Ab Initio Studies on the Preferred Site of Protonation in Cytisine in the Gas Phase and Water
Abstract
:Introduction
Computational Details
Results and Discussion
1. Preferred Structures for Isolated and Solvated Neutral Molecules
Compound | Method | Phase | ΔE | ΔG | Preferred Conformation |
---|---|---|---|---|---|
1 | HF/6-31G*b | gas | -0.365 | -0.315 | 1a |
HF/6-311G**c | gas | -0.435 | -0.58 | 1a | |
MP2/6-31G*b | gas | -0.005 | 1a | ||
MP2/6-311G**c | gas | -0.11 | 1a | ||
DFT(B3LYP)/6-31G*b | gas | 0.29 | 1b | ||
DFT(B3LYP)/6-311G**c | gas | 0.08 | 1b | ||
PCMb | water | -0.66 | 1a | ||
PCMc | water | -0.78 | 1a | ||
2 | HF/6-31G*b | gas | 0.63 | 0.10 | 2b |
HF/6-311G**c | gas | 0.58 | 1.30 | 2b | |
MP2/6-31G*b | gas | 0.79 | 2b | ||
MP2/6-311G**c | gas | 0.85 | 2b | ||
DFT(B3LYP)/6-31G*b | gas | 0.55 | 2b | ||
DFT(B3LYP)/6-311G**c | gas | 0.41 | 2b | ||
PCMb | water | 1.00 | 2b | ||
PCMc | water | 0.80 | 2b | ||
3 | HF/6-31G* b | gas | -0.82 | -0.66 | 3a |
HF/6-311G**c | gas | -0.88 | -0.71 | 3a | |
MP2/6-31G*b | gas | -0.49 | 3a | ||
MP2/6-311G**c | gas | -0.53 | 3a | ||
DFT(B3LYP)/6-31G*b | gas | -0.30 | 3a | ||
DFT(B3LYP)/6-311G**c | gas | -0.55 | 3a | ||
PCMb | water | -0.33 | 3a | ||
PCMc | water | -0.42 | 3a |
2. Geometrical Parameters
3. Possible Basic Sites
4. Favoured Site of Protonation in the Gas Phase
Isomer | Method | -Eprot/gas | ||||
---|---|---|---|---|---|---|
Osp | Oap | Npyr | Npip | |||
1a | HF/6-31G*c | 239.5 | 244.7 | 203.4 | 236.3 | 8.4 |
HF/6-311G**d | 242.0 | 247.2 | 204.7 | 237.4 | 9.8 | |
MP2/6-31G*c | 235.2 | 239.9 | 199.3 | 233.7 | 6.2 | |
MP2/6-311G**d | 238.1 | 242.4 | 201.1 | 233.6 | 8.8 | |
DFT(B3LYP)/6-31G*c | 237.5 | 241.9 | 201.4 | 234.4 | 7.5 | |
DFT(B3LYP)/6-311G**d | 237.5 | 241.8 | 200.5 | 233.2 | 8.6 | |
1b | HF/6-31G*c | 233.9 | 239.4 | 197.9 | 236.7 | 2.7 |
HF/6-311G**d | 236.8 | 242.2 | 199.6 | 237.9 | 4.3 | |
MP2/6-31G*c | 229.2 | 234.2 | 193.4 | 233.7 | 0.5 | |
MP2/6-311G**d | 232.5 | 237.1 | 195.8 | 233.7 | 3.4 | |
DFT(B3LYP)/6-31G*c | 232.7 | 237.4 | 196.3 | 234.1 | 3.3 | |
DFT(B3LYP)/6-311G**d | 233.0 | 237.6 | 195.7 | 233.1 | 4.5 |
Isomer | Method | -Eprot/gas | |||
---|---|---|---|---|---|
Osp(2) | Oap(2) | Npip(3) | |||
a | HF/6-31G*c | 230.4 | 234.7 | 241.4 | 6.7 |
HF/6-311G**d | 232.7 | 237.0 | 242.7 | 5.7 | |
MP2/6-31G*c | 225.8 | 229.8 | 238.2 | 8.4 | |
MP2/6-311G**d | 229.0 | 232.9 | 238.2 | 5.3 | |
DFT(B3LYP)/6-31G*c | 228.0 | 231.7 | 239.3 | 7.6 | |
DFT(B3LYP)/6-311G**d | 227.7 | 231.5 | 238.1 | 6.6 | |
b | HF/6-31G*c | 229.8 | 235.0 | 242.2 | 7.2 |
HF/6-311G**d | 232.1 | 237.4 | 243.5 | 6.1 | |
MP2/6-31G*c | 225.0 | 230.2 | 238.7 | 8.5 | |
MP2/6-311G**d | 228.1 | 233.1 | 238.8 | 5.7 | |
DFT(B3LYP)/6-31G*c | 227.4 | 232.1 | 239.6 | 7.5 | |
DFT(B3LYP)/6-311G**d | 227.3 | 232.0 | 238.6 | 6.6 |
Method | PA | ΔPAb | GB | |||
---|---|---|---|---|---|---|
Oap(2b) | Npip(3a) | Oap(2b) | Npip(3a) | |||
Experiment | 221.3 | 228.0 | 6.7 | 213.9 | 220.1 | 6.2 |
HF/6-31G*c | 224.8 | 229.6 | 4.8 | 217.0 | 222.0 | 5.0 |
HF/6-311G**d | 227.0 | 230.9 | 3.9 | 218.9 | 223.3 | 4.4 |
MP2/6-31G*c | 220.0 | 226.5 | 6.5 | 212.2 | 218.9 | 6.7 |
MP2/6-311G**d | 222.7 | 226.4 | 3.7 | 214.6 | 218.8 | 4.2 |
DFT(B3LYP)/6-31G*c | 221.9 | 227.5 | 5.6 | 214.1 | 219.9 | 5.8 |
DFT(B3LYP)/6-311G**d | 221.6 | 226.3 | 4.7 | 213.5 | 218.7 | 5.2 |
5. Basic Site Preference in Water
Site | -Eprot/aq | |||||
---|---|---|---|---|---|---|
1a | 1b | 2a | 2b | 3a | 3b | |
Oap | 28.0 | 27.0 | 26.2 | 26.2 | ||
Osp | 24.1 | 22.8 | 23.7 | 22.7 | ||
Npip | 37.8 | 38.5 | 44.9 | 45.2 |
Acknowledgments
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Raczyńska, E.D.; Makowski, M.; Górnicka, E.; Darowska, M. Ab Initio Studies on the Preferred Site of Protonation in Cytisine in the Gas Phase and Water. Int. J. Mol. Sci. 2005, 6, 143-156. https://doi.org/10.3390/i6010143
Raczyńska ED, Makowski M, Górnicka E, Darowska M. Ab Initio Studies on the Preferred Site of Protonation in Cytisine in the Gas Phase and Water. International Journal of Molecular Sciences. 2005; 6(1):143-156. https://doi.org/10.3390/i6010143
Chicago/Turabian StyleRaczyńska, Ewa D., Mariusz Makowski, Elżbieta Górnicka, and Małgorzata Darowska. 2005. "Ab Initio Studies on the Preferred Site of Protonation in Cytisine in the Gas Phase and Water" International Journal of Molecular Sciences 6, no. 1: 143-156. https://doi.org/10.3390/i6010143