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<p>Arsine (AsH<sub>3</sub>) clusters—heavy Group 15 hydride systems of critical importance in semiconductor manufacturing and atmospheric arsenic chemistry—lack rigorous high-accuracy ab initio quantification of their binding energetics, hindering the development of reliable computational methods for larger arsenic-containing systems. Here we present a systematic investigation of the structures and binding energies of arsine clusters ranging from dimers to hexamers, employing a validated composite scheme to establish benchmark energies at the CCSD(T)/CBS (coupled-cluster singles, doubles, and perturbative triples extrapolated to the complete basis set) limit. We further evaluate the performance of ten density functional theory functionals spanning hybrid, dispersion-corrected, and long-range corrected categories against our benchmark dataset. Our results reveal that dispersion interactions contribute nearly 40% of the total attractive energy in arsine clusters, nearly equal to electrostatic contributions from weak As-H⋯As hydrogen bonds—a distinct contrast to light Group 15/16 hydride clusters where electrostatic interactions dominate. Cooperativity analysis reveals a striking transition from anti-cooperative behavior in the trimer to cooperative strengthening in the tetramer and larger clusters, driven by the relief of angular strain and enhanced dispersion contributions. Among all tested functionals, M06-2X achieves the lowest mean absolute deviation (0.60&#xa0;kcal/mol per monomer) among the four structurally robust functionals, while CAM-B3LYP exhibits the most consistent performance with the smallest maximum deviation (7.10&#xa0;kcal/mol). Although APFD yields a lower total binding energy MAD (2.56&#xa0;kcal/mol), its failure to locate all isomeric structures limits its general applicability. This work fills a critical gap in the benchmark dataset for heavy main-group hydride clusters, and the recommended M06-2X and CAM-B3LYP functionals enable cost-effective, accurate simulations of large arsine systems relevant to semiconductor deposition, atmospheric arsenic nucleation, and toxic gas detection.</p>

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Benchmarking of CCSD(T)/CBS binding energies and density functional theory performance for small arsine clusters (AsH3)n (n = 2–6): unraveling the delicate balance between weak hydrogen bonding and dispersion interactions

  • 期刊论文

  • 发表日期：

    2026年6月3日

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  • Jian Zhang,
  • Jing Liu

摘要

Arsine (AsH3) clusters—heavy Group 15 hydride systems of critical importance in semiconductor manufacturing and atmospheric arsenic chemistry—lack rigorous high-accuracy ab initio quantification of their binding energetics, hindering the development of reliable computational methods for larger arsenic-containing systems. Here we present a systematic investigation of the structures and binding energies of arsine clusters ranging from dimers to hexamers, employing a validated composite scheme to establish benchmark energies at the CCSD(T)/CBS (coupled-cluster singles, doubles, and perturbative triples extrapolated to the complete basis set) limit. We further evaluate the performance of ten density functional theory functionals spanning hybrid, dispersion-corrected, and long-range corrected categories against our benchmark dataset. Our results reveal that dispersion interactions contribute nearly 40% of the total attractive energy in arsine clusters, nearly equal to electrostatic contributions from weak As-H⋯As hydrogen bonds—a distinct contrast to light Group 15/16 hydride clusters where electrostatic interactions dominate. Cooperativity analysis reveals a striking transition from anti-cooperative behavior in the trimer to cooperative strengthening in the tetramer and larger clusters, driven by the relief of angular strain and enhanced dispersion contributions. Among all tested functionals, M06-2X achieves the lowest mean absolute deviation (0.60 kcal/mol per monomer) among the four structurally robust functionals, while CAM-B3LYP exhibits the most consistent performance with the smallest maximum deviation (7.10 kcal/mol). Although APFD yields a lower total binding energy MAD (2.56 kcal/mol), its failure to locate all isomeric structures limits its general applicability. This work fills a critical gap in the benchmark dataset for heavy main-group hydride clusters, and the recommended M06-2X and CAM-B3LYP functionals enable cost-effective, accurate simulations of large arsine systems relevant to semiconductor deposition, atmospheric arsenic nucleation, and toxic gas detection.