Quantum Chemical Calculation of Metal-backboned Polymer

Yi-feng Zhang; Kai-wen Zeng; Yi-bei Yang; Wei-qiang Tang; Hui-sheng Peng

doi:10.11777/j.issn1000-3304.2022.22451

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Quantum Chemical Calculation of Metal-backboned Polymer

Rapid Communication | 更新时间：2023-03-08

- Quantum Chemical Calculation of Metal-backboned Polymer
- ACTA POLYMERICA SINICA Vol. 54, Issue 4, Pages: 413-417(2023)
- 作者机构：
  
  1.聚合物分子工程国家重点实验室复旦大学高分子科学系先进材料实验室上海 200438
  2.华东理工大学化学工程学院化学工程国家重点实验室上海 200237
- 作者简介：
  
  Hui-sheng Peng, E-mail: penghs@fudan.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2022.22451
  CLC：
- Published：20 April 2023，
  
  Published Online：15 February 2023，
  
  Received：28 December 2022，
  
  Accepted：03 February 2023
扫描看全文
张义锋,曾凯雯,杨依蓓等.金属主链高分子的量子化学计算[J].高分子学报,2023,54(04):413-417.

Zhang Yi-feng,Zeng Kai-wen,Yang Yi-bei,et al.Quantum Chemical Calculation of Metal-backboned Polymer[J].ACTA POLYMERICA SINICA,2023,54(04):413-417.
张义锋,曾凯雯,杨依蓓等.金属主链高分子的量子化学计算[J].高分子学报,2023,54(04):413-417. DOI： 10.11777/j.issn1000-3304.2022.22451.

Zhang Yi-feng,Zeng Kai-wen,Yang Yi-bei,et al.Quantum Chemical Calculation of Metal-backboned Polymer[J].ACTA POLYMERICA SINICA,2023,54(04):413-417. DOI： 10.11777/j.issn1000-3304.2022.22451.

摘要

金属主链高分子是一类完全以金属原子作为主链的新材料，在光电、传感、电化学储能等领域都具有重要的应用前景. 但是，如何获得具有较高分子量的金属主链高分子，仍然是一个挑战. 本文通过密度泛函理论计算方法，对镍金属主链高分子进行了结构优化和稳定性分析，发现随着聚合物分子量的增加，镍金属主链高分子的单点能逐渐降低，说明高分子量的金属主链高分子具有稳定的分子构型. 但是，随着分子量的进一步提高，计算量显著增加，密度泛函理论计算方法收敛困难. 为此，本文进一步通过Hartree-Fock计算方法对该系列镍金属主链高分子进行了分子构型优化，得到了与密度泛函理论计算结果相似的规律，并且发现当分子量超过1×10

时，金属主链高分子仍然具有较高的结构稳定性. 此外，这种电子离域在整个金属主链上的独特金属-金属的相互作用有利于实现电荷的高效传输；以金属原子为重复单元的分子结构，有望实现金属和高分子材料性能的有效结合，可以获得较高的热失重温度和熵弹性.

Abstract

Metal-backboned polymers (MBPs) are a new class of materials with metal atoms for backbones

which offer excellent electronic properties for promising applications in a variety of fields such as optoelectronics

sensing

and energy storage. However

it remains challenges to synthesize MBPs with high molecular weights for practical applications. Here

the structures of nickel-backboned polymers (NiBPs) with increasing molecular weights were optimized by density functional theory (DFT) method

based on which their stabilities were further studied. It was found that the energies of NiBPs gradually decreased with the increasing molecular weight

indicating that NiBPs with higher molecular weights showed stable molecular configurations. However

with the further increase of molecular weights

it was difficult for NiBPs to converge by DFT method. To this end

these structures were further studied by Hartree-Fock method. Similar results had been concluded as DFT calculation did

and it also proved that an NiBP with molecular weight exceeding 1×10

was also stable. In addition

the unique metal-metal interaction of the electron delocalization on the whole metal backbone is conducive to the efficient transmission of charge. As polymers with repeating metal atom units

MBPs are expected to have combined properties of metal and polymer materials

and may demonstrate high thermal weight loss temperatures and entropy elasticities. This work provides a theoretical basis for the synthesis of MBP materials.

关键词

金属主链镍原子高分子理论计算

Keywords

Metal-backbonedNickelPolymerMolecular simulation

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