Robust All-Electron Optimization in Orbital-Free Density-Functional Theory Using the Trust-Region Image Method.
Robust All-Electron Optimization in Orbital-Free Density-Functional Theory Using the Trust-Region Image Method.
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DOI：
10.1021/acs.jpca.0c09502
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发表时间：
2020-12
期刊：
影响因子：
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通讯作者：
Matthew S. Ryley;M. Withnall;Tom J. P. Irons;T. Helgaker;A. M. Teale
中科院分区：
文献类型：
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作者：
Matthew S. Ryley;M. Withnall;Tom J. P. Irons;T. Helgaker;A. M. Teale
提出了无轨道密度泛函理论(OF-DFT)的高斯基实现，其中信赖域镜像法(TRIM)用于优化。这种二阶优化方案的构建是为了提供基准的全电子结果，其中粒子数约束、相关的化学势和电子密度具有非常紧密的收敛。结果表明，通过保持优化的鞍点性质，同时优化密度和化学势，收敛所需的迭代次数减少了数量级。将该方法与Chan、Cohen和Handy提出的嵌套优化方案的新实现进行了比较。我们的实现允许在全电子计算中自洽地处理半局部动能(和交换关联)泛函。这些计算的全电子高斯基设置将允许与广泛的标准高精度量子化学方法以及Kohn-Sham密度泛函理论进行直接比较。我们期望这一实现将为分析有限系统中近似动能泛函的性能提供一个有用的工具。
We present a Gaussian-basis implementation of orbital-free density-functional theory (OF-DFT) in which the trust-region image method (TRIM) is used for optimization. This second-order optimization scheme has been constructed to provide benchmark all-electron results with very tight convergence of the particle-number constraint, associated chemical potential, and electron density. It is demonstrated that, by preserving the saddle-point nature of the optimization and simultaneously optimizing the density and chemical potential, an order of magnitude reduction in the number of iterations required for convergence is obtained. The approach is compared and contrasted with a new implementation of the nested optimization scheme put forward by Chan, Cohen, and Handy. Our implementation allows for semilocal kinetic-energy (and exchange-correlation) functionals to be handled self-consistently in all-electron calculations. The all-electron Gaussian-basis setting for these calculations will enable direct comparison with a wide range of standard high-accuracy quantum-chemical methods as well as with Kohn-Sham density-functional theory. We expect that the present implementation will provide a useful tool for analyzing the performance of approximate kinetic-energy functionals in finite systems.