Table 3. Adsorption Energies (Eads and EadsGD3(BJ)) Computed with and without Considering the Empirical Dispersion and Short Intermolecular Distances in the Presence of Watera.
| species | short intermolecular distances (Å) | Eads (kJ/mol) | EadsGD3(BJ) (kJ/mol) | BSSE (kJ/mol) | ||
|---|---|---|---|---|---|---|
| (1) Physisorption | ||||||
| T1 (OH) | H2O-AC-4NP(OH) | (AC) CH---O (H2O) | 2.235 | –25 | –43 | 2.60 |
| (AC) C---HC (4NP) | 2.367 | |||||
| (AC) C---HO (4NP) | 2.115 | |||||
| T2 (OH) | H2O-AC-2NP(OH) | (AC) C---H (H2O) | 1.962 | –10 | –56 | 2.60 |
| (2NP) NO2---H (H2O) | 2.175 | |||||
| (AC) C---HO (2NP) | 3.184 | |||||
| T3 | H2O-AC-9NAnt | (AC) CH---O1 (NO2-9NAnt) | 2.534 | –15 | –93 | 1.57 |
| (AC) CH---O2 (NO2-9NAnt) | 2.592 | |||||
| (AC) C---H (H2O) | 1.926 | |||||
| T4 (NO2) | H2O-AC-4NP(NO2) | (AC) C---H (H2O) | 1.939 | –19 | –38 | 2.60 |
| (4NP) NO2---H (H2O) | 2.189 | |||||
| (4NP) CH---O (H2O) | 2.206 | |||||
| (AC) C---H (4NP) | 4.303 | |||||
| T5 (NO2) | H2O-AC-2NP(NO2) | (AC) C---H (H2O) | 1.928 | –13 | –20 | 1.80 |
| (2NP-O2N) O1---HC (AC) | 2.591 | |||||
| (2NP-O2N) O2---HC (AC) | 2.593 | |||||
| (2) Simultaneous complete and partial chemical adsorptions | ||||||
| T6 (OH) | H2O-AC-4NP | (AC) C–O (H2O) | 1.369 | –456 | –495 | 10.23 |
| (AC) C–H (H2O) | 1.085 | |||||
| (AC) C–CH (4NP) | 1.534 | |||||
| (AC) C–HO (4NP) | 1.084 | |||||
| T7 (OH) | H2O-AC-2NP | (AC) C–O (H2O) | 1.371 | –487 | –514 | 11.28 |
| (AC) C–H (H2O) | 1.082 | |||||
| (AC) C–O (OH–2NP) | 1.386 | |||||
| (AC) C–H (OH–2NP) | 1.083 | |||||
| T8 (NO2) | H2O-AC-9NAnt | (AC) C–O (H2O) | 1.345 | –300 | –362 | 7.30 |
| (AC) C–H (H2O) | 1.085 | |||||
| (AC) C–O (NO2-9NAnt) | 1.234 | |||||
| (9NAnt) H---O (9NAnt-AC) | 2.409 | |||||
| (9NAnt) H---C (AC) | 3.125 | |||||
| (AC-H2O) OH---CH (9NAnt) | 2.912 | |||||
| (3) Capture of the pollutant by the water molecule | ||||||
| T9 (OH) | AC-H2O-4NP | (AC-H2O) HO---HO (OH-4NP) | 1.851 | –29 | –69 | 2.62 |
| (AC) CH---OH (OH-4NP) | 3.118 | |||||
| (AC) C---HC (4NP) | 3.295 | |||||
| (AC) C–O (H2O) | 1.390 | |||||
| (AC) C–H (H2O) | 1.084 | |||||
| T10 (OH) | AC-H2O-2NP | (AC-H2O) H---O (NO2-2NP) | 1.977 | –25 | –32 | 2.36 |
| (AC) CH---O (NO2-2NP) | 2.654 | |||||
| (AC) C–O (H2O) | 1.361 | |||||
| (AC) C–H (H2O) | 1.086 | |||||
| T11 (NO2) | AC-H2O-9NAnt | (AC-H2O) H---O (NO2-9NAnt) | 1.933 | –27 | –79 | 2.60 |
| (AC) C–O (H2O) | 1.359 | |||||
| (AC) C–H (H2O) | 1.086 | |||||
a
Estimation of the superposition basis set error (BSSE) on the energy. Dotted (---) refers to the physical interactions and direct line (−) refers to a covalent bound.