State Key laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001, PR China.
Chemphyschem. 2013 Apr 15;14(6):1182-9. doi: 10.1002/cphc.201201043. Epub 2013 Mar 7.
The structures and energies of the electronic ground states of the FeS(0/-), FeS2(0/-), Fe2S2(0/-), Fe3S4(0/-), and Fe4S4(0/-) neutral and anionic clusters have been computed systematically with nine computational methods in combination with seven basis sets. The computed adiabatic electronic affinities (AEA) have been compared with available experimental data. Most reasonable agreements between theory and experiment have been found for both hybrid B3LYP and B3PW91 functionals in conjugation with 6-311+G* and QZVP basis sets. Detailed comparisons between the available experimental and computed AEA data at the B3LYP/6-311+G* level identified the electronic ground state of (5)Δ for FeS, (4)Δ for FeS(-), (5)B2 for FeS2, (6)A1 for FeS2(-), (1)A1 for Fe2S2, (8)A' for Fe2S2(-), (5)A'' for Fe3S4, (6)A'' for Fe3S4(-), (1)A1 for Fe4S4, and (1)A2 for Fe4S4(-). In addition, Fe2S2, Fe3S4, Fe3S4(-), Fe4S4, and Fe4S4(-) are antiferromagnetic at the B3LYP/6-311+G* level. The magnetic properties are discussed on the basis of natural bond orbital analysis.
系统地使用九种计算方法和七种基组计算了 FeS(0/-)、FeS2(0/-)、Fe2S2(0/-)、Fe3S4(0/-)和 Fe4S4(0/-)中性和阴离子团簇的电子基态结构和能量。将计算得到的绝热电子亲和能（AEA）与可用的实验数据进行了比较。对于 B3LYP 和 B3PW91 泛函与 6-311+G和 QZVP 基组相结合，理论与实验之间存在最合理的一致性。在 B3LYP/6-311+G水平上，对可用的实验和计算 AEA 数据进行详细比较，确定了 FeS 的电子基态为(5)Δ，FeS(-)的电子基态为(4)Δ，FeS2 的电子基态为(5)B2，FeS2(-)的电子基态为(6)A1，Fe2S2 的电子基态为(1)A1，Fe2S2(-)的电子基态为(8)A'，Fe3S4 的电子基态为(5)A''，Fe3S4(-)的电子基态为(6)A''，Fe4S4 的电子基态为(1)A1，Fe4S4(-)的电子基态为(1)A2。此外，在 B3LYP/6-311+G*水平上，Fe2S2、Fe3S4、Fe3S4(-)、Fe4S4 和 Fe4S4(-) 均为反铁磁性。基于自然键轨道分析讨论了磁性性质。
