Theoretical Study of Alkali-metal Doping Effects on the Electronic Structure and Electronic Thermoelectric Response of Poly[Ni-ett] Coordination Polymer Chains

Abstract

Alkali-metal doping is an effective chemical strategy for tuning the electronic structure of coordination polymers. In this work, single-chain models of alkali-metal doped poly[Ax (Ni-ett)] (A=Li, Na, K; ett=ethene-1,1,2,2-tetrathiolate) were constructed, and their structural stability, electronic structure, and electronic thermoelectric response were investigated using the first-principles density functional theory combined with nonequilibrium Green’s function method. Calculation results show that alkali-metal atoms donate electrons to the Ni-ett backbone and regulate the local coordination environment through structural relaxation and dopant-backbone orbital hybridization. These chemical effects reshape the electronic states near the Fermi level and further regulate the coherent electronic transport channels along the chain. Among the three dopants, K gives more favorable binding with the Ni-ett framework and preserves higher electronic transmission in selected valence-band energy windows than Li and Na. For the x =1/3 K-doped model, the optimized electronic structure leads to a pronounced electronic power factor and a relatively high electronic figure of merit ZT_e, with a maximum value of approximately 0.13. This study clarifies the atomic-scale relationship between alkali-metal doping, electronicstructure modulation, and electronic thermoelectric response in poly[Ni-ett] coordination polymer chains, providing theoretical guidance for chemical doping design in low-dimensional coordination-polymer thermoelectric materials.

Keywords

Poly[Ni-ett] / Coordination polymer / Alkali-metal doping / Electronic structure / Electronic thermoelectric response

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