title: Oscillation of absorption bands of Zn(1-x)Mn(x)S clusters: an experimental and theoretical study.
abstract: Electroporation of synthetic vesicles is utilized for the preparation of molecular size uncapped Zn(1-x)Mn(x)S clusters. The absence of caps permits (i) continued growth of the Zn(1-x)Mn(x)S clusters formed, (ii) the assessment of their true absorption spectra unaltered by stabilizing ligands, and (iii) the previously inaccessible live observation of the growth of the clusters in the molecular size regime. Upon cluster growth, the UV spectra exhibit novel, time-dependent, oscillation of red and blue shifts of the characteristic absorption band. The structure and electronic properties of Zn(N-1)MnS(N) clusters with N = 1-9 are calculated using the first-principles DMol(3) package. On the basis of similarities between the oscillating trend of the experimentally observed absorption spectra and that of the calculated highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap of Zn(N-1)MnS(N) clusters with N = 1-9, the wavelengths of the sequential spectral peaks can be assigned to Zn(2)MnS(3), Zn(3)MnS(4), Zn(4)MnS(5), Zn(6)MnS(7), and Zn(8)MnS(9), respectively. Our results demonstrate that both the cluster size and the composition can be used to tune the optical properties.
authors.affiliation: Laboratory of Special Functional Materials, Henan University, Kaifeng 475001, People's Republic of China. Center for Colloidal and Interfacial Dynamics, Department of Chemistry and Biochemistry, University of Texas at Arlington, Arlington, TX 76019-0065, USA.
authors.forename: Sixin
authors.initials: S
authors.lastname: Wu
authors.forename: Heying
authors.initials: H
authors.lastname: Chu
authors.forename: Hongtao
authors.initials: H
authors.lastname: Xu
authors.forename: Xinshou
authors.initials: X
authors.lastname: Wang
authors.forename: Na
authors.initials: N
authors.lastname: Yuan
authors.forename: Yuncai
authors.initials: Y
authors.lastname: Li
authors.forename: Zhishen
authors.initials: Z
authors.lastname: Wu
authors.forename: Zuliang
authors.initials: Z
authors.lastname: Du
authors.forename: Zoltan A
authors.initials: ZA
authors.lastname: Schelly