Edelstein Norman M
MS 70A3317, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
J Phys Chem A. 2025 Jan 9;129(1):50-57. doi: 10.1021/acs.jpca.4c05837. Epub 2024 Dec 18.
The analysis of the solution absorption spectrum of the plutonyl ion in an aqueous environment was given by Eisenstein and Pryce (E&P) in 1968. In 2011 a new spectrum was published of the (PuO) ion in 1 M HClO. We have been provided with the original data of this spectrum and have found in the data a previously unreported low-lying transition at 7385 cm which we have assigned as a magnetic dipole transition. We have fit most of the near-infrared and optical transitions with Gaussian fits and tabulated a new energy level list up to 22,000 cm which mostly agrees with the data of E&P. We assumed a crystal field of D (only axial symmetry) and utilized the intensity calculations published for the isoelectronic (NpO) ion using a complete basis set for the 5f problem including the Coulombic, spin-orbit as well as the crystal field Hamiltonian. Our results differ substantially from those of E&P. Subsequently, we used a truncated Hamiltonian to try to establish the effects of assuming the σ antibonding orbitals are at such high energies that we can ignore their contributions to the lower lying φ and δ orbitals.
1968年，艾森斯坦和普赖斯（E&P）对水环境中钚酰离子的溶液吸收光谱进行了分析。2011年，发表了1 M高氯酸中（PuO）离子的新光谱。我们已获得该光谱的原始数据，并在数据中发现了一个先前未报告的位于7385 cm处的低能级跃迁，我们将其指定为磁偶极跃迁。我们用高斯拟合对大部分近红外和光学跃迁进行了拟合，并列出了一个新的能级列表，最高到22000 cm，该列表与E&P的数据大多一致。我们假设了一个D晶体场（仅具有轴对称性），并利用为等电子（NpO）离子发表的强度计算，使用了针对5f问题的完整基组，包括库仑、自旋轨道以及晶体场哈密顿量。我们的结果与E&P的结果有很大不同。随后，我们使用了一个截断的哈密顿量，试图确定假设σ反键轨道处于如此高的能量以至于我们可以忽略它们对较低能级的φ和δ轨道的贡献所产生的影响。
