Molecular mechanics, molecular dynamics and semi empirical quantum chemical method have been used to study the geometric and electronic structures of six phosphonate ester as rare earth extractants. The results show ...Molecular mechanics, molecular dynamics and semi empirical quantum chemical method have been used to study the geometric and electronic structures of six phosphonate ester as rare earth extractants. The results show that the phosphorus atom exhibits sp 3 hybridization. The structures of the extractants are determined by the repulsion of the hydrocarbon groups. In the extractants that have two 2 ethyl hexyl groups, one 2 ethyl hexyl extends straight, and the other extends twistily. When the number of oxygen atom decreases, the negative charge of the phosphoryl oxygen atom increases, but the negative charge of oxygen atom and the positive charge of hydrogen of the hydroxyl group decreases, and the energies of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital(LUMO) increase. The energies of the occupied frontier orbitals are close to each other.展开更多
The alcoholysis mechanism of 1,2-thiazetidine-1,1-dioxide with methanol, in which the relatively stable product is sulfonate ester, has been investigated by quantum chemical method. Our calculations indicate the react...The alcoholysis mechanism of 1,2-thiazetidine-1,1-dioxide with methanol, in which the relatively stable product is sulfonate ester, has been investigated by quantum chemical method. Our calculations indicate the reaction for alcoholysis of 1,2-thiazetidine-1,1-dioxide proceeds via two possible mechanisms: concerted and stepwise. In the stepwise mechanism, two possible reaction pathways can be followed while only one possible reaction pathway can be followed in the concerted mechanism.展开更多
The electronic structures of the species Ni(DMG)_2, (Ni(DMG)_2)^- and (Ni(DMG)_2)_(2-) have been studied by INDO quantum chemical method. The results have clearly shown that in the first stage of the electroreduction ...The electronic structures of the species Ni(DMG)_2, (Ni(DMG)_2)^- and (Ni(DMG)_2)_(2-) have been studied by INDO quantum chemical method. The results have clearly shown that in the first stage of the electroreduction of Ni(DMG)_2, one electron interacts with the d orbitals on the nickel atom, while in the further stage the second electron interacts with the p orbitals on the nitrogen atoms. It conforms with our electrochemical experimental studies which showed that not only Ni(Ⅱ) is reduced but also DMG is catalytically reduced during the reduction of Ni(DMG)_2.展开更多
An interactive web tool,PredPotS,has been developed for predicting one-electron standard reduction potentials of organic molecules in aqueous solutions.The predictions are generated using deep learning models trained ...An interactive web tool,PredPotS,has been developed for predicting one-electron standard reduction potentials of organic molecules in aqueous solutions.The predictions are generated using deep learning models trained and validated on a chemically diverse database comprising reduction potentials of approximately 8000 organic compounds.The reduction potentials of this database were computed using a composite computational protocol that combines the semiempirical quantum chemical method(GFN2-xTB)and awell-established DFT approach(M06-2X functional along with the SMD solvent model).While this computational approach is cost-effective,it is subject to certain limitations,which are nonetheless duly accounted for in the development of the database.The applied graph-based deep learning methods perform remarkably well in terms of the standard performance metrics.By entering or uploading the SMILES codes of the molecules,PredPotS provides fast and sensible predictions for one-electron standard reduction potentials for a diverse set of organic molecules also in the range compatible with the electrochemical stability of aqueous electrolytes.The PredPotS web tool is particularly well-suited for screening redox-active candidates for aqueous organic redox flow batteries,but it may also prove useful in a variety of other electrochemical applications.展开更多
文摘Molecular mechanics, molecular dynamics and semi empirical quantum chemical method have been used to study the geometric and electronic structures of six phosphonate ester as rare earth extractants. The results show that the phosphorus atom exhibits sp 3 hybridization. The structures of the extractants are determined by the repulsion of the hydrocarbon groups. In the extractants that have two 2 ethyl hexyl groups, one 2 ethyl hexyl extends straight, and the other extends twistily. When the number of oxygen atom decreases, the negative charge of the phosphoryl oxygen atom increases, but the negative charge of oxygen atom and the positive charge of hydrogen of the hydroxyl group decreases, and the energies of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital(LUMO) increase. The energies of the occupied frontier orbitals are close to each other.
文摘The alcoholysis mechanism of 1,2-thiazetidine-1,1-dioxide with methanol, in which the relatively stable product is sulfonate ester, has been investigated by quantum chemical method. Our calculations indicate the reaction for alcoholysis of 1,2-thiazetidine-1,1-dioxide proceeds via two possible mechanisms: concerted and stepwise. In the stepwise mechanism, two possible reaction pathways can be followed while only one possible reaction pathway can be followed in the concerted mechanism.
基金Project supported by the National Natural Science Foundstion of China.
文摘The electronic structures of the species Ni(DMG)_2, (Ni(DMG)_2)^- and (Ni(DMG)_2)_(2-) have been studied by INDO quantum chemical method. The results have clearly shown that in the first stage of the electroreduction of Ni(DMG)_2, one electron interacts with the d orbitals on the nickel atom, while in the further stage the second electron interacts with the p orbitals on the nitrogen atoms. It conforms with our electrochemical experimental studies which showed that not only Ni(Ⅱ) is reduced but also DMG is catalytically reduced during the reduction of Ni(DMG)_2.
基金funded by the European Union’s Horizon 2020 research and innovation programme under grant agreement No 875565 (CompBat project).
文摘An interactive web tool,PredPotS,has been developed for predicting one-electron standard reduction potentials of organic molecules in aqueous solutions.The predictions are generated using deep learning models trained and validated on a chemically diverse database comprising reduction potentials of approximately 8000 organic compounds.The reduction potentials of this database were computed using a composite computational protocol that combines the semiempirical quantum chemical method(GFN2-xTB)and awell-established DFT approach(M06-2X functional along with the SMD solvent model).While this computational approach is cost-effective,it is subject to certain limitations,which are nonetheless duly accounted for in the development of the database.The applied graph-based deep learning methods perform remarkably well in terms of the standard performance metrics.By entering or uploading the SMILES codes of the molecules,PredPotS provides fast and sensible predictions for one-electron standard reduction potentials for a diverse set of organic molecules also in the range compatible with the electrochemical stability of aqueous electrolytes.The PredPotS web tool is particularly well-suited for screening redox-active candidates for aqueous organic redox flow batteries,but it may also prove useful in a variety of other electrochemical applications.
