论文标题

YO的光谱从第一原理

Spectroscopy of YO from first principles

论文作者

Smirnov, Alexander N., Solomonik, Victor G., Yurchenko, Sergei N., Tennyson, Jonathan

论文摘要

我们报告了一项关于开壳双原子分子Yttrium氧化物的初始研究。该研究考虑了六个最低的双重态,$ x \,{}^{2}σ^{+} $,$ a \,{}^{2}^{2}π$,$ c \,{}^{2}^{2}π$, $ b \,{}^{2}σ^{+} $,$ d \,{}^{2}σ^{+} $以及一些使用高水平的电子结构理论和准确的核运动计算的高级四重奏状态。耦合群集单打,双打和扰动三元组,CCSD(T)以及多连接配置互动(MRCI)方法与对YTTrium原子的相对论伪能力相结合,并在yttrium和相关基础基础上均与$ $ $ $ quint $ quint- $ quint $ quint quinte $ quint-考虑到CCSD(T)进行核心价相关效应,并进行完整的基集限制外推。通过使用MRCI状态相互作用与自旋轨道(SI-SO)进近和四分量相对论方程CCSD计算,包括自旋轨道耦合。使用AB Initi算数据的键长到1.0至2.5 a,我们计算6个势能,12个旋转轨道,8个电子角动量,6个电偶极矩和12个过渡偶极矩(4平行和8个垂直曲线)曲线,这些曲线提供了六个最低级别的六个最低次数的系统的完整描述。 Duo核运动计划用于解决这六个电子状态的耦合核运动Schrödinger方程。 $^{89} $ y $^{16} $ o的光谱与几个可用的高分辨率实验研究进行了比较;一旦对电子激发能进行了少量调整,就会发现良好的一致性。

We report an ab initio study on the spectroscopy of the open-shell diatomic molecule yttrium oxide, YO. The study considers the six lowest doublet states, $X\,{}^{2}Σ^{+}$, $A\,{}^{2}Π$, $C\,{}^{2}Π$, $A'\,{}^{2}Δ$, $B\,{}^{2}Σ^{+}$, $D\,{}^{2}Σ^{+}$ and a few higher-lying quartet states using high levels of electronic structure theory and accurate nuclear motion calculations. The coupled cluster singles, doubles, and perturbative triples, CCSD(T), and multireference configuration interaction (MRCI) methods are employed in conjunction with a relativistic pseudopotential on the yttrium atom and a series of correlation-consistent basis sets ranging in size from triple-$ζ$ to quintuple-$ζ$ quality. Core-valence correlation effects are taken into account and complete basis set limit extrapolation is performed for CCSD(T). Spin-orbit coupling is included through the use of both MRCI state-interaction with spin-orbit (SI-SO) approach and four-component relativistic equation-of-motion CCSD calculations. Using the ab initio data for bond lengths ranging from 1.0 to 2.5 A, we compute 6 potential energy, 12 spin-orbit, 8 electronic angular momentum, 6 electric dipole moment and 12 transition dipole moment (4 parallel and 8 perpendicular) curves which provide a complete description of the spectroscopy of the system of six lowest doublet states. The Duo nuclear motion program is used to solve the coupled nuclear motion Schrödinger equation for these six electronic states. The spectra of $^{89}$Y$^{16}$O simulated for different temperatures are compared with several available high resolution experimental studies; good agreement is found once minor adjustments are made to the electronic excitation energies.

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