Tran Van Tan, Tran Quoc Tri
Theoretical and Physical Chemistry Division, Dong Thap University , 783-Pham Huu Lau, Ward 6, Cao Lanh City, Dong Thap Vietnam.
J Phys Chem A. 2016 May 26;120(20):3670-6. doi: 10.1021/acs.jpca.6b02631. Epub 2016 May 9.
The B3LYP functional and CASPT2 method have been applied to investigate the geometrical and electronic structures of η(2)-(S2)MnS(-/0), η(2)-(S3)Mn(-/0), and MnS3(-/0) isomers of MnS3(-/0) clusters. The ground state of the anionic cluster is computed to be the (5)B2 of η(2)-(S2)MnS(-) isomer, whereas that of the anionic cluster is calculated to be the (4)B1 of the same isomer. The photoelectron spectrum of MnS3(-) cluster is interpreted by electron detachment processes from the most stable η(2)-(S2)MnS(-) and from the metastable η(2)-(S3)Mn(-) and MnS3(-) isomers. The first and second bands with low intensities are, respectively, attributed to the (7)A' → (6)A' and (7)A' → (8)A' transitions within the η(2)-(S3)Mn(-/0) isomers. The third band with the highest intensity in the spectrum can be assigned to the (5)B2 → (4)B1, (5)B2 → (6)B1, and (5)B2 → (4)A2 transitions within the most stable η(2)-(S2)MnS(-/0) isomers, the (3)B1 → (2)A1 transition within the metastable MnS3(-/0) isomers, and the (7)A' → 3(6)A' transition within the metastable η(2)-(S3)Mn(-/0) isomers. Because the η(2)-(S2)MnS(-) is computed to be the most stable isomer of the MnS3(-) cluster, we believe that the highest intensity third band in the spectrum is mainly the result of electron detachments from this isomer.
采用B3LYP泛函和CASPT2方法研究了MnS3(-/0)团簇的η(2)-(S2)MnS(-/0)、η(2)-(S3)Mn(-/0)和MnS3(-/0)异构体的几何结构和电子结构。计算得出阴离子团簇的基态为η(2)-(S2)MnS(-)异构体的(5)B2，而阴离子团簇的基态计算为同一异构体的(4)B1。MnS3(-)团簇的光电子能谱通过从最稳定的η(2)-(S2)MnS(-)以及亚稳的η(2)-(S3)Mn(-)和MnS3(-)异构体的电子脱离过程来解释。强度较低的第一和第二条谱带分别归因于η(2)-(S3)Mn(-/0)异构体中的(7)A'→(6)A'和(7)A'→(8)A'跃迁。光谱中强度最高的第三条谱带可归因于最稳定的η(2)-(S2)MnS(-/0)异构体中的(5)B2→(4)B1、(5)B2→(6)B1和(5)B2→(4)A2跃迁，亚稳的MnS3(-/0)异构体中的(3)B1→(2)A1跃迁，以及亚稳的η(2)-(S3)Mn(-/0)异构体中的(7)A'→3(6)A'跃迁。由于计算得出η(2)-(S2)MnS(-)是MnS3(-)团簇最稳定的异构体，我们认为光谱中强度最高的第三条谱带主要是该异构体电子脱离的结果。
