Scholarlink

<p>Quantum confinement in 2D materials strongly enhances electronic correlation effects. Therefore, predicting the properties of these unique materials, with both a high level of accuracy and computational efficiency, without relying on adjustable parameters or functionals, remains an outstanding theoretical challenge. The majority of theoretical studies are based on the approximations of density functional theory (DFT). The reliability of DFT predictions are heavily dependent on the choice of an approximated exchange-correlation functional. Here, we estimate the magnitude of impact of correlation on the total energy for the quintessential 2D material, graphene, by performing and comparing state-of-the-art selected CI and quantum Monte Carlo extrapolated calculations for a single unit cell at the <InlineEquation ID="IEq1"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="41598_2025_17564_Article_IEq1.gif" Format="GIF" Height="14" Rendition="HTML" Resolution="72" Type="Linedraw" Width="12" /> </InlineMediaObject> <EquationSource Format="TEX">\(\Gamma\)</EquationSource> </InlineEquation> point. We demonstrate that Self-Healing Diffusion Monte Carlo (SHDMC) obtains a very compact, but high-quality wavefunction for this system that lacks the strong basis set dependence displayed by state of the art quantum chemistry methods. The SHDMC wavefunction is of higher quality compared to that obtained from sCI, in the same orbital basis, while being <InlineEquation ID="IEq2"> <InlineMediaObject> <ImageObject Color="BlackWhite" FileRef="41598_2025_17564_Article_IEq2.gif" Format="GIF" Height="6" Rendition="HTML" Resolution="72" Type="Linedraw" Width="17" /> </InlineMediaObject> <EquationSource Format="TEX">\(\sim\)</EquationSource> </InlineEquation>&#xa0;1000 times smaller in terms of determinant count compared to sCI. We also demonstrate that extrapolating SHDMC results to the infinite determinant limit compares extremely well with complete basis set extrapolated sCI. Our work paves the way for future validation of SHDMC applied to challenging 2D materials.</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

Multireference diffusion Monte Carlo reaches 2D materials

  • 期刊论文

  • 出版模式：

    开放获取

  • 发表日期：

    2025年9月26日

查看全文
  • Nicole Spanedda,
  • Anouar Benali,
  • Fernando A. Reboredo,
  • Jaron T. Krogel

摘要

Quantum confinement in 2D materials strongly enhances electronic correlation effects. Therefore, predicting the properties of these unique materials, with both a high level of accuracy and computational efficiency, without relying on adjustable parameters or functionals, remains an outstanding theoretical challenge. The majority of theoretical studies are based on the approximations of density functional theory (DFT). The reliability of DFT predictions are heavily dependent on the choice of an approximated exchange-correlation functional. Here, we estimate the magnitude of impact of correlation on the total energy for the quintessential 2D material, graphene, by performing and comparing state-of-the-art selected CI and quantum Monte Carlo extrapolated calculations for a single unit cell at the \(\Gamma\) point. We demonstrate that Self-Healing Diffusion Monte Carlo (SHDMC) obtains a very compact, but high-quality wavefunction for this system that lacks the strong basis set dependence displayed by state of the art quantum chemistry methods. The SHDMC wavefunction is of higher quality compared to that obtained from sCI, in the same orbital basis, while being \(\sim\)  1000 times smaller in terms of determinant count compared to sCI. We also demonstrate that extrapolating SHDMC results to the infinite determinant limit compares extremely well with complete basis set extrapolated sCI. Our work paves the way for future validation of SHDMC applied to challenging 2D materials.