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| DFT Study of Mono-Manganese-Substituted Keggin-Type Polyoxometalates with Atmospheric Small Molecules X (X=H2O, N2, O2, NO, N2O, CO and CO2) |
| Author Name | Affiliation | E-mail | | LIU Chun-Guang | College of Chemical Engineering, Northeast Electric Power University, Jilin, Jilin 132012, China | liucg407@163.com | | ZHANG Han-Yu | College of Chemical Engineering, Northeast Electric Power University, Jilin, Jilin 132012, China | | | JIANG Meng-Xu | College of Chemical Engineering, Northeast Electric Power University, Jilin, Jilin 132012, China | |
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| Abstract: Geometries, electronic structure, and bonding nature of a series of mono-manganese-substituted Keggin-type (POMs) with atmospheric small molecules X (X=H2O, N2, O2, NO, N2O, CO and CO2) have been studied based on density functional theory (DFT) method with M06L functional. Due to the poly-anionic nature of polyoxometalates (POMs), the counterions effects have firstly been considered by means of a full treatment of the cesium salt Cs4[PW11O39MnⅢH2O]. DFT-M06L calculations show that the key geometric a nd electronic parameters are almost constants as change of the four Cs counterions. The optimized calculations for[PW11O39MnⅢH2O]4-both in gas phase and solution provide an analogous result, no significant variation of key geometric and electronic parameters was found when compared with the cesium salt. The calculated relative energy of different spin states indicates that the lowest energy spin state is the high-spin quintet state for[PW11O39MnⅢX]4-(X=H2O, N2, N2O, CO and CO2), triplet state for[PW11O39MnⅢO2]4-, and doublet state for[PW11O39MnⅢNO]4-. The calculated adsorption energy of those atmospheric small molecules over the porphyrin-like POM ligand increases in the following order:N2 < N2O < CO≈CO2 < O2 < H2O < NO. The Mn-NO POM complex provides considerable adsorption energy. Mulliken population analysis shows that coordination of NO ligand to the MnⅢ center in its doublet ground state arises from an antiferromagnetic coupling between an intermediate-spin MnⅢ center and NO· unit. |
| Keywords: density functional theory electronic configuration polyoxometalates atmospheric small molecules |
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| LIU Chun-Guang,ZHANG Han-Yu,JIANG Meng-Xu.DFT Study of Mono-Manganese-Substituted Keggin-Type Polyoxometalates with Atmospheric Small Molecules X (X=H2O, N2, O2, NO, N2O, CO and CO2)[J].Chinese Journal of Inorganic Chemistry,2018,34(6):1127-1136. |
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