简化的ROHF理论
ROHF Theory Made Simple
摘要：
通过对自旋密度本征值的数学约束，将受限开壳层Hartree-Fock（ROHF）理论表述为投影自洽的非受限HF（UHF）模型。由此产生的约束UHF（CUHF）波函数是相同的，从Roothaan的有效Fock算子。我们的$α$和$β$ CUHF Fock算子是无参数的，并且具有与UHF一样具有物理意义的正则轨道和轨道能量，除了消除自旋污染。本方法消除了ROHF轨道能量的模糊性和建立在它们基础上的方法的非唯一性。我们提出的基准证明CUHF的物理正确性和良好的协议与实验结果。
英文摘要：
Restricted open-shell Hartree-Fock (ROHF) theory is formulated as a projected self-consistent unrestricted HF (UHF) model by mathematically constraining spin density eigenvalues. The resulting constrained UHF (CUHF) wave function is identical to that obtained from Roothaan's effective Fock operator. Our $α$ and $β$ CUHF Fock operators are parameter-free and have canonical orbitals and orbital energies that are physically meaningful as in UHF, except for eliminating spin contamination. The present approach removes ambiguities in ROHF orbital energies and the non-uniqueness of methods that build upon them. We present benchmarks to demonstrate CUHF physical correctness and good agreement with experimental results.
机构、总结、中文摘要均由AI分析而来，可能存在错误，请以论文正文为准。
