Scholarlink

<p>While the structures and energetics of arsine (AsH<sub>3</sub>) clusters have been characterized in the gas phase, their behavior under condensed-phase conditions, relevant to semiconductor deposition and atmospheric chemistry, remains unexplored. In this work, we present the first systematic investigation of solvent effects on the structures, relative stabilities, binding energies, and hydrogen bond networks of arsine clusters from dimer to hexamer using density functional theory at the PBEPBE/6–31 +  + G(d,p) level with the Integral Equation Formalism Polarizable Continuum Model (IEF-PCM). The potential energy surfaces of all cluster sizes are thoroughly explored using the ABCluster program based on the artificial bee colony algorithm. Our results reveal several key findings: (1) The implicit solvent environment stabilizes numerous isomers that are unstable in the gas phase, demonstrating that the solvent expands the accessible configurational space of arsine clusters. (2) The relative energy gaps between isomers are systematically reduced in the solvent phase, compressing the energy landscape and increasing the structural diversity of thermally accessible configurations. (3) The binding energies in the solvent phase are consistently smaller than those in the gas phase, indicating that the dielectric continuum weakens intermolecular As-H⋯As hydrogen bonds. (4) The hydrogen bond network analysis reveals that BD, BBD, and BBDD-type molecular interactions enhance cluster stability, while B or D-type interactions reduce it. These results provide the first comprehensive picture of how implicit solvation modifies the potential energy surface of arsine clusters, with implications for understanding arsine aggregation in condensed-phase environments. These findings were further characterized by atoms in molecules topological analysis and the molecular tailoring approach, and contextualized by MP2/CBS calculations.</p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

Solvent effects on the structures and binding energies of arsine clusters (AsH3)n (n = 2–6): a DFT study with implicit solvation

  • 期刊论文

  • 发表日期：

    2026年8月5日

查看全文
  • Jian Zhang,
  • Xiaoxin Guo,
  • Jing Liu

摘要

While the structures and energetics of arsine (AsH3) clusters have been characterized in the gas phase, their behavior under condensed-phase conditions, relevant to semiconductor deposition and atmospheric chemistry, remains unexplored. In this work, we present the first systematic investigation of solvent effects on the structures, relative stabilities, binding energies, and hydrogen bond networks of arsine clusters from dimer to hexamer using density functional theory at the PBEPBE/6–31 +  + G(d,p) level with the Integral Equation Formalism Polarizable Continuum Model (IEF-PCM). The potential energy surfaces of all cluster sizes are thoroughly explored using the ABCluster program based on the artificial bee colony algorithm. Our results reveal several key findings: (1) The implicit solvent environment stabilizes numerous isomers that are unstable in the gas phase, demonstrating that the solvent expands the accessible configurational space of arsine clusters. (2) The relative energy gaps between isomers are systematically reduced in the solvent phase, compressing the energy landscape and increasing the structural diversity of thermally accessible configurations. (3) The binding energies in the solvent phase are consistently smaller than those in the gas phase, indicating that the dielectric continuum weakens intermolecular As-H⋯As hydrogen bonds. (4) The hydrogen bond network analysis reveals that BD, BBD, and BBDD-type molecular interactions enhance cluster stability, while B or D-type interactions reduce it. These results provide the first comprehensive picture of how implicit solvation modifies the potential energy surface of arsine clusters, with implications for understanding arsine aggregation in condensed-phase environments. These findings were further characterized by atoms in molecules topological analysis and the molecular tailoring approach, and contextualized by MP2/CBS calculations.