.0 / H10-C4-O3 / 106.1 / 105.7
H11-O5-C2 / 108.0 / 107.2
C4-O3-C2-O1 / 175.3 / 177.8
O5-C2-O3-C4 / -62.9 / -60.7
H6-O1-C2-O3 / 50.3 / 50.0
H7-C2-O1-H6 / 170.7 / 170.6
H8-C4-O3-C2 / -56.1 / -53.6
H9-C4-O3-C2 / 65.8 / 68.3
H10-C4-O3-C2 / 185.5 / 188.0
H11-O5-C2-O3 / 181.4 / 183.60

Table S9: Optimized parameters for (CH3O)(CH3)COand (CH3O)(CH3)C(OH)2at B3LYP/6-31++G (d,p)and MP2/6-31++G(d,p) theoretical levels.

Parameters / (CH3O)(CH3)CO / Parameters / (CH3O)(CH3)C(OH)2
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.214 / 1.223 / C2-O1 / 1.408 / 1.408
O3-C2 / 1.356 / 1.359 / C3-C2 / 1.523 / 1.513
C4-O3 / 1.442 / 1.443 / O4-C2 / 1.4234 / 1.423
C5-C2 / 1.509 / 1.503 / C5-O4 / 1.427 / 1.432
H6-C4 / 1.090 / 1.087 / O6-C2 / 1.399 / 1.400
H7-C4 / 1.092 / 1.084 / H7-O1 / 0.968 / 0.969
H8-C4 / 1.092 / 1.087 / H8-C3 / 1.093 / 1.088
H9-C5 / 1.090 / 1.085 / H9-C3 / 1.093 / 1.088
H10-C5 / 1.094 / 1.089 / H10-C3 / 1.092 / 1.087
H11-C5 / 1.094 / 1.089 / H11-C5 / 1.095 / 1.090
O3-C2-O1 / 124.1 / 123.3 / H12-C5 / 1.097 / 1.091
C4-O3-C2 / 118.1 / 114.5 / H13-C5 / 1.091 / 1.086
C5-C2-O1 / 125.3 / 126.0 / H14-O6 / 0.969 / 0.970
H6-C4-O3 / 110.5 / 110.2 / C3-C2-O1 / 111.4 / 111.6
H7-C4-O3 / 107.6 / 105.0 / O4-C2-O1 / 103.9 / 103.9
H8-C4-O3 / 107.6 / 110.2 / C5-O4-C2 / 116.7 / 115.1
H9-C5-C2 / 109.4 / 109.2 / O6-C2-O4 / 111.6 / 111.7
H10-C5-C2 / 110.0 / 109.7 / H7-O1-C2 / 106.9 / 106.2
H11-C5-C2 / 110.0 / 109.7 / H8-C3-C2 / 109.7 / 109.3
C4-O3-C2-O1 / -0.004 / 0.001 / H9-C3-C2 / 111.2 / 110.9
C5-C2-O1-O3 / 180.0 / 180.0 / H10-C3-C2 / 108.6 / 108.2
H6-C4-O3-C2 / 60.4 / 60.4 / H11-C5-O4 / 111.0 / 110.6
H7-C4-O3-C2 / 180.0 / 180.0 / H12-C5-O4 / 111.5 / 111.1
H8-C4-O3-C2 / 299.6 / 299.5 / H13-C5-O4 / 106.1 / 105.7
H9-C5-C2-O1 / -0.004 / -0.006 / H14-O6-C2 / 106.9 / 106.1
H10-C5-C2-O1 / 120.9 / 120.8 / O4-C2-O1-C3 / 122.5 / 122.6
H11-C5-C2-O1 / 238.1 / 239.2 / C5-O4-C2-O1 / 178.2 / 179.6
O6-C2-O4-C5 / 61.1 / 62.6
H7-O1-C2-C3 / -108.9 / -108.7
H8-C3-C2-O4 / -51.6 / -51.4
H9-C3-C2-O4 / 69.8 / 70.0
H10-C3-C2-O4 / 189.1 / 189.3
H11-C5-O4-C2 / -49.2 / -47.5
H12-C5-O4-C2 / 73.4 / 75.1
H13-C5-O4-C2 / 191.9 / 193.6
H14-O6-C2-O4 / 72.1 / 71.3

Table S10: Optimized parameters for (CH3O)(ClCH2)COand (CH3O)(ClCH2)C(OH)2at B3LYP/6-31++G (d,p)and MP2/6-31++G(d,p) theoretical levels.

Parameters / (CH3O)(ClCH2)CO / Parameters / (CH3O)(ClCH2)C(OH)2
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.213 / 1.223 / C2-O1 / 1.402 / 1.404
O3-C2 / 1.342 / 1.348 / C3-C2 / 1.545 / 1.528
C4-O3 / 1.443 / 1.446 / O4-C2 / 1.396 / 1.397
C5-C2 / 1.519 / 1.511 / C5-O4 / 1.438 / 1.442
H6-C4 / 1.092 / 1.087 / O6-C2 / 1.404 / 1.406
H7-C4 / 1.089 / 1.084 / H7-O1 / 0.970 / 0.970
H8-C4 / 1.092 / 1.087 / H8-C3 / 1.089 / 1.086
H9-C5 / 1.088 / 1.085 / Cl9-C3 / 1.806 / 1.775
H10-C5 / 1.091 / 1.087 / H10-C3 / 1.091 / 1.088
Cl11-C5 / 1.810 / 1.782 / H11-C5 / 1.092 / 1.087
O3-C2-O1 / 124.6 / 124.7 / H12-C5 / 1.093 / 1.086
C4-O3-C2 / 116.1 / 114.6 / H13-C5 / 1.091 / 1.086
C5-C2-O1 / 123.7 / 124.4 / H14-O6 / 0.967 / 0.968
H6-C4-O3 / 110.1 / 109.9 / C3-C2-O1 / 102.6 / 103.2
H7-C4-O3 / 105.3 / 104.9 / O4-C2-O1 / 106.5 / 107.7
H8-C4-O3 / 110.2 / 110.1 / C5-O4-C2 / 119.4 / 118.2
H9-C5-C2 / 108.7 / 108.4 / O6-C2-O4 / 107.9 / 118.2
H10-C5-C2 / 110.8 / 110.1 / H7-O1-C2 / 106.6 / 106.0
Cl11-C5-C2 / 111.4 / 110.7 / H8-C3-C2 / 108.4 / 107.8
C4-O3-C2-O1 / 2.7 / 2.7 / Cl9-C3-C2 / 114.7 / 112.7
C5-C2-O1-O3 / 181.2 / 180.9 / H10-C3-C2 / 109.3 / 109.4
H6-C4-O3-C2 / 59.7 / 59.7 / H11-C5-O4 / 111.0 / 110.7
H7-C4-O3-C2 / 179.2 / 179.1 / H12-C5-O4 / 111.3 / 111.3
H8-C4-O3-C2 / 298.9 / 298.7 / H13-C5-O4 / 104.8 / 104.2
H9-C5-C2-O1 / 8.1 / 6.4 / H14-O6-C2 / 108.8 / 107.1
H10-C5-C2-O1 / 130.5 / 128.2 / O4-C2-O1-C3 / 120.0 / 119.1
Cl11-C5-C2-O1 / 249.6 / 247.5 / C5-O4-C2-O1 / 160.3 / 145.5
O6-C2-O4-C5 / 40.1 / 24.7
H7-O1-C2-C3 / -158.6 / -158.6
H8-C3-C2-O4 / -43.7 / -51.7
Cl9-C3-C2-O4 / 76.8 / 68.2
H10-C3-C2-O4 / 196.9 / 188.8
H11-C5-O4-C2 / -56.3 / -66.5
H12-C5-O4-C2 / 66.4 / 56.3
H13-C5-O4-C2 / 184.9 / 174.9
H14-O6-C2-O4 / 175.7 / 169.7

Table S11: Optimized parameters for (CH3O)(FCH2)COand (CH3O)(FCH2)C(OH)2at B3LYP/6-31++G (d,p)and MP2/6-31++G(d,p) theoretical levels.

Parameters / (CH3O)(FCH2)CO / Parameters / (CH3O)(FCH2)C(OH)2
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.215 / 1.223 / C2-O1 / 1.398 / 1.399
O3-C2 / 1.335 / 1.340 / C3-C2 / 1.539 / 1.527
C4-O3 / 1.445 / 1.447 / O4-C2 / 1.395 / 1.396
C5-C2 / 1.520 / 1.515 / C5-O4 / 1.438 / 1.443
H6-C4 / 1.092 / 1.087 / O6-C2 / 1.408 / 1.408
H7-C4 / 1.089 / 1.084 / H7-O1 / 0.970 / 0.970
H8-C4 / 1.092 / 1.087 / H8-C3 / 1.092 / 1.087
H9-C5 / 1.095 / 1.089 / F9-C3 / 1.398 / 1.402
H10-C5 / 1.095 / 1.089 / H10-C3 / 1.094 / 1.090
F11-C5 / 1.388 / 1.393 / H11-C5 / 1.092 / 1.087
O3-C2-O1 / 125.3 / 125.4 / H12-C5 / 1.093 / 1.087
C4-O3-C2 / 115.8 / 114.2 / H13-C5 / 1.091 / 1.086
C5-C2-O1 / 120.9 / 121.0 / H14-O6 / 0.967 / 0.968
H6-C4-O3 / 110.2 / 110.0 / C3-C2-O1 / 103.7 / 103.6
H7-C4-O3 / 105.2 / 104.7 / O4-C2-O1 / 107.0 / 107.1
H8-C4-O3 / 110.2 / 110.0 / C5-O4-C2 / 118.3 / 117.1
H9-C5-C2 / 108.3 / 108.4 / O6-C2-O4 / 107.5 / 107.5
H10-C5-C2 / 108.3 / 108.4 / H7-O1-C2 / 106.9 / 106.1
F11-C5-C2 / 113.6 / 113.1 / H8-C3-C2 / 109.2 / 109.0
C4-O3-C2-O1 / -0.006 / -0.002 / F9-C3-C2 / 111.0 / 110.5
C5-C2-O1-O3 / 180.0 / 180.0 / H10-C3-C2 / 110.0 / 110.1
H6-C4-O3-C2 / 60.4 / 60.5 / H11-C5-O4 / 110.9 / 110.6
H7-C4-O3-C2 / 180.0 / 180.0 / H12-C5-O4 / 111.2 / 111.1
H8-C4-O3-C2 / 299.6 / 299.5 / H13-C5-O4 / 105.0 / 104.4
H9-C5-C2-O1 / -59.1 / -59.5 / H14-O6-C2 / 108.8 / 107.8
H10-C5-C2-O1 / 59.0 / 59.5 / O4-C2-O1-C3 / 120.6 / 120.4
F11-C5-C2-O1 / 180.0 / 180.0 / C5-O4-C2-O1 / 168.1 / 164.9
O6-C2-O4-C5 / 47.6 / 44.1
H7-O1-C2-C3 / -160.3 / -160.5
H8-C3-C2-O4 / -47.2 / -48.9
F9-C3-C2-O4 / 72.3 / 70.2
H10-C3-C2-O4 / 191.7 / 189.4
H11-C5-O4-C2 / -58.3 / -61.8
H12-C5-O4-C2 / 64.2 / 60.9
H13-C5-O4-C2 / 182.8 / 179.6
H14-O6-C2-O4 / 176.8 / 174.2

Table S12: Optimized parameters for (H2N)CHOand (H2N)CH(OH)2at B3LYP/6-31++G (d,p)and MP2/6-31++G(d,p) theoretical levels.

Parameters / (H2N)CHO / Parameters / (H2N)CH(OH)2
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.219 / 1.228 / C2-O1 / 1.404 / 1.405
N3-C2 / 1.361 / 1.364 / O3-C2 / 1.413 / 1.412
H4-C2 / 1.106 / 1.099 / N4-C2 / 1.441 / 1.437
H5-N3 / 1.010 / 1.008 / H5-N4 / 1.015 / 1.013
H6-N3 / 1.008 / 1.006 / H6-N4 / 1.015 / 1.013
N3-C2-O1 / 124.7 / 124.5 / H7-O1 / 0.971 / 0.971
H4-C2-O1 / 122.6 / 122.6 / H8-C2 / 1.101 / 1.095
H5-N3-C2 / 119.3 / 118.4 / H9-O3 / 0.967 / 0.967
H6-N3-C2 / 121.5 / 120.4 / O3-C2-O1 / 112.6 / 112.7
H4-C2-O1-N3 / 180.0 / 181.8 / N4-C2-O1 / 110.1 / 109.8
H5-N3-C2-O1 / 0.1 / 8.4 / H5-N4-C2 / 111.2 / 110.6
H6-N3-C2-O1 / 179.9 / 170.0 / H6-N4-H5 / 109.8 / 109.5
H7-O1-C2 / 106.2 / 105.4
H8-C2-N4 / 115.2 / 115.6
H9-O3-C2 / 107.6 / 107.0
N4-C2-O1-O3 / 116.8 / 116.2
H5-N4-C2-O1 / 73.5 / 72.2
H6-N4-H5-C2 / 236.6 / 237.8
H7-O1-C2-N4 / 44.7 / 45.5
H8-C2-N4-O1 / 242.6 / 242.6
H9-O3-C2-H8 / 59.4 / 59.7

Table S13: Optimized parameters for (H2N)(CH3)CO and (H2N)(CH3)C(OH)2at B3LYP/6-31++G (d,p)and MP2/6-31++G(d,p) theoretical levels.

Parameters / (H2N)(CH3)CO / Parameters / (H2N)(CH3)C(OH)2
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.225 / 1.233 / C2-O1 / 1.422 / 1.421
N3-C2 / 1.368 / 1.374 / O3-C2 / 1.412 / 1.412
C4-C2 / 1.520 / 1.513 / N4-C2 / 1.450 / 1.445
H5-N3 / 1.010 / 1.008 / H5-N4 / 1.015 / 1.014
H6-N3 / 1.007 / 1.006 / H6-N4 / 1.015 / 1.014
H7-C4 / 1.093 / 1.090 / H7-O1 / 0.967 / 0.968
H8-C4 / 1.093 / 1.089 / C8-C2 / 1.531 / 1.521
H9-C4 / 1.093 / 1.086 / H9-O3 / 0.970 / 0.971
N3-C2-O1 / 121.9 / 121.9 / H10-C8 / 1.095 / 1.090
C4-C2-O1 / 122.1 / 122.6 / H11-C8 / 1.094 / 1.089
H5-N3-C2 / 118.3 / 116.8 / H12-C8 / 1.093 / 1.088
H6-N3-C2 / 122.7 / 120.7 / O3-C2-O1 / 110.8 / 111.3
H7-C4-C2 / 108.6 / 108.7 / N4-C2-O1 / 103.8 / 103.4
H8-C4-C2 / 113.8 / 112.5 / H5-N4-C2 / 110.5 / 110.2
H9-C4-C2 / 108.6 / 108.6 / H6-N4-H5 / 109.4 / 109.2
C4-C2-O1-N3 / 180.0 / 184.6 / H7-O1-C2 / 107.3 / 106.8
H5-N3-C2-O1 / -0.006 / 10.4 / C8-C2-O1 / 111.0 / 111.1
H6-N3-C2-O1 / 180.0 / 164.9 / H9-O3-C2 / 105.8 / 105.2
H7-C4-C2-O1 / 58.4 / 87.0 / H10-C8-C2 / 110.4 / 110.1
H8-C4-C2-O1 / 180.1 / 207.2 / H11-C8-C2 / 110.3 / 109.9
H9-C4-C2-O1 / 301.8 / 329.0 / H12-C8-C2 / 109.7 / 109.3
N4-C2-O1-O3 / 117.0 / 116.7
H5-N4-C2-O1 / 38.1 / 44.7
H6-N4-H5-C2 / 237.1 / 238.5
H7-O1-C2-N4 / -192.2 / -186.8
C8-C2-O1-O3 / -117.9 / -117.9
H9-O3-C2-C8 / 194.0 / 190.4
H10-C8-C2-O3 / -56.9 / -57.8
H11-C8-C2-O3 / 62.2 / 61.4
H12-C8-C2-O3 / 182.9 / 182.0

Table S14: ΔHhyd(g)(in kcal/mol) for hydration reaction of carbonyl compoundswithout explicit water molecules and with explicit water molecules in gas phase at B3LYP/6-31++G(d,p)and MP2/6-31++G(d,p) theoretical levels.

Carbonylcompounds / ΔHhyd(g)
B3LYP / MP2
HCHO / -6.47 / -5.01
CH3CHO / -2.71 / -3.74
ClCH2CHO / -4.14 / -5.58
FCH2CHO / -4.19 / -4.93
CH3COCH3 / -1.78 / -2.77
ClCH2COCH3 / -4.58 / -8.68
FCH2COCH3 / -5.36 / -9.16
(CH3O)CHO / 6.96 / 6.50
(CH3O)(CH3)CO / 9.66 / 6.54
(CH3O)(ClCH2)CO / 9.11 / 5.49
(CH3O)(FCH2)CO / 8.16 / 4.95
(H2N)CHO / 8.33 / 6.30
(H2N)(CH3)CO / 10.32 / 6.00
HCHO-H2O / -12.91 / -12.44
CH3CHO-H2O / -5.52 / -7.19
ClCH2CHO-H2O / -7.54 / -9.40
FCH2CHO-H2O / -7.44 / -8.69
CH3COCH3-H2O / -3.45 / -8.24
ClCH2COCH3-H2O / -5.40 / -10.56
FCH2COCH3-H2O / -6.02 / -10.90
(CH3O)CHO-H2O / 4.28 / 2.97
(CH3O)(CH3)CO-H2O / 8.78 / 4.58
(CH3O)(ClCH2)CO-H2O / 6.69 / 2.02
(CH3O)(FCH2)CO-H2O / 6.11 / 1.81
(H2N)CHO-H2O / 5.60 / 3.76
(H2N)(CH3)CO-H2O / 8.89 / 4.07
HCHO-(H2O)2 / -12.11 / -11.15
HCHO-(H2O)3 / -8.93 / -8.49
HCHO-(H2O)4 / -22.63 / -23.34
CH3CHO-(H2O)2 / -6.72 / -8.78
CH3CHO-(H2O)3 / -3.63 / -6.36
CH3CHO-(H2O)4 / -3.95 / -6.95

Table S15: Second order delocalization eneries E(2) in kcal/mol associated with orbital Interactions in carbonyl compounds and their adducts with water at MP2/6-31++G(d,p) theoretical level using NBO analysis.

Adduct / Orbital
interactions / E(2) / Adduct / Orbital
interactions / E(2)
HCHO / nO1 → σ*C2-H3 / 24.26 / HCHO-H2O / nO1 → σ*C2-H3 / 22.90
nO1 → σ*C2-H4 / 24.26 / nO1 → σ*C2-H4 / 21.25
CH3CHO / nO1 → σ*C2-C3 / 22.59 / CH3CHO-H2O / nO1 → σ*C2-C3 / 21.59
nO1 → σ*C2-H4 / 26.42 / nO1 → σ*C2-H4 / 22.31
ClCH2CHO / nO1 → σ*C2-C3 / 25.12 / ClCH2CHO-H2O / nO1 → σ*C2-C3 / 23.70
nO1 → σ*C2-H4 / 25.20 / nO1 → σ*C2-H4 / 21.91
FCH2CHO / nO1 → σ*C2-C3 / 24.71 / FCH2CHO-H2O / nO1 → σ*C2-C3 / 23.30
nO1 → σ*C2-H4 / 25.03 / nO1 → σ*C2-H4 / 21.75
CH3COCH3 / nO1 → σ*C2-C3 / 24.08 / CH3COCH3-H2O / nO1→ σ*C2-C3 / 23.93
nO1 → σ*C2-C4 / 24.08 / nO1 → σ*C2-C4 / 19.32
ClCH2COCH3 / nO1 → σ*C2-C3 / 28.98 / ClCH2COCH3-H2O / nO1 → σ*C2-C3 / 28.13
nO1 → σ*C2-C4 / 24.35 / nO1 → σ*C2-C4 / 20.56
FCH2COCH3 / nO1 → σ*C2-C3 / 27.90 / FCH2COCH3-H2O / nO1 → σ*C2-C3 / 27.04
nO1 → σ*C2-C4 / 24.32 / nO1 → σ*C2-C4 / 20.52
(CH3O)CHO / nO1 → σ*C2-O3 / 40.83 / (CH3O)CHO-H2O / nO1 → σ*C2-O3 / 37.84
nO1 → σ*C2-H5 / 23.84 / nO1 → σ*C2-H5 / 20.91
nO3 → π*O1-C2 / 66.26 / nO3 → π*O1-C2 / 53.81
(CH3O)(CH3)CO / nO1 → σ*C2-O3 / 43.33 / (CH3O)(CH3)CO-H2O / nO1 → σ*C2-O3 / 40.62
nO1 → σ*C2-C5 / 21.50 / nO1 → σ*C2-C5 / 18.26
nO3 → σ*O1-C2 / 10.67 / nO3 → σ*O1-C2 / 10.84
nO3 → π*O1-C2 / 63.58 / nO3 → π*O1-C2 / 68.15
(CH3O)(ClCH2)CO / nO1 → σ*C2-O3 / 42.03 / (CH3O)(ClCH2)CO-H2O / nO1 → σ*C2-O3 / 40.14
nO1 → σ*C2-C5 / 23.26 / nO1 → σ*C2-C5 / 20.52
nO3 → σ*O1-C2 / 11.63 / nO3 → σ*O1-C2 / 11.75
nO3 → π*O1-C2 / 66.56 / nO3 → π*O1-C2 / 71.54
(CH3O)(FCH2)CO / nO1 → σ*C2-O3 / 41.00 / (CH3O)(FCH2)CO-H2O / nO1 → σ*C2-O3 / 38.90
nO1 → σ*C2-C5 / 23.02 / nO1 → σ*C2-C5 / 20.45
nO3 → σ*O1-C2 / 11.68 / nO3 → σ*O1-C2 / 11.47
nO3 → π*O1-C2 / 72.58 / nO3→ π*O1-C2 / 69.51
(H2N)CHO / nO1 → σ*C2-N3 / 31.18 / (H2N)CHO-H2O / nO1 → σ*C2-N3 / 29.12
nO1 → σ*C2-H4 / 26.76 / nO1 → σ*C2-H4 / 22.49
nN3 → π*O1-C2 / 49.64 / nN3 → π*O1-C2 / 66.34
(H2N)(CH3)CO / nO1 → σ*C2-N3 / 32.39 / (H2N)(CH3)CO-H2O / nO1 → σ*C2-N3 / 31.09
nO1 → σ*C2-C4 / 23.91 / nO1 → σ*C2-C4 / 19.14
nN3 → π*O1-C2 / 62.91 / nN3 → π*O1-C2 / 90.74
HCHO-(H2O)2 / nO1 → σ*C2-H3 / 20.52
nO1 → σ*C2-H4 / 20.52
HCHO-(H2O)3 / nO1 → σ*C2-H3 / 20.53
nO1 → σ*C2-H4 / 17.69
HCHO-(H2O)4 / nO1 → σ*C2-H3 / 17.88
nO1 → σ*C2-H4 / 17.87
CH3CHO-(H2O)2 / nO1 → σ*C2-C3 / 19.49
nO1 → σ*C2-H4 / 22.55
CH3CHO-(H2O)3 / nO1 → σ*C2-C3 / 19.72
nO1 → σ*C2-H4 / 18.99
CH3CHO-(H2O)4 / nO1 → σ*C2-C3 / 18.71
nO1 → σ*C2-H4 / 19.42

Table S16: Optimized parameters for HCHO-H2O and CH2(OH)2-H2O at B3LYP/6-31++G(d,p) and MP2/6-31++G(d,p) theoretical levels.

Parameters / HCHO-H2O / Parameters / CH2(OH)2-H2O
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.214 / 1.228 / C2-O1 / 1.396 / 1.400
H3-C2 / 1.106 / 1.096 / O3-C2 / 1.433 / 1.433
H4-C2 / 1.105 / 1.096 / H4-C2 / 1.094 / 1.088
H5-O1 / 1.981 / 2.103 / H5-O1 / 0.975 / 0.973
O6-H5 / 0.973 / 0.970 / H6-O3 / 0.968 / 0.968
H7-O6 / 0.964 / 0.963 / H7-C2 / 1.095 / 1.089
H3-C2-O1 / 121.2 / 121.00 / O8-H5 / 2.030 / 2.033
H4-C2-O1 / 121.5 / 121.3 / H9-O8 / 0.964 / 0.963
H5-O1-C2 / 104.1 / 100.7 / H10-O8 / 0.974 / 0.972
O6-H5-O1 / 149.8 / 146.8 / O3-C2-O1 / 112.6 / 112.4
H7-O6-H5 / 106.4 / 106.0 / H4-C2-O1 / 106.6 / 106.3
H4-C2-O1-H3 / 180.0 / 180.0 / H5-O1-C2 / 107.6 / 106.8
H5-O1-C2-H4 / 0.01 / 0.6 / H6-O3-C2 / 107.9 / 107.1
O6-H5-O1-C2 / 0.02 / 0.7 / H7-C2-O1 / 112.6 / 112.4
H7-O6-H5-O1 / 180.1 / 182.8 / O8-H5-O1 / 141.1 / 140.4
H9-O8-H5 / 140.9 / 141.9
H10-O8-H9 / 107.7 / 107.2
H4-C2-O1-O3 / 121.2 / 121.0
H5-O1-C2-O3 / 63.8 / 65.2
H6-O3-C2-H4 / -56.9 / -57.5
H7-C2-O1-H4 / 121.2 / 121.7
O8-H5-O1-C2 / -23.3 / -19.7
H9-O8-H5-O1 / -133.0 / -140.9
H10-O8-H9-H5 / -110.3 / -113.5

Table S17:Optimized parameters for CH3CHO-H2O and CH3CH(OH)2-H2O at B3LYP/6-31++G(d,p) and MP2/6-31++G(d,p) theoretical levels.

Parameters / CH3CHO-H2O / Parameters / CH3CH(OH)2-H2O
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.219 / 1.232 / C2-O1 / 1.387 / 1.391
C3-C2 / 1.500 / 1.496 / O3-C2 / 1.456 / 1.453
H4-C2 / 1.109 / 1.101 / C4-C2 / 1.517 / 1.509
H5-C3 / 1.091 / 1.086 / H5-O1 / 0.977 / 0.974
H6-C3 / 1.097 / 1.091 / H6-O3 / 0.967 / 0.968
H7-C3 / 1.097 / 1.091 / H7-C4 / 1.094 / 1.089
H8-O1 / 1.931 / 1.968 / H8-C4 / 1.095 / 1.090
O9-H8 / 0.975 / 0.971 / H9-C4 / 1.093 / 1.088
H10-O9 / 0.964 / 0.963 / H10-C2 / 1.103 / 1.097
C3-C2-O1 / 124.1 / 123.8 / O11-H5 / 1.974 / 1.983
H4-C2-O1 / 119.6 / 119.4 / H12-O11 / 0.964 / 0.963
H5-C3-C2 / 111.1 / 110.5 / H13-O11 / 0.976 / 0.973
H6-C3-C2 / 109.3 / 109.3 / O3-C2-O1 / 107.4 / 107.2
H7-C3-C2 / 109.4 / 109.3 / C4-C2-O1 / 108.8 / 108.4
H8-O1-C2 / 106.7 / 101.65 / H5-O1-C2 / 108.5 / 107.7
O9-H8-O1 / 157.2 / 152.3 / H6-O3-C2 / 108.9 / 108.2
H10-O9-H8 / 106.2 / 105.9 / H7-C4-C2 / 109.8 / 109.7
H4-C2-O1-C3 / 180.0 / 180.0 / H8-C4-C2 / 110.9 / 110.7
H5-C3-C2-O1 / -0.2 / 0.2 / H9-C4-C2 / 109.4 / 108.7
H6-C3-C2-O1 / 121.6 / 121.8 / H10-C2-O1 / 111.1 / 111.0
H7-C3-C2-O1 / 237.9 / 238.8 / O11-H5-O1 / 115.0 / 146.0
H8-O1-C2-H4 / -0.02 / -1.0 / H12-O11-H5 / 120.4 / 125.8
O9-H8-O1-C2 / 0.1 / -0.7 / H13-O11-H12 / 107.0 / 106.7
H10-O9-H8-O1 / 181.6 / 173.5 / C4-C2-O1-O3 / 120.4 / 119.9
H5-O1-C2-O3 / 57.3 / 60.3
H6-O3-C2-C4 / 67.7 / 63.2
H7-C4-C2-O1 / 61.1 / 61.3
H8-C4-C2-O1 / -179.0 / -178.7
H9-C4-C2-O1 / -58.5 / -58.4
H10-C2-O1-C4 / 122.7 / 123.0
O11-H5-O1-C2 / -39.1 / -34.2
H12-O11-H5-O1 / -105.9 / -114.7
H13-O11-H12-H5 / -90.0 / -93.8

Table S18: Optimized parameters for ClCH2CHO-H2O and ClCH2CH(OH)2-H2O at B3LYP/6-31++G(d,p) and MP2/6-31++G(d,p) theoretical levels.

Parameters / ClCH2CHO-H2O / Parameters / ClCH2CH(OH)2-H2O
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.215 / 1.228 / C2-O1 / 1.379 / 1.383
C3-C2 / 1.514 / 1.509 / O3-C2 / 1.451 / 1.447
H4-C2 / 1.105 / 1.099 / C4-C2 / 1.525 / 1.515
H5-C3 / 1.090 / 1.086 / Cl5-C4 / 1.808 / 1.778
H6-C3 / 1.095 / 1.090 / H6-O1 / 0.977 / 0.975
Cl7-C3 / 1.804 / 1.778 / H7-O3 / 0.968 / 0.969
H8-O1 / 1.998 / 2.040 / H8-C4 / 1.091 / 1.088
O9-H8 / 0.972 / 0.969 / H9-C4 / 1.090 / 1.087
H10-O9 / 0.964 / 0.963 / H10-C2 / 1.101 / 1.097
C3-C2-O1 / 121.4 / 121.5 / O11-H6 / 1.950 / 1.959
H4-C2-O1 / 121.5 / 121.2 / H12-O11 / 0.965 / 0.964
H5-C3-C2 / 110.4 / 109.6 / H13-O11 / 0.974 / 0.971
H6-C3-C2 / 109.0 / 108.8 / O3-C2-O1 / 108.1 / 107.9
Cl7-C3-C2 / 111.2 / 110.7 / C4-C2-O1 / 108.9 / 108.2
H8-O1-C2 / 104.0 / 100.1 / Cl5-C4-C2 / 111.9 / 111.3
O9-H8-O1 / 147.8 / 143.0 / H6-O1-C2 / 108.7 / 108.0
H10-O9-H8 / 106.5 / 106.1 / H7-O3-C2 / 109.0 / 108.4
H4-C2-O1-C3 / 178.4 / 178.1 / H8-C4-C2 / 110.5 / 110.0
H5-C3-C2-O1 / -28.6 / -25.2 / H9-C4-C2 / 109.4 / 108.3
H6-C3-C2-O1 / 91.7 / 94.9 / H10-C2-O1 / 112.2 / 112.1
Cl7-C3-C2-O1 / 210.1 / 213.6 / O11-H6-O1 / 145.9 / 145.1
H8-O1-C2-H4 / 4.3 / 7.3 / H12-O11-H6 / 123.7 / 127.4
O9-H8-O1-C2 / 4.9 / 8.0 / H13-O11-H12 / 84.0 / 106.9
H10-O9-H8-O1 / 191.4 / 194.1 / C4-C2-O1-O3 / 117.5 / 117.3
Cl5-C4-C2-O1 / 73.1 / 70.3
H6-O1-C2-C4 / 177.9 / 180.0
H7-O3-C2-O1 / 197.6 / 194.8
H8-C4-C2-O1 / 191.9 / 189.9
H9-C4-C2-O1 / 313.4 / 310.4
H10-C2-O1-C4 / 123.1 / 123.1
O11-H6-O1-C2 / -44.9 / -42.0
H12-O11-H6-O1 / -108.8 / -114.8
H13-O11-H12-H6 / -94.7 / -96.8

Table S19: Optimized parameters for FCH2CHO-H2O and FCH2CH(OH)2-H2O at B3LYP/6-31++G(d,p) and MP2/6-31++G(d,p) theoretical levels.

Parameters / FCH2CHO-H2O / Parameters / FCH2CH(OH)2-H2O
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.216 / 1.228 / C2-O1 / 1.380 / 1.384
C3-C2 / 1.513 / 1.509 / O3-C2 / 1.450 / 1.448
H4-C2 / 1.107 / 1.099 / C4-C2 / 1.523 / 1.513
H5-C3 / 1.096 / 1.090 / F5-C4 / 1.399 / 1.403
H6-C3 / 1.096 / 1.090 / H6-O1 / 0.977 / 0.974
F7-C3 / 1.394 / 1.401 / H7-O3 / 0.968 / 0.969
H8-O1 / 1.988 / 2.038 / H8-C4 / 1.095 / 1.090
O9-H8 / 0.972 / 0.969 / H9-C4 / 1.093 / 1.088
H10-O9 / 0.964 / 0.963 / H10-C2 / 1.102 / 1.096
C3-C2-O1 / 121.7 / 121.1 / O11-H6 / 1.961 / 1.972
H4-C2-O1 / 122.0 / 121.9 / H12-O11 / 0.965 / 0.964
H5-C3-C2 / 110.0 / 110.2 / H13-O11 / 0.974 / 0.971
H6-C3-C2 / 110.0 / 110.2 / O3-C2-O1 / 108.4 / 108.3
F7-C3-C2 / 109.9 / 109.5 / C4-C2-O1 / 108.7 / 108.1
H8-O1-C2 / 104.3 / 100.55 / F5-C4-C2 / 109.9 / 109.5
O9-H8-O1 / 148.6 / 143.1 / H6-O1-C2 / 108.7 / 108.0
H10-O9-H8 / 106.5 / 106.1 / H7-O3-C2 / 109.1 / 108.4
H4-C2-O1-C3 / 180.0 / 179.9 / H8-C4-C2 / 110.6 / 110.7
H5-C3-C2-O1 / -60.4 / -59.4 / H9-C4-C2 / 109.7 / 109.4
H6-C3-C2-O1 / 60.0 / 62.0 / H10-C2-O1 / 112.0 / 112.1
F7-C3-C2-O1 / 179.8 / 181.2 / O11-H6-O1 / 144.9 / 143.7
H8-O1-C2-H4 / -0.001 / 2.074 / H12-O11-H6 / 123.4 / 128.0
O9-H8-O1-C2 / -0.07 / 2.952 / H13-O11-H12 / 107.2 / 106.9
H10-O9-H8-O1 / 180.4 / 190.1 / C4-C2-O1-O3 / 118.0 / 117.3
F5-C4-C2-O1 / 73.6 / 71.9
H6-O1-C2-C4 / 179.3 / 181.7
H7-O3-C2-O1 / 198.3 / 196.8
H8-C4-C2-O1 / 192.2 / 190.4
H9-C4-C2-O1 / 314.3 / 312.9
H10-C2-O1-C4 / 122.1 / 122.5
O11-H6-O1-C2 / -45.3 / -43.3
H12-O11-H6-O1 / -108.2 / -115.0
H13-O11-H12-H6 / 279.8 / 277.5

Table S20: Optimized parameters for CH3COCH3-H2O(CH3)2C(OH)2-H2O at B3LYP/6-31++G(d,p) and MP2/6-31++G(d,p) theoretical levels.

Parameters / CH3COCH3-H2O / Parameters / (CH3)2C(OH)2-H2O
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.225 / 1.235 / C2-O1 / 1.410 / 1.413
C3-C2 / 1.514 / 1.508 / O3-C2 / 1.449 / 1.446
C4-C2 / 1.513 / 1.508 / C4-C2 / 1.526 / 1.515
H5-C3 / 1.091 / 1.086 / C5-C2 / 1.528 / 1.517
H6-C3 / 1.095 / 1.090 / H6-O1 / 0.975 / 0.974
H7-C3 / 1.097 / 1.092 / H7-O3 / 0.969 / 0.970
H8-C4 / 1.091 / 1.086 / H8-C4 / 1.095 / 1.090
H9-C4 / 1.095 / 1.090 / H9-C4 / 1.093 / 1.088
H10-C4 / 1.098 / 1.092 / H10-C4 / 1.093 / 1.088
H11-O1 / 1.903 / 1.935 / H11-C5 / 1.094 / 1.089
O12-H11 / 0.976 / 0.972 / H12-C5 / 1.093 / 1.088
H13-O12 / 0.964 / 0.963 / H13-C5 / 1.093 / 1.089
C3-C2-O1 / 120.7 / 120.9 / O14-H6 / 2.053 / 2.046
C4-C2-O1 / 121.4 / 122.0 / H15-O14 / 0.976 / 0.973
H5-C3-C2 / 110.3 / 110.0 / H16-O14 / 0.964 / 0.963
H6-C3-C2 / 110.9 / 110.4 / O3-C2-O1 / 109.6 / 109.9
H7-C3-C2 / 109.2 / 109.1 / C4-C2-O3 / 110.1 / 110.1
H8-C4-C2 / 111.0 / 110.8 / C5-C2-C4 / 112.9 / 113.1
H9-C4-C2 / 110.8 / 110.3 / H6-O1-C2 / 108.4 / 107.7
H10-C4-C2 / 108.7 / 108.6 / H7-O3-C2 / 107.3 / 106.6
H11-O1-C2 / 117.8 / 116.7 / H8-C4-C2 / 110.0 / 109.6
O12-H11-O1 / 163.6 / 163.2 / H9-C4-C2 / 110.4 / 110.0
H13-O12-H11 / 106.4 / 105.9 / H10-C4-C2 / 110.1 / 109.9
C4-C2-O1-C3 / 179.6 / 179.7 / H11-C5-C2 / 110.2 / 109.9
H5-C3-C2-O1 / 9.4 / 9.0 / H12-C5-C2 / 109.5 / 109.2
H6-C3-C2-O1 / 131.8 / 131.1 / H13-C5-C2 / 110.7 / 110.3
H7-C3-C2-O1 / 249.3 / 248.8 / O14-H6-O1 / 175.0 / 144.3
H8-C4-C2-O1 / 13.0 / 12.2 / H15-O14-H6 / 104.6 / 84.7
H9-C4-C2-O1 / 136.2 / 134.9 / H16-O14-H15 / 105.1 / 107.2
H10-C4-C2-O1 / 253.3 / 252.2 / C4-C2-O3-O1 / 116.9 / 116.7
H11-O1-C2-C4 / -3.0 / -1.1 / C5-C2-C4-O1 / 123.6 / 123.4
O12-H11-O1-C2 / -1.5 / -1.8 / H6-O1-C2-C4 / 184.2 / 182.8
H13-O12-H11-O1 / 191.4 / 193.8 / H7-O3-C2-O1 / -63.1 / -62.7
H8-C4-C2-O1 / 57.1 / 57.1
H9-C4-C2-O1 / 177.7 / 177.5
H10-C4-C2-O1 / 298.4 / 298.3
H11-C5-C2-O1 / -58.9 / -58.9
H12-C5-C2-O1 / 60.4 / 60.4
H13-C5-C2-O1 / 180.8 / 180.7
O14-H6-O1-C2 / 43.3 / 43.1
H15-O14-H6-O1 / -16.4 / -15.2
H16-O14-H15-H6 / 146.1 / 150.0

Table S21: Optimized parameters for ClCH2COCH3-H2O and (ClCH2)(CH3)C(OH)2

-H2O at B3LYP/6-31++G(d,p) and MP2/6-31++G(d,p) theoretical levels.

Parameters / ClCH2COCH3-H2O / Parameters / (ClCH2)(CH3)C(OH)2
-H2O
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.217 / 1.228 / C2-O1 / 1.400 / 1.403
C3-C2 / 1.526 / 1.520 / O3-C2 / 1.447 / 1.444
C4-C2 / 1.514 / 1.508 / C4-C2 / 1.536 / 1.524
Cl5-C3 / 1.789 / 1.765 / C5-C2 / 1.525 / 1.515
H6-C3 / 1.094 / 1.090 / H6-O1 / 0.975 / 0.975
H7-C3 / 1.095 / 1.091 / H7-O3 / 0.970 / 0.971
H8-C4 / 1.091 / 1.087 / H8-C4 / 1.092 / 1.089
H9-C4 / 1.094 / 1.090 / H9-C4 / 1.089 / 1.087
H10-C4 / 1.098 / 1.092 / Cl10-C4 / 1.808 / 1.778
H11-O1 / 1.939 / 1.962 / H11-C5 / 1.093 / 1.088
O12-H11 / 0.974 / 0.971 / H12-C5 / 1.091 / 1.087
H13-O12 / 0.964 / 0.963 / H13-C5 / 1.093 / 1.089
C3-C2-O1 / 122.4 / 122.4 / O14-H6 / 2.037 / 2.022
C4-C2-O1 / 123.0 / 123.0 / H15-O14 / 0.973 / 0.971
Cl5-C3-C2 / 114.5 / 113.9 / H16-O14 / 0.964 / 0.964
H6-C3-C2 / 109.4 / 108.8 / O3-C2-O1 / 109.9 / 110.2
H7-C3-C2 / 108.5 / 108.0 / C4-C2-O3 / 106.2 / 106.7
H8-C4-C2 / 110.2 / 110.1 / C5-C2-C4 / 113.8 / 113.9
H9-C4-C2 / 111.9 / 111.3 / H6-O1-C2 / 108.4 / 107.6
H10-C4-C2 / 108.4 / 108.3 / H7-O3-C2 / 107.2 / 106.5
H11-O1-C2 / 116.6 / 115.3 / H8-C4-C2 / 109.3 / 108.6
O12-H11-O1 / 158.4 / 158.0 / H9-C4-C2 / 109.6 / 109.0
H13-O12-H11 / 106.5 / 106.1 / Cl10-C4-C2 / 114.1 / 113.3
C4-C2-O1-C3 / 179.4 / 179.1 / H11-C5-C2 / 109.7 / 109.3
Cl5-C3-C2-O1 / 6.5 / 6.9 / H12-C5-C2 / 109.7 / 109.6
H6-C3-C2-O1 / 128.4 / 128.8 / H13-C5-C2 / 110.6 / 110.1
H7-C3-C2-O1 / 245.7 / 245.8 / O14-H6-O1 / 143.4 / 143.9
H8-C4-C2-O1 / 22.4 / 24.5 / H15-O14-H6 / 88.4 / 89.6
H9-C4-C2-O1 / 146.0 / 147.6 / H16-O14-H15 / 107.8 / 107.3
H10-C4-C2-O1 / 264.2 / 266.0 / C4-C2-O3-O1 / 115.7 / 115.5
H11-O1-C2-C4 / -5.3 / -4.9 / C5-C2-C4-O1 / 126.2 / 125.8
O12-H11-O1-C2 / -4.4 / -5.3 / H6-O1-C2-C4 / 183.7 / 183.2
H13-O12-H11-O1 / 193.2 / 193.9 / H7-O3-C2-O1 / 63.0 / 62.5
H8-C4-C2-O1 / 52.4 / 54.7
H9-C4-C2-O1 / 173.2 / 174.6
Cl10-C4-C2-O1 / 293.3 / 295.2
H11-C5-C2-O1 / -58.0 / -59.5
H12-C5-C2-O1 / 61.5 / 60.0
H13-C5-C2-O1 / 182.0 / 180.6
O14-H6-O1-C2 / 44.6 / 44.0
H15-O14-H6-O1 / -17.8 / -17.3
H16-O14-H15-H6 / 151.5 / 153.0

Table S22: Optimized parameters for FCH2COCH3-H2O and (FCH2)(CH3)C(OH)2-H2Oat B3LYP/6-31++G(d,p) and MP2/6-31++G(d,p) theoretical levels.

Parameters / FCH2COCH3-H2O / Parameters / (FCH2)(CH3)C(OH)2-H2O
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.218 / 1.229 / C2-O1 / 1.401 / 1.404
C3-C2 / 1.522 / 1.516 / O3-C2 / 1.445 / 1.443
C4-C2 / 1.512 / 1.507 / C4-C2 / 1.532 / 1.520
F5-C3 / 1.381 / 1.388 / C5-C2 / 1.524 / 1.514
H6-C3 / 1.098 / 1.093 / H6-O1 / 0.975 / 0.975
H7-C3 / 1.098 / 1.093 / H7-O3 / 0.970 / 0.971
H8-C4 / 1.092 / 1.087 / H8-C4 / 1.095 / 1.091
H9-C4 / 1.095 / 1.090 / H9-C4 / 1.093 / 1.089
H10-C4 / 1.097 / 1.092 / F10-C4 / 1.398 / 1.402
H11-O1 / 1.934 / 1.966 / H11-C5 / 1.093 / 1.088
O12-H11 / 0.975 / 0.971 / H12-C5 / 1.092 / 1.087
H13-O12 / 0.964 / 0.963 / H13-C5 / 1.094 / 1.089
C3-C2-O1 / 121.1 / 121.3 / O14-H6 / 2.050 / 2.037
C4-C2-O1 / 123.4 / 123.4 / H15-O14 / 0.973 / 0.971
F5-C3-C2 / 112.0 / 111.7 / H16-O14 / 0.964 / 0.964
H6-C3-C2 / 109.7 / 109.6 / O3-C2-O1 / 110.0 / 110.3
H7-C3-C2 / 109.1 / 109.3 / C4-C2-O3 / 107.1 / 107.2
H8-C4-C2 / 110.2 / 110.0 / C5-C2-C4 / 112.7 / 112.7
H9-C4-C2 / 112.0 / 111.5 / H6-O1-C2 / 108.5 / 107.7
H10-C4-C2 / 108.4 / 108.3 / H7-O3-C2 / 107.1 / 106.4
H11-O1-C2 / 115.8 / 114.2 / H8-C4-C2 / 109.8 / 109.8
O12-H11-O1 / 158.8 / 157.4 / H9-C4-C2 / 109.8 / 109.8
H13-O12-H11 / 106.5 / 106.1 / F10-C4-C2 / 111.1 / 110.5
C4-C2-O1-C3 / 179.1 / 178.7 / H11-C5-C2 / 109.9 / 109.6
F5-C3-C2-O1 / 4.6 / 4.5 / H12-C5-C2 / 109.4 / 109.0
H6-C3-C2-O1 / 125.6 / 125.0 / H13-C5-C2 / 110.6 / 110.2
H7-C3-C2-O1 / 244.2 / 244.4 / O14-H6-O1 / 142.3 / 142.5
H8-C4-C2-O1 / 27.8 / 30.9 / H15-O14-H6 / 88.5 / 90.2
H9-C4-C2-O1 / 151.4 / 154.0 / H16-O14-H15 / 107.7 / 107.2
H10-C4-C2-O1 / 270.0 / 272.9 / C4-C2-O3-O1 / 115.9 / 115.6
H11-O1-C2-C4 / -6.6 / -6.4 / C5-C2-C4-O1 / 125.1 / 124.9
O12-H11-O1-C2 / -5.5 / -6.2 / H6-O1-C2-C4 / 181.5 / 180.6
H13-O12-H11-O1 / 195.4 / 192.8 / H7-O3-C2-O1 / 64.5 / 64.7
H8-C4-C2-O1 / 50.2 / 50.8
H9-C4-C2-O1 / 172.0 / 173.0
F10-C4-C2-O1 / 291.3 / 292.1
H11-C5-C2-O1 / -56.5 / -57.6
H12-C5-C2-O1 / 63.1 / 62.0
H13-C5-C2-O1 / 183.4 / 182.3
O14-H6-O1-C2 / 45.1 / 44.6
H15-O14-H6-O1 / -18.1 / -17.3
H16-O14-H15-H6 / 151.9 / 153.7

Table S23: Optimized parameters for (CH3O)CHO-H2O and (CH3O)CH(OH)2-H2O at B3LYP/6-31++G(d,p) and MP2/6-31++G(d,p) theoretical levels.

Parameters / (CH3O)CHO-H2O / Parameters / (CH3O)CH(OH)2-H2O
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.216 / 1.225 / C2-O1 / 1.409 / 1.407
O3-C2 / 1.333 / 1.340 / O3-C2 / 1.388 / 1.390
C4-O3 / 1.447 / 1.448 / C4-O3 / 1.429 / 1.434
H5-C2 / 1.097 / 1.091 / O5-C2 / 1.397 / 1.399
H6-C4 / 1.092 / 1.087 / H6-O1 / 0.971 / 0.971
H7-C4 / 1.092 / 1.087 / H7-C2 / 1.101 / 1.096
H8-C4 / 1.089 / 1.083 / H8-C4 / 1.093 / 1.088
H9-O1 / 1.948 / 2.008 / H9-C4 / 1.091 / 1.085
O10-H9 / 0.973 / 0.970 / H10-C4 / 1.099 / 1.093
H11-O10 / 0.964 / 0.963 / H11-O5 / 0.976 / 0.975
O3-C2-O1 / 125.2 / 125.0 / O12-H11 / 1.978 / 1.980
C4-O3-C2 / 116.3 / 114.8 / H13-O12 / 0.974 / 0.971
H5-C2-O1 / 124.4 / 124.4 / H14-O12 / 0.964 / 0.963
H6-C4-O3 / 110.1 / 109.9 / O3-C2-O1 / 107.4 / 107.3
H7-C4-O3 / 110.1 / 109.9 / C4-O3-C2 / 114.8 / 113.2
H8-C4-O3 / 105.2 / 104.9 / O5-C2-O3 / 108.7 / 108.2
H9-O1-C2 / 106.9 / 100.1 / H6-O1-C2 / 106.7 / 105.9
O10-H9-O1 / 157.2 / 147.1 / H7-C2-O1 / 105.5 / 105.6
H11-O10-H9 / 106.3 / 106.1 / H8-C4-O3 / 111.2 / 110.9
C4-O3-C2-O1 / -0.06 / -0.1 / H9-C4-O3 / 106.0 / 105.6
H5-C2-O1-O3 / 180.0 / 180.0 / H10-C4-O3 / 110.7 / 110.4
H6-C4-O3-C2 / -60.3 / -60.5 / H11-O5-C2 / 107.8 / 106.9
H7-C4-O3-C2 / 60.6 / 60.4 / O12-H11-O5 / 145.4 / 144.8
H8-C4-O3-C2 / 180.1 / 179.9 / H13-O12-H11 / 88.1 / 90.2
H9-O1-C2-H5 / -0.5 / -3.2 / H14-O12-H13 / 107.6 / 107.2
O10-H9-O1-C2 / -1.3 / -2.9 / C4-O3-C2-O1 / 177.3 / 179.4
H11-O10-H9-O1 / 168.0 / 164.2 / O5-C2-O3-C4 / -60.9 / -58.9
H6-O1-C2-O3 / 49.5 / 49.5
H7-C2-O1-H6 / 168.7 / 168.9
H8-C4-O3-C2 / 64.7 / 67.3
H9-C4-O3-C2 / 184.3 / 187.1
H10-C4-O3-C2 / 302.7 / 305.4
H11-O5-C2-O3 / 182.7 / 180.6
O12-H11-O5-C2 / 36.3 / 33.2
H13-O12-H11-O5 / -6.4 / -0.9
H14-O12-H13-H11 / 144.3 / 150.5

Table S24: Optimized parameters for (CH3O)(CH3)CHO-H2O and (CH3O)(CH3)C(OH)2-H2O at B3LYP/6-31++G(d,p) and MP2/6-31++G(d,p) theoretical levels.

Parameters / (CH3O)(CH3)CHO-H2O / Parameters / (CH3O)(CH3)C(OH)2-H2O
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.222 / 1.229 / C2-O1 / 1.420 / 1.418
O3-C2 / 1.345 / 1.351 / C3-C2 / 1.526 / 1.516
C4-O3 / 1.443 / 1.446 / O4-C2 / 1.404 / 1.404
C5-C2 / 1.505 / 1.500 / C5-O4 / 1.429 / 1.434
H6-C4 / 1.092 / 1.087 / O6-C2 / 1.405 / 1.407
H7-C4 / 1.089 / 1.084 / H7-O1 / 0.970 / 0.971
H8-C4 / 1.092 / 1.087 / H8-C3 / 1.092 / 1.087
H9-C5 / 1.090 / 1.086 / H9-C3 / 1.092 / 1.087
H10-C5 / 1.095 / 1.090 / H10-C3 / 1.093 / 1.089
H11-C5 / 1.093 / 1.087 / H11-C5 / 1.093 / 1.087
H12-O1 / 1.907 / 1.941 / H12-C5 / 1.097 / 1.091
O13-H12 / 0.975 / 0.972 / H13-C5 / 1.091 / 1.086
H14-O13 / 0.964 / 0.963 / H14-O6 / 0.976 / 0.975
O3-C2-O1 / 122.4 / 122.5 / O15-H14 / 1.978 / 1.978
C4-O3-C2 / 116.4 / 114.9 / H16-O15 / 0.970 / 0.972
C5-C2-O1 / 125.6 / 125.8 / H17-O15 / 0.960 / 0.964
H6-C4-O3 / 110.3 / 110.1 / C3-C2-O1 / 107.1 / 107.0
H7-C4-O3 / 105.3 / 104.8 / O4-C2-O1 / 105.0 / 105.0
H8-C4-O3 / 110.3 / 110.1 / C5-O4-C2 / 117.0 / 115.6
H9-C5-C2 / 110.0 / 109.7 / O6-C2-O4 / 107.6 / 107.3
H10-C5-C2 / 109.1 / 108.6 / H7-O1-C2 / 105.8 / 105.1
H11-C5-C2 / 110.2 / 110.1 / H8-C3-C2 / 109.8 / 109.2
H12-O1-C2 / 116.2 / 114.4 / H9-C3-C2 / 110.0 / 109.7
O13-H12-O1 / 162.2 / 161.1 / H10-C3-C2 / 109.9 / 109.7
H14-O13-H12 / 106.5 / 105.9 / H11-C5-O4 / 111.2 / 111.0
C4-O3-C2-O1 / -0.3 / -0.7 / H12-C5-O4 / 111.4 / 111.2
C5-C2-O1-O3 / 180.8 / 181.6 / H13-C5-O4 / 105.5 / 105.1
H6-C4-O3-C2 / 60.6 / 60.8 / H14-O6-C2 / 107.8 / 106.9
H7-C4-O3-C2 / 180.2 / 180.4 / O15-H14-O6 / 148.2 / 147.9
H8-C4-O3-C2 / 299.7 / 299.9 / H16-O15-H14 / 85.1 / 86.6
H9-C5-C2-O1 / -10.2 / -17.8 / H17-O15-H16 / 107.4 / 106.9
H10-C5-C2-O1 / 109.7 / 101.3 / O4-C2-O1-C3 / 121.0 / 121.0
H11-C5-C2-O1 / 227.5 / 219.6 / C5-O4-C2-O1 / 168.9 / 168.0
H12-O1-C2-O3 / 181.4 / 181.9 / O6-C2-O4-C5 / 50.9 / 49.7
O13-H12-O1-C2 / -1.3 / 1.8 / H7-O1-C2-C3 / -161.2 / -162.5
H14-O13-H12-O1 / 171.8 / 163.0 / H8-C3-C2-O4 / -55.5 / -55.5
H9-C3-C2-O4 / 65.2 / 65.1
H10-C3-C2-O4 / 184.3 / 184.3
H11-C5-O4-C2 / -59.0 / -62.2
H12-C5-O4-C2 / 63.6 / 60.4
H13-C5-O4-C2 / 181.7 / 178.5
H14-O6-C2-O4 / 169.1 / 171.2
O15-H14-O6-C2 / -30.0 / -29.4
H16-O15-H14-O6 / -7.0 / -9.6
H17-O15-H16-H14 / 129.7 / 132.6

TableS25:Optimized parameters for (CH3O)(ClCH2)CO-H2O and (CH3O)(ClCH2)C(OH)2-H2O at B3LYP/6-31++G(d,p) and MP2/6-31++G(d,p) theoretical levels.

Parameters / (CH3O)(ClCH2)CO-H2O / Parameters / (CH3O)(ClCH2)C(OH)2
-H2O
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.219 / 1.227 / C2-O1 / 1.430 / 1.426
O3-C2 / 1.336 / 1.343 / C3-C2 / 1.542 / 1.528
C4-O3 / 1.445 / 1.447 / O4-C2 / 1.397 / 1.398
C5-C2 / 1.517 / 1.510 / C5-O4 / 1.439 / 1.442
H6-C4 / 1.092 / 1.087 / O6-C2 / 1.387 / 1.391
H7-C4 / 1.089 / 1.084 / H7-O1 / 0.970 / 0.971
H8-C4 / 1.092 / 1.087 / H8-C3 / 1.089 / 1.086
H9-C5 / 1.089 / 1.085 / Cl9-C3 / 1.807 / 1.776
H10-C5 / 1.090 / 1.086 / H10-C3 / 1.090 / 1.087
Cl11-C5 / 1.813 / 1.785 / H11-C5 / 1.092 / 1.087
H12-O1 / 1.964 / 1.998 / H12-C5 / 1.092 / 1.086
O13-H12 / 0.973 / 0.970 / H13-C5 / 1.091 / 1.086
H14-O13 / 0.964 / 0.963 / H14-O6 / 0.978 / 0.977
O3-C2-O1 / 123.7 / 123.9 / O15-H14 / 1.921 / 1.934
C4-O3-C2 / 116.5 / 114.9 / H16-O15 / 0.973 / 0.971
C5-C2-O1 / 124.1 / 124.9 / H17-O15 / 0.964 / 0.964
H6-C4-O3 / 110.0 / 109.8 / C3-C2-O1 / 102.8 / 103.2
H7-C4-O3 / 105.2 / 104.8 / O4-C2-O1 / 105.8 / 106.3
H8-C4-O3 / 110.2 / 110.0 / C5-O4-C2 / 118.9 / 117.7
H9-C5-C2 / 109.4 / 109.3 / O6-C2-O4 / 109.6 / 109.1
H10-C5-C2 / 110.7 / 110.2 / H7-O1-C2 / 105.7 / 105.1
Cl11-C5-C2 / 110.1 / 109.0 / H8-C3-C2 / 108.8 / 108.0
H12-O1-C2 / 115.6 / 113.9 / Cl9-C3-C2 / 113.5 / 112.1
O13-H12-O1 / 152.3 / 149.7 / H10-C3-C2 / 109.8 / 109.6
H14-O13-H12 / 106.7 / 106.3 / H11-C5-O4 / 111.1 / 110.8
C4-O3-C2-O1 / 2.4 / 2.3 / H12-C5-O4 / 111.2 / 111.1
C5-C2-O1-O3 / 180.6 / 179.5 / H13-C5-O4 / 104.7 / 104.2
H6-C4-O3-C2 / 60.2 / 59.3 / H14-O6-C2 / 108.2 / 107.1
H7-C4-O3-C2 / 179.7 / 178.8 / O15-H14-O6 / 149.8 / 148.8
H8-C4-O3-C2 / 299.3 / 298.4 / H16-O15-H14 / 88.8 / 90.3
H9-C5-C2-O1 / 11.8 / 17.6 / H17-O15-H16 / 107.7 / 107.2
H10-C5-C2-O1 / 135.3 / 140.9 / O4-C2-O1-C3 / 118.5 / 118.2
Cl11-C5-C2-O1 / 253.5 / 259.2 / C5-O4-C2-O1 / 147.8 / 143.7
H12-O1-C2-O3 / 168.2 / 168.1 / O6-C2-O4-C5 / 27.5 / 23.1
O13-H12-O1-C2 / -11.6 / -13.2 / H7-O1-C2-C3 / -147.5 / -151.8
H14-O13-H12-O1 / 158.8 / 162.3 / H8-C3-C2-O4 / -49.9 / -51.4
Cl9-C3-C2-O4 / 69.6 / 68.0
H10-C3-C2-O4 / 189.3 / 188.1
H11-C5-O4-C2 / -61.3 / -66.1
H12-C5-O4-C2 / 61.3 / 56.5
H13-C5-O4-C2 / 179.8 / 175.2
H14-O6-C2-O4 / 168.8 / 172.7
O15-H14-O6-C2 / -29.3 / -28.1
H16-O15-H14-O6 / -12.1 / -15.9
H17-O15-H16-H14 / 132.1 / 134.8

Table S26: Optimized parameters for (CH3O)(FCH2)CO-H2O and (CH3O)(FCH2)C(OH)2-H2O at B3LYP/6-31++G(d,p) and MP2/6-31++G(d,p) theoretical levels.

Parameters / (CH3O)(FCH2)CO-H2O / Parameters / (CH3O)(FCH2)C(OH)2
-H2O
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.222 / 1.229 / C2-O1 / 1.422 / 1.420
O3-C2 / 1.329 / 1.334 / C3-C2 / 1.539 / 1.526
C4-O3 / 1.446 / 1.449 / O4-C2 / 1.397 / 1.398
C5-C2 / 1.519 / 1.515 / C5-O4 / 1.439 / 1.443
H6-C4 / 1.092 / 1.087 / O6-C2 / 1.391 / 1.394
H7-C4 / 1.089 / 1.083 / H7-O1 / 0.970 / 0.971
H8-C4 / 1.092 / 1.087 / H8-C3 / 1.092 / 1.087
H9-C5 / 1.094 / 1.088 / F9-C3 / 1.399 / 1.403
H10-C5 / 1.094 / 1.089 / H10-C3 / 1.093 / 1.089
F11-C5 / 1.388 / 1.394 / H11-C5 / 1.092 / 1.087
H12-O1 / 1.941 / 1.983 / H12-C5 / 1.093 / 1.087
O13-H12 / 0.974 / 0.970 / H13-C5 / 1.091 / 1.086
H14-O13 / 0.964 / 0.963 / H14-O6 / 0.977 / 0.976
O3-C2-O1 / 124.3 / 124.5 / O15-H14 / 1.943 / 1.949
C4-O3-C2 / 116.2 / 114.5 / H16-O15 / 0.973 / 0.970
C5-C2-O1 / 121.5 / 121.6 / H17-O15 / 0.964 / 0.964
H6-C4-O3 / 110.1 / 109.9 / C3-C2-O1 / 103.8 / 103.7
H7-C4-O3 / 105.1 / 104.6 / O4-C2-O1 / 105.6 / 105.9
H8-C4-O3 / 110.1 / 109.9 / C5-O4-C2 / 118.0 / 116.7
H9-C5-C2 / 108.7 / 108.9 / O6-C2-O4 / 109.0 / 108.6
H10-C5-C2 / 108.6 / 108.7 / H7-O1-C2 / 105.9 / 105.1
F11-C5-C2 / 112.8 / 112.2 / H8-C3-C2 / 109.3 / 109.0
H12-O1-C2 / 114.9 / 113.3 / F9-C3-C2 / 110.3 / 109.8
O13-H12-O1 / 153.9 / 149.9 / H10-C3-C2 / 110.2 / 110.4
H14-O13-H12 / 106.8 / 106.3 / H11-C5-O4 / 110.8 / 110.6
C4-O3-C2-O1 / 0.05 / 0.5 / H12-C5-O4 / 111.1 / 111.0
C5-C2-O1-O3 / 180.1 / 180.5 / H13-C5-O4 / 104.9 / 104.4
H6-C4-O3-C2 / 60.4 / 60.6 / H14-O6-C2 / 108.3 / 107.3
H7-C4-O3-C2 / 179.9 / 180.1 / O15-H14-O6 / 148.9 / 148.3
H8-C4-O3-C2 / 299.5 / 299.6 / H16-O15-H14 / 88.4 / 90.4
H9-C5-C2-O1 / -57.9 / -56.9 / H17-O15-H16 / 107.6 / 107.1
H10-C5-C2-O1 / 59.7 / 61.7 / O4-C2-O1-C3 / 119.2 / 119.1
F11-C5-C2-O1 / 180.8 / 182.0 / C5-O4-C2-O1 / 162.8 / 160.1
H12-O1-C2-O3 / 181.1 / 192.1 / O6-C2-O4-C5 / 42.4 / 39.4
O13-H12-O1-C2 / 0.3 / 3.1 / H7-O1-C2-C3 / -151.0 / -152.4
H14-O13-H12-O1 / 178.6 / 177.8 / H8-C3-C2-O4 / -50.0 / -50.6
F9-C3-C2-O4 / 68.8 / 67.8
H10-C3-C2-O4 / 187.9 / 186.8
H11-C5-O4-C2 / -59.1 / -63.5
H12-C5-O4-C2 / 63.4 / 59.1
H13-C5-O4-C2 / 182.0 / 177.8
H14-O6-C2-O4 / 169.9 / 172.3
O15-H14-O6-C2 / -30.4 / -29.4
H16-O15-H14-O6 / -11.0 / -14.9
H17-O15-H16-H14 / 131.5 / 134.6

Table S27: Optimized parameters for (H2N)CHO-H2O and (H2N)CH(OH)2-H2O at B3LYP/6-31++G(d,p) and MP2/6-31++G(d,p) theoretical levels.

Parameters / (H2N)CHO-H2O / Parameters / (H2N)CH(OH)2-H2O
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.227 / 1.235 / C2-O1 / 1.390 / 1.393
N3-C2 / 1.353 / 1.355 / O3-C2 / 1.414 / 1.413
H4-C2 / 1.103 / 1.096 / N4-C2 / 1.462 / 1.455
H5-N3 / 1.011 / 1.008 / H5-N4 / 1.017 / 1.016
H6-N3 / 1.008 / 1.005 / H6-N4 / 1.017 / 1.016
H7-O1 / 1.893 / 1.930 / H7-O1 / 0.982 / 0.980
O8-H7 / 0.977 / 0.973 / H8-C2 / 1.100 / 1.094
H9-O8 / 0.964 / 0.962 / H9-O3 / 0.967 / 0.967
N3-C2-O1 / 124.1 / 124.0 / O10-H7 / 1.917 / 1.924
H4-C2-O1 / 122.1 / 122.0 / H11-O10 / 0.965 / 0.964
H5-N3-C2 / 119.5 / 119.1 / H12-O10 / 0.983 / 0.978
H6-N3-C2 / 121.3 / 120.8 / O3-C2-O1 / 113.2 / 113.3
H7-O1-C2 / 105.2 / 100.6 / N4-C2-O1 / 111.3 / 110.9
O8-H7-O1 / 158.5 / 153.8 / H5-N4-C2 / 109.8 / 109.2
H9-O8-H7 / 106.2 / 105.9 / H6-N4-H5 / 108.4 / 108.3
H4-C2-O1-N3 / 180.0 / 181.0 / H7-O1-C2 / 108.4 / 107.4
H5-N3-C2-O1 / 0.01 / 5.2 / H8-C2-N4 / 113.1 / 113.9
H6-N3-C2-O1 / 180.0 / 174.0 / H9-O3-C2 / 107.3 / 106.8
H7-O1-C2-H4 / 0.2 / 3.7 / O10-H7-O1 / 153.5 / 153.8
O8-H7-O1-C2 / 0.2 / 2.1 / H11-O10-H7 / 125.1 / 128.5
H9-O8-H7-O1 / 185.1 / 203.9 / H12-O10-H11 / 107.3 / 106.7
N4-C2-O1-O3 / 117.0 / 116.2
H5-N4-C2-O1 / 75.5 / 70.2
H6-N4-H5-C2 / 240.3 / 241.1
H7-O1-C2-N4 / 47.1 / 50.3
H8-C2-N4-O1 / 241.8 / 241.6
H9-O3-C2-H8 / 72.3 / 68.6
O10-H7-O1-C2 / -27.2 / -22.6
H11-O10-H7-O1 / -103.8 / -109.5
H12-O10-H11-H7 / -90.3 / -92.5

Table S28: Optimized parameters for (H2N)(CH3)CO-H2O and (H2N)(CH3)C(OH)2-H2O at B3LYP/6-31++G(d,p) and MP2/6-31++G(d,p) theoretical levels.

Parameters / (H2N)(CH3)CO-H2O / Parameters / (H2N)(CH3)C(OH)2-H2O
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.234 / 1.240 / C2-O1 / 1.397 / 1.400
N3-C2 / 1.361 / 1.363 / O3-C2 / 1.423 / 1.421
C4-C2 / 1.515 / 1.509 / N4-C2 / 1.473 / 1.463
H5-N3 / 1.010 / 1.008 / H5-N4 / 1.017 / 1.016
H6-N3 / 1.007 / 1.005 / H6-N4 / 1.017 / 1.016
H7-C4 / 1.092 / 1.087 / H7-O1 / 0.981 / 0.980
H8-C4 / 1.093 / 1.088 / C8-C2 / 1.530 / 1.520
H9-C4 / 1.095 / 1.090 / H9-O3 / 0.967 / 0.968
H10-O1 / 1.861 / 1.890 / H10-C8 / 1.094 / 1.089
O11-H10 / 0.979 / 0.975 / H11-C8 / 1.094 / 1.089
H12-O11 / 0.964 / 0.963 / H12-C8 / 1.093 / 1.088
N3-C2-O1 / 121.0 / 121.1 / O13-H7 / 1.903 / 1.917
C4-C2-O1 / 122.4 / 122.6 / H14-O13 / 0.965 / 0.964
H5-N3-C2 / 118.5 / 117.9 / H15-O13 / 0.985 / 0.979
H6-N3-C2 / 122.4 / 121.5 / O3-C2-O1 / 111.5 / 111.9
H7-C4-C2 / 109.1 / 109.1 / N4-C2-O1 / 110.2 / 110.0
H8-C4-C2 / 113.1 / 112.2 / H5-N4-C2 / 109.1 / 108.9
H9-C4-C2 / 108.5 / 108.6 / H6-N4-H5 / 108.2 / 108.1
H10-O1-C2 / 115.1 / 113.8 / H7-O1-C2 / 108.5 / 107.5
O11-H10-O1 / 165.6 / 163.8 / C8-C2-O1 / 107.0 / 106.6
H12-O11-H10 / 106.2 / 105.8 / H9-O3-C2 / 107.0 / 106.6
C4-C2-O1-N3 / 179.0 / 179.5 / H10-C8-C2 / 109.8 / 109.7
H5-N3-C2-O1 / 0.6 / 7.5 / H11-C8-C2 / 110.5 / 110.1
H6-N3-C2-O1 / 179.9 / 171.2 / H12-C8-C2 / 109.9 / 109.6
H7-C4-C2-O1 / 43.6 / 36.4 / O13-H7-O1 / 155.0 / 154.5
H8-C4-C2-O1 / 166.3 / 158.7 / H14-O13-H7 / 123.8 / 127.3
H9-C4-C2-O1 / 287.3 / 279.2 / H15-O13-H14 / 107.3 / 106.6
H10-O1-C2-C4 / -7.8 / -9.5 / N4-C2-O1-O3 / -113.9 / -113.4
O11-H10-O1-C2 / -6.9 / -5.9 / H5-N4-C2-O1 / 161.0 / 168.6
H12-O11-H10-O1 / 198.8 / 198.6 / H6-N4-H5-C2 / -119.7 / -118.5
H7-O1-C2-N4 / -44.6 / -49.0
C8-C2-O1-O3 / 121.4 / 121.7
H9-O3-C2-C8 / -80.2 / -72.7
H10-C8-C2-O3 / 64.1 / 63.4
H11-C8-C2-O3 / -176.8 / -177.4
H12-C8-C2-O3 / -55.7 / -56.6
O13-H7-O1-C2 / 26.9 / 23.1
H14-O13-H7-O1 / 103.2 / 108.0
H15-O13-H14-H7 / 88.2 / 90.4

Table S29: Optimized parameters for HCHO-(H2O)2 and CH2(OH)2-(H2O)2 at B3LYP/6-31++G(d,p) and MP2/6-31++G(d,p) theoretical levels.

Parameters / HCHO-(H2O)2 / Parameters / CH2(OH)2-(H2O)2
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.219 / 1.233 / C2-O1 / 1.390 / 1.393
H3-C2 / 1.103 / 1.094 / O3-C2 / 1.436 / 1.436
H4-C2 / 1.103 / 1.094 / H4-O3 / 0.977 / 0.975
H5-O1 / 2.012 / 2.039 / H5-C2 / 1.095 / 1.089
O6-H5 / 0.972 / 0.969 / H6-C2 / 1.102 / 1.095
H7-O6 / 0.964 / 0.963 / H7-O1 / 0.975 / 0.973
H8-O1 / 2.012 / 2.039 / O8-H7 / 2.061 / 2.063
O9-H8 / 0.972 / 0.969 / H9-O8 / 0.965 / 0.963
H10-O9 / 0.964 / 0.963 / H10-O8 / 0.980 / 0.976
H3-C2-O1 / 120.7 / 120.5 / O11-H4 / 1.869 / 1.882
H4-C2-O1 / 120.7 / 120.5 / H12-O11 / 0.966 / 0.964
H5-O1-C2 / 103.0 / 100.6 / H13-O11 / 0.966 / 0.964
O6-H5-O1 / 145.1 / 143.1 / O3-C2-O1 / 109.7 / 109.3
H7-O6-H5 / 106.6 / 106.1 / H4-O3-C2 / 109.2 / 108.2
H8-O1-C2 / 103.0 / 100.6 / H5-C2-O1 / 106.5 / 106.3
O9-H8-O1 / 145.0 / 143.1 / H6-C2-O1 / 112.0 / 111.9
H10-O9-H8 / 106.6 / 106.1 / H7-O1-C2 / 108.4 / 107.7
H4-C2-O1-H3 / 180.0 / 180.0 / O8-H7-O1 / 142.6 / 142.5
H5-O1-C2-H4 / 0.008 / 2.7 / H9-O8-H7 / 116.4 / 119.9
O6-H5-O1-C2 / 0.005 / 3.9 / H10-O8-H9 / 106.8 / 106.4
H7-O6-H5-O1 / -179.7 / -166.7 / O11-H4-O3 / 177.2 / 175.8
H8-O1-C2-H4 / 0.023 / 2.7 / H12-O11-H4 / 119.4 / 121.4
O9-H8-O1-C2 / 0.007 / 4.2 / H13-O11-H12 / 106.4 / 106.0
H10-O9-H8-O1 / -179.7 / -167.7 / H4-O3-C2-O1 / 160.9 / 163.4
H5-C2-O1-O3 / -119.1 / -119.0
H6-C2-O1-O3 / 120.7 / 120.4
H7-O1-C2-O3 / -57.6 / -59.9
O8-H7-O1-C2 / 44.6 / 43.4
H9-O8-H7-O1 / 97.1 / 100.2
H10-O8-H9-H7 / 83.0 / 84.5
O11-H4-O3-C2 / -70.4 / -70.1
H12-O11-H4-O3 / -168.1 / -171.6
H13-O11-H12-H4 / -137.2 / -140.7

Table S30: Optimized parameters for HCHO-(H2O)3 and CH2(OH)2-(H2O)3 at B3LYP/6-31++G(d,p) and MP2/6-31++G(d,p) theoretical levels.

Parameters / HCHO-(H2O)3 / Parameters / CH2(OH)2-(H2O)3
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.224 / 1.236 / C2-O1 / 1.400 / 1.402
H3-C2 / 1.103 / 1.095 / O3-C2 / 1.429 / 1.430
H4-C2 / 1.102 / 1.093 / H4-O3 / 0.977 / 0.975
H5-O1 / 1.988 / 2.017 / H5-C2 / 1.095 / 1.089
O6-H5 / 0.972 / 0.969 / H6-C2 / 1.100 / 1.094
H7-O6 / 0.964 / 0.963 / H7-O1 / 0.978 / 0.975
H8-O1 / 1.902 / 1.928 / O8-H7 / 1.966 / 1.978
O9-H8 / 0.978 / 0.974 / H9-O8 / 0.965 / 0.964
H10-O9 / 0.965 / 0.963 / H10-O8 / 0.979 / 0.976
H11-O9 / 1.851 / 1.883 / O11-H4 / 1.853 / 1.874
O12-H11 / 0.979 / 0.975 / H12-O11 / 0.966 / 0.964
H13-O12 / 0.964 / 0.963 / H13-O11 / 0.966 / 0.965
H3-C2-O1 / 119.8 / 119.6 / H14-O1 / 1.894 / 1.900
H4-C2-O1 / 120.8 / 120.7 / O15-H14 / 0.975 / 0.972
H5-O1-C2 / 104.5 / 101.5 / H16-O15 / 0.964 / 0.963
O6-H5-O1 / 149.4 / 145.9 / O3-C2-O1 / 109.1 / 108.7
H7-O6-H5 / 106.5 / 106.1 / H4-O3-C2 / 109.0 / 107.9
H8-O1-C2 / 116.0 / 115.7 / H5-C2-O1 / 106.3 / 106.1
O9-H8-O1 / 162.5 / 162.3 / H6-C2-O1 / 111.4 / 111.3
H10-O9-H8 / 106.7 / 106.2 / H7-O1-C2 / 108.5 / 107.9
H11-O9-H8 / 98.9 / 99.2 / O8-H7-O1 / 145.2 / 144.3
O12-H11-O9 / 158.6 / 157.9 / H9-O8-H7 / 119.9 / 124.0
H13-O12-H11 / 106.7 / 106.1 / H10-O8-H9 / 107.1 / 106.8
H4-C2-O1-H3 / 179.9 / 179.9 / O11-H4-O3 / 177.1 / 174.7
H5-O1-C2-H4 / 1.1 / 2.8 / H12-O11-H4 / 121.2 / 123.4
O6-H5-O1-C2 / 4.5 / 6.1 / H13-O11-H12 / 106.6 / 106.1
H7-O6-H5-O1 / -166.8 / -162.1 / H14-O1-C2 / 115.9 / 113.9
H8-O1-C2-H4 / 0.6 / -0.6 / O15-H14-O1 / 175.0 / 171.9
O9-H8-O1-C2 / 5.7 / 3.0 / H16-O15-H14 / 105.6 / 105.1
H10-O9-H8-O1 / -135.3 / -134.0 / H4-O3-C2-O1 / 160.2 / 165.4
H11-O9-H8-H10 / 128.1 / 130.9 / H5-C2-O1-O3 / -119.3 / -119.2
O12-H11-O9-H8 / 0.1 / 0.1 / H6-C2-O1-O3 / 120.8 / 120.4
H13-O12-H11-H4 / 145.3 / 147.6 / H7-O1-C2-O3 / -56.2 / -59.9
O8-H7-O1-C2 / 42.7 / 39.5
H9-O8-H7-O1 / 101.4 / 107.4
H10-O8-H9-H7 / 88.1 / 90.2
O11-H4-O3-C2 / -69.9 / -39.8
H12-O11-H4-O3 / -172.2 / 152.1
H13-O11-H12-H4 / -143.1 / -148.6
H14-O1-C2-O3 / 167.3 / 159.9
O15-H14-O1-C2 / 3.3 / -14.8
H16-O15-H14-O1 / -131.0 / -112.7

Table S31: Optimized parameters for HCHO-(H2O)4 and CH2(OH)2-(H2O)4 at B3LYP/6-31++G(d,p) and MP2/6-31++G(d,p) theoretical levels.

Parameters / HCHO-(H2O)4 / Parameters / CH2(OH)2-(H2O)4
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.229 / 1.240 / C2-O1 / 1.420 / 1.421
H3-C2 / 1.102 / 1.093 / O3-C2 / 1.412 / 1.414
H4-C2 / 1.102 / 1.093 / H4-O3 / 0.984 / 0.980
H5-O1 / 1.890 / 1.913 / H5-C2 / 1.094 / 1.088
O6-H5 / 0.978 / 0.975 / H6-C2 / 1.094 / 1.088
H7-O6 / 0.965 / 0.963 / H7-O1 / 0.987 / 0.982
H8-O1 / 1.890 / 1.913 / O8-H7 / 1.765 / 1.786
O9-H8 / 0.978 / 0.975 / H9-O8 / 0.989 / 0.983
H10-O9 / 0.965 / 0.964 / H10-O8 / 0.964 / 0.963
H11-O9 / 1.852 / 1.884 / O11-H4 / 1.800 / 1.812
O12-H11 / 0.979 / 0.975 / H12-O11 / 0.982 / 0.977
H13-O12 / 0.964 / 0.963 / H13-O11 / 0.964 / 0.963
H14-O6 / 1.852 / 1.884 / H14-O3 / 1.925 / 1.915
O15-H14 / 0.979 / 0.975 / O15-H14 / 0.980 / 0.977
H16-O15 / 0.964 / 0.963 / H16-O15 / 0.971 / 0.969
H3-C2-O1 / 119.9 / 119.8 / H17-O1 / 1.753 / 1.772
H4-C2-O1 / 119.9 / 119.8 / O18-H17 / 0.992 / 0.987
H5-O1-C2 / 115.9 / 115.9 / H19-O18 / 0.965 / 0.964
O6-H5-O1 / 164.0 / 163.7 / O3-C2-O1 / 113.3 / 112.9
H7-O6-H5 / 106.7 / 106.2 / H4-O3-C2 / 109.2 / 108.2
H8-O1-C2 / 115.9 / 115.9 / H5-C2-O1 / 106.3 / 106.2
O9-H8-O1 / 164.1 / 163.7 / H6-C2-O1 / 109.8 / 109.8
H10-O9-H8 / 106.7 / 106.2 / H7-O1-C2 / 109.4 / 108.5
H11-O9-H8 / 98.3 / 98.5 / O8-H7-O1 / 163.4 / 163.4
O12-H11-O9 / 158.8 / 158.0 / H9-O8-H7 / 97.2 / 97.2
H13-O12-H11 / 106.7 / 106.1 / H10-O8-H9 / 108.1 / 107.5
H14-O6-H7 / 121.7 / 124.1 / O11-H4-O3 / 164.4 / 163.9
O15-H14-O6 / 158.8 / 158.0 / H12-O11-H4 / 97.9 / 99.1
H16-O15-H14 / 106.7 / 106.1 / H13-O11-H12 / 107.6 / 107.2
H4-C2-O1-H3 / 180.0 / 180.0 / H14-O3-H4 / 100.9 / 101.6
H5-O1-C2-H4 / -0.4 / 0.5 / O15-H14-O3 / 161.0 / 162.6
O6-H5-O1-C2 / -6.6 / -7.0 / H16-O15-H14 / 103.5 / 103.3
H7-O6-H5-O1 / 134.9 / 135.8 / H17-O1-H7 / 103.7 / 104.7
H8-O1-C2-H4 / -0.4 / 0.4 / O18-H17-O1 / 166.6 / 166.7
O9-H8-O1-C2 / -6.3 / -6.2 / H19-O18-H17 / 107.1 / 106.3
H10-O9-H8-O1 / 134.7 / 135.3 / H4-O3-C2-O1 / -81.9 / -82.9
H11-O9-H8-H10 / -126.8 / -129.4 / H5-C2-O1-O3 / -121.5 / -121.1
O12-H11-O9-H8 / 0.2 / 0.8 / H6-C2-O1-O3 / 119.2 / 118.8
H13-O12-H11-H4 / -143.8 / -145.9 / H7-O1-C2-O3 / -79.5 / -80.6
H14-O6-H7-H5 / 111.3 / 112.6 / O8-H7-O1-C2 / 94.1 / 92.1
O15-H14-O6-H5 / -0.1 / 1.2 / H9-O8-H7-O1 / -21.7 / -17.6
H16-O15-H14-H3 / -143.6 / -146.2 / H10-O8-H9-H7 / 138.8 / 141.7
O11-H4-O3-C2 / 67.8 / 63.0
H12-O11-H4-O3 / 7.7 / 15.7
H13-O11-H12-H4 / -127.1 / -131.1
H14-O3-H4-C2 / -121.8 / -121.5
O15-H14-O3-C2 / -35.9 / -32.0
H16-O15-H14-O3 / -45.9 / -50.8
H17-O1-H7-C2 / -122.9 / -123.6
O18-H17-O1-H7 / 80.1 / 83.4
H19-O18-H17-O1 / -169.9 / -172.2

Table S32:Optimized parameters for CH3CHO-(H2O)2 and CH3CH(OH)2-(H2O)2 at B3LYP/6-31++G(d,p) and MP2/6-31++G(d,p) theoretical levels.

Parameters / CH3CHO-(H2O)2 / Parameters / CH3CH(OH)2-(H2O)2
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.225 / 1.236 / C2-O1 / 1.395 / 1.398
C3-C2 / 1.496 / 1.493 / O3-C2 / 1.444 / 1.443
H4-C2 / 1.106 / 1.099 / C4-C2 / 1.518 / 1.509
H5-C3 / 1.091 / 1.086 / H5-O1 / 0.975 / 0.974
H6-C3 / 1.098 / 1.092 / H6-O3 / 0.976 / 0.975
H7-C3 / 1.098 / 1.092 / H7-C4 / 1.094 / 1.089
H8-O1 / 1.965 / 1.995 / H8-C4 / 1.094 / 1.089
O9-H8 / 0.973 / 0.970 / H9-C4 / 1.094 / 1.088
H10-O9 / 0.964 / 0.963 / H10-C2 / 1.103 / 1.098
H11-O1 / 1.959 / 1.987 / O11-H5 / 2.044 / 2.037
O12-H11 / 0.973 / 0.970 / H12-O11 / 0.965 / 0.963
H13-O12 / 0.964 / 0.963 / H13-O11 / 0.981 / 0.977
C3-C2-O1 / 124.6 / 124.2 / O14-H6 / 1.879 / 1.890
H4-C2-O1 / 118.6 / 118.5 / H15-O14 / 0.966 / 0.965
H5-C3-C2 / 112.0 / 111.4 / H16-O14 / 0.966 / 0.965
H6-C3-C2 / 108.8 / 108.7 / O3-C2-O1 / 108.1 / 107.8
H7-C3-C2 / 108.8 / 108.7 / C4-C2-O1 / 108.4 / 108.1
H8-O1-C2 / 104.4 / 101.4 / H5-O1-C2 / 108.5 / 107.7
O9-H8-O1 / 151.3 / 147.8 / H6-O3-C2 / 109.2 / 107.9
H10-O9-H8 / 106.5 / 106.0 / H7-C4-C2 / 110.1 / 110.0
H11-O1-C2 / 116.2 / 116.0 / H8-C4-C2 / 110.4 / 110.2
O12-H11-O1 / 158.0 / 157.3 / H9-C4-C2 / 109.3 / 108.7
H13-O12-H11 / 106.7 / 106.1 / H10-C2-C4 / 110.8 / 111.3
H4-C2-O1-C3 / 180.0 / -179.9 / O11-H5-O1 / 144.6 / 144.9
H5-C3-C2-O1 / -0.2 / -0.6 / H12-O11-H5 / 116.0 / 120.9
H6-C3-C2-O1 / 122.1 / 121.3 / H13-O11-H12 / 106.8 / 106.5
H7-C3-C2-O1 / -122.5 / -122.6 / O14-H6-O3 / 176.0 / 176.3
H8-O1-C2-H4 / -0.2 / -3.2 / H15-O14-H6 / 118.1 / 120.3
O9-H8-O1-C2 / -0.4 / -5.4 / H16-O14-H15 / 106.4 / 105.9
H10-O9-H8-O1 / 177.7 / 163.3 / C4-C2-O1-O3 / 120.7 / 120.2
H11-O1-C2-H4 / 179.9 / 178.4 / H5-O1-C2-O3 / 55.5 / 57.9
O12-H11-O1-C2 / -0.4 / -5.4 / H6-O3-C2-C4 / 78.0 / 71.5
H13-O12-H11-O1 / 178.7 / 166.6 / H7-C4-C2-O1 / 60.3 / 60.6
H8-C4-C2-O1 / -179.6 / -179.1
H9-C4-C2-O1 / -59.4 / -59.0
H10-C2-C4-O1 / -121.6 / -121.8
O11-H5-O1-C2 / -43.2 / -38.4
H12-O11-H5-O1 / -96.8 / -103.2
H13-O11-H12-H5 / -82.2 / -85.2
O14-H6-O3-C2 / 124.4 / 18.0
H15-O14-H6-O3 / -21.8 / 85.4
H16-O14-H15-H6 / -136.7 / -140.4

Table S33:Optimized parameters for CH3CHO-(H2O)3 and CH3CH(OH)2-(H2O)3 at B3LYP/6-31++G(d,p) and MP2/6-31++G(d,p) theoretical levels.

Parameters / CH3CHO-(H2O)3 / Parameters / CH3CH(OH)2-(H2O)3
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.230 / 1.240 / C2-O1 / 1.408 / 1.409
C3-C2 / 1.495 / 1.492 / O3-C2 / 1.437 / 1.437
H4-C2 / 1.105 / 1.097 / C4-C2 / 1.517 / 1.508
H5-C3 / 1.091 / 1.086 / H5-O1 / 0.979 / 0.977
H6-C3 / 1.098 / 1.092 / H6-O3 / 0.977 / 0.975
H7-C3 / 1.098 / 1.092 / H7-C4 / 1.094 / 1.089
H8-O1 / 1.866 / 1.893 / H8-C4 / 1.094 / 1.089
O9-H8 / 0.980 / 0.976 / H9-C4 / 1.094 / 1.089
H10-O9 / 0.964 / 0.963 / H10-C2 / 1.102 / 1.097
H11-O1 / 1.950 / 1.972 / O11-H5 / 1.950 / 1.957
O12-H11 / 0.974 / 0.971 / H12-O11 / 0.965 / 0.963
H13-O12 / 0.964 / 0.963 / H13-O11 / 0.980 / 0.976
H14-O9 / 1.844 / 1.877 / O14-H6 / 1.863 / 1.879
O15-H14 / 0.980 / 0.975 / H15-O14 / 0.966 / 0.965
H16-O15 / 0.964 / 0.963 / H16-O14 / 0.966 / 0.965
C3-C2-O1 / 123.7 / 123.4 / H17-O1 / 1.894 / 1.899
H4-C2-O1 / 118.8 / 118.8 / O18-H17 / 0.976 / 0.973
H5-C3-C2 / 112.2 / 111.6 / H19-O18 / 0.964 / 0.963
H6-C3-C2 / 108.8 / 108.8 / O3-C2-O1 / 107.5 / 107.1
H7-C3-C2 / 108.6 / 108.6 / C4-C2-O1 / 108.5 / 108.1
H8-O1-C2 / 115.3 / 114.8 / H5-O1-C2 / 108.4 / 107.6
O9-H8-O1 / 164.7 / 164.1 / H6-O3-C2 / 109.0 / 107.6
H10-O9-H8 / 106.7 / 106.2 / H7-C4-C2 / 110.2 / 110.1
H11-O1-C2 / 116.6 / 116.7 / H8-C4-C2 / 110.1 / 109.8
O12-H11-O1 / 160.6 / 160.0 / H9-C4-C2 / 109.4 / 108.7
H13-O12-H11 / 106.6 / 106.1 / H10-C2-C4 / 109.9 / 110.0
H14-O9-H8 / 98.8 / 99.2 / O11-H5-O1 / 148.5 / 147.9
O15-H14-O9 / 159.9 / 159.0 / H12-O11-H5 / 119.1 / 123.5
H16-O15-H14 / 106.5 / 106.0 / H13-O11-H12 / 107.1 / 106.8
H4-C2-O1-C3 / -179.9 / -179.9 / O14-H6-O3 / 178.4 / 174.6
H5-C3-C2-O1 / 0.9 / 1.0 / H15-O14-H6 / 120.4 / 122.0
H6-C3-C2-O1 / 123.5 / 123.2 / H16-O14-H15 / 106.5 / 106.0
H7-C3-C2-O1 / -121.5 / -121.0 / H17-O1-H5 / 114.8 / 116.4
H8-O1-C2-H4 / -0.3 / -1.1 / O18-H17-O1 / 172.4 / 168.9
O9-H8-O1-C2 / 2.7 / 3.6 / H19-O18-H17 / 105.8 / 105.5
H10-O9-H8-O1 / -130.9 / -133.5 / C4-C2-O1-O3 / 121.1 / 120.5
H11-O1-C2-H4 / -179.8 / -179.4 / H5-O1-C2-O3 / 51.9 / 55.4
O12-H11-O1-C2 / 7.5 / 8.8 / H6-O3-C2-C4 / 78.4 / 72.5
H13-O12-H11-O1 / -168.7 / -161.2 / H7-C4-C2-O1 / 60.0 / 60.6
H14-O9-H8-H10 / 126.8 / 129.9 / H8-C4-C2-O1 / 179.9 / 180.9
O15-H14-O9-H10 / 116.8 / 111.6 / H9-C4-C2-O1 / 299.8 / 300.6
H16-O15-H14-O9 / 145.2 / 146.7 / H10-C2-C4-O1 / 121.5 / 121.9
O11-H5-O1-C2 / -40.9 / -36.8
H12-O11-H5-O1 / -99.6 / -106.0
H13-O11-H12-H5 / -86.5 / -88.8
O14-H6-O3-C2 / 137.7 / 19.1
H15-O14-H6-O3 / -37.7 / 82.2
H16-O14-H15-H6 / -140.5 / -146.8
H17-O1-H5-C2 / -128.8 / 124.8
O18-H17-O1-C2 / -3.0 / -0.2
H19-O18-H17-O1 / 145.9 / 157.4

Table S34:Optimized parameters for CH3CHO-(H2O)4 and CH3CH(OH)2-(H2O)4 at B3LYP/6-31++G(d,p) and MP2/6-31++G(d,p) theoretical levels.

Parameters / CH3CHO-(H2O)4 / Parameters / CH3CH(OH)2-(H2O)4
B3LYP / MP2 / B3LYP / MP2
C2-O1 / 1.233 / 1.241 / C2-O1 / 1.412 / 1.413
C3-C2 / 1.491 / 1.489 / O3-C2 / 1.437 / 1.437
H4-C2 / 1.105 / 1.097 / C4-C2 / 1.516 / 1.507
H5-C3 / 1.092 / 1.087 / H5-O1 / 0.979 / 0.978
H6-C3 / 1.099 / 1.092 / H6-O3 / 0.977 / 0.975
H7-C3 / 1.098 / 1.092 / H7-C4 / 1.094 / 1.089
H8-O1 / 1.878 / 1.903 / H8-C4 / 1.095 / 1.090
O9-H8 / 0.979 / 0.975 / H9-C4 / 1.094 / 1.089
H10-O9 / 0.964 / 0.963 / H10-C2 / 1.101 / 1.096
H11-O1 / 1.872 / 1.897 / O11-H5 / 1.930 / 1.935
O12-H11 / 0.978 / 0.975 / H12-O11 / 0.965 / 0.963
H13-O12 / 0.964 / 0.963 / H13-O11 / 0.980 / 0.977
H14-O9 / 1.845 / 1.879 / O14-H6 / 1.864 / 1.878
O15-H14 / 0.979 / 0.975 / H15-O14 / 0.966 / 0.965
H16-O15 / 0.964 / 0.963 / H16-O14 / 0.966 / 0.965
H17-O12 / 1.834 / 1.867 / H17-O1 / 1.805 / 1.813
O18-H17 / 0.979 / 0.975 / O18-H17 / 0.982 / 0.978
H19-O18 / 0.964 / 0.963 / H19-O18 / 0.965 / 0.963
C3-C2-O1 / 124.4 / 124.0 / H20-O18 / 1.830 / 1.854
H4-C2-O1 / 118.3 / 118.4 / O21-H20 / 0.980 / 0.976
H5-C3-C2 / 113.8 / 113.1 / H22-O21 / 0.964 / 0.963
H6-C3-C2 / 108.3 / 108.2 / O3-C2-O1 / 106.7 / 106.6
H7-C3-C2 / 108.4 / 108.4 / C4-C2-O1 / 109.1 / 108.6
H8-O1-C2 / 114.2 / 113.3 / H5-O1-C2 / 108.4 / 107.6
O9-H8-O1 / 164.5 / 163.8 / H6-O3-C2 / 109.0 / 107.6
H10-O9-H8 / 106.8 / 106.3 / H7-C4-C2 / 110.9 / 110.6
H11-O1-C2 / 128.8 / 129.0 / H8-C4-C2 / 109.6 / 109.4
O12-H11-O1 / 176.3 / 175.4 / H9-C4-C2 / 109.5 / 108.8
H13-O12-H11 / 106.5 / 106.0 / H10-C2-C4 / 110.9 / 111.4
H14-O9-H8 / 99.6 / 100.3 / O11-H5-O1 / 149.0 / 148.6
O15-H14-O9 / 159.6 / 158.6 / H12-O11-H5 / 119.8 / 124.2
H16-O15-H14 / 106.6 / 106.0 / H13-O11-H12 / 107.1 / 106.8
H17-O12-H11 / 103.4 / 103.7 / O14-H6-O3 / 178.6 / 175.0
O18-H17-O12 / 163.7 / 162.8 / H15-O14-H6 / 121.7 / 123.9
H19-O18-H17 / 106.3 / 105.9 / H16-O14-H15 / 106.5 / 106.0
H4-C2-O1-C3 / 179.9 / 179.9 / H17-O1-H5 / 115.4 / 115.1
H5-C3-C2-O1 / -1.3 / -2.6 / O18-H17-O1 / 176.8 / 175.4
H6-C3-C2-O1 / 121.5 / 119.9 / H19-O18-H17 / 106.2 / 105.7
H7-C3-C2-O1 / -124.3 / -125.1 / H20-O18-H17 / 103.8 / 103.9
H8-O1-C2-H4 / -2.2 / -3.0 / O21-H20-O18 / 168.8 / 167.2
O9-H8-O1-C2 / -1.7 / -2.1 / H22-O21-H20 / 106.0 / 105.6
H10-O9-H8-O1 / 133.5 / 137.3 / C4-C2-O1-O3 / 121.3 / 120.7
H11-O1-C2-H4 / -178.1 / -177.5 / H5-O1-C2-O3 / 52.4 / 55.3
O12-H11-O1-C2 / 0.9 / 1.4 / H6-O3-C2-C4 / 73.3 / 69.9
H13-O12-H11-O1 / -130.0 / -130.9 / H7-C4-C2-O1 / 63.4 / 64.8
H14-O9-H8-H10 / -128.0 / -131.6 / H8-C4-C2-O1 / -177.2 / -176.0
O15-H14-O9-H10 / -117.8 / -120.2 / H9-C4-C2-O1 / -57.8 / -56.7
H16-O15-H14-O9 / -145.1 / -145.4 / H10-C2-C4-O1 / -120.9 / -121.1
H17-O12-H11-H13 / 126.7 / 129.0 / O11-H5-O1-C2 / -38.6 / -34.9
O18-H17-O12-H11 / -3.7 / -4.4 / H12-O11-H5-O1 / -101.9 / -108.1
H19-O18-H17-O12 / 142.2 / 143.9 / H13-O11-H12-H5 / -87.6 / -90.0
O14-H6-O3-C2 / 84.3 / 14.9
H15-O14-H6-O3 / 19.3 / 88.7
H16-O14-H15-H6 / -144.1 / -152.1
H17-O1-H5-C2 / -144.3 / -139.1
O18-H17-O1-C2 / -24.4 / -17.9
H19-O18-H17-O1 / 146.9 / 140.7
H20-O18-H17-H19 / -122.0 / -126.6
O21-H20-O18-H17 / 14.6 / 13.5
H22-O21-H20-O18 / -143.2 / -141.8

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