title: Charge-transfer interactions between TCNQ and silver clusters Ag20 and Ag13.
abstract: Interactions between tetracyanoquinodimethane (TCNQ) and two typical silver clusters Ag13 and Ag20 are studied by first-principles DFT calculations. Charge transfer (CT) from silver clusters to TCNQ molecules initiates the Ag-N bond formation at selective sites resulting in the formation of different isomers of Ag13-TCNQ and Ag20-TCNQ complexes. We show here a comprehensive spectroscopic analysis for the two CT complexes on the basis of Raman and infrared activities. Furthermore, frontier molecular orbital (FMO) and natural bond orbital (NBO) analysis of the complexes provides a vivid illustration of electron cloud overlap and interactions. The behavior of TCNQ adsorbed on the tetrahedral Ag20 cluster was even found in good agreement with the experimental measurement of TCNQ molecules on a single-crystal Ag(111) surface. This study not only endeavors to clarify the charge-transfer interactions of TCNQ with silver, but also presents a finding of enhanced charge transfer between Ag13 and TCNQ indicating potential for candidate building blocks of granular materials.
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Photochemistry, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China. zxluo@iccas.ac.cn jnyao@iccas.ac.cn.
authors.forename: Jing
authors.initials: J
authors.lastname: Chen
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Photochemistry, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China. zxluo@iccas.ac.cn jnyao@iccas.ac.cn.
authors.forename: Hanyu
authors.initials: H
authors.lastname: Zhang
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Photochemistry, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China. zxluo@iccas.ac.cn jnyao@iccas.ac.cn.
authors.forename: Xianhu
authors.initials: X
authors.lastname: Liu
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Photochemistry, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China. zxluo@iccas.ac.cn jnyao@iccas.ac.cn.
authors.forename: Chengqian
authors.initials: C
authors.lastname: Yuan
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Photochemistry, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China. zxluo@iccas.ac.cn jnyao@iccas.ac.cn.
authors.forename: Meiye
authors.initials: M
authors.lastname: Jia
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Photochemistry, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China. zxluo@iccas.ac.cn jnyao@iccas.ac.cn.
authors.forename: Zhixun
authors.initials: Z
authors.lastname: Luo
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Photochemistry, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China. zxluo@iccas.ac.cn jnyao@iccas.ac.cn.
authors.forename: Jiannian
authors.initials: J
authors.lastname: Yao