Theoretical study of manganese hydrides and halides, MnX_n with X = H, F, Cl, Br and n = 1-4

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• 作者：Pham Vu Nhat^a ; ^b ; Ngo Tuan Cuong^a ; Pham Khac Duy^c ; Minh Tho Nguyen^a ; ^d ; ^{minh.nguyen@chem.kuleuven.be}
• 关键词：Manganese hydrides ; Manganese halides ; Manganese fluorides ; Manganese chlorides ; Manganese bromides
• 刊名：Chemical Physics
• 出版年：2012
• 出版时间：25 May, 2012
• 年：2012
• 卷：400
• 期：Complete
• 页码：185-197
• 全文大小：1916 K

文摘

Properties of a series of MnX_n with X = H, F, Cl, Br and n = 1-4 are investigated using DFT, CCSD(T) and CASPT2 computations. The B3P86/6-311++G(3df,2d) method appears to be suitable for predicting their structures whose geometries and IR spectra are dependent on the charge state. While MnX₂ are linear, MnX₃ and MnX₄ are characterized by high symmetry shape. The ¦Ð-bonding type is observed for and . In halides, a different type of bonds is formed as p-orbitals of halogens can overlap with empty metal d-orbitals allowing a more effective electron transfer and high spin ground electronic states. Vibrational frequencies and basic energetic quantities are computed and compared with available experiments. Several previous thermochemical quantities are re-evaluated, and the heats of formation of Mn-compounds can be determined with reasonable accuracy using the B3LYP functional. However, while calculated ionization energies are in agreement with experiment, electron affinities are obtained with large deviations.