Citation: 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. doi: 10.11862/CJIC.2018.143 shu

DFT Study of Mono-Manganese-Substituted Keggin-Type Polyoxometalates with Atmospheric Small Molecules X (X=H₂O, N₂, O₂, NO, N₂O, CO and CO₂)

College of Chemical Engineering, Northeast Electric Power University, Jilin, Jilin 132012, China

Corresponding author: LIU Chun-Guang, liucg407@163.com
Received Date: 24 October 2017
Revised Date: 13 February 2018

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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[PW₁₁O₃₉Mn^ⅢH₂O]. 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[PW₁₁O₃₉Mn^ⅢH₂O]^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[PW₁₁O₃₉Mn^ⅢX]^4-(X=H₂O, N₂, N₂O, CO and CO₂), triplet state for[PW₁₁O₃₉Mn^ⅢO₂]^4-, and doublet state for[PW₁₁O₃₉Mn^ⅢNO]^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 Mn^Ⅲ center in its doublet ground state arises from an antiferromagnetic coupling between an intermediate-spin Mn^Ⅲ center and NO^· unit.
- density functional theory,
- electronic configuration,
- polyoxometalates,
- atmospheric small molecules
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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)

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通讯作者: 陈斌, bchen63@163.com

DFT Study of Mono-Manganese-Substituted Keggin-Type Polyoxometalates with Atmospheric Small Molecules X (X=H₂O, N₂, O₂, NO, N₂O, CO and CO₂)