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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Spin-Orbit Effects in the Ground States of Singly Positive and Neutral V_2, VNb, and Nb_2: INDO/S and Empirical Model Calculations
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Spin-Orbit Effects in the Ground States of Singly Positive and Neutral V_2, VNb, and Nb_2: INDO/S and Empirical Model Calculations

机译：V_2，VNb和Nb_2分别为正态和中性的基态中的自旋轨道效应：INDO / S和经验模型计算

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摘要

Ground-state spin-orbit splittings in V_2~+, VNb~+, and Nb_2~+ were investigated with spin-orbit configuration interaction (SOCI) calculations using the intermediate neglect of differential overlap method for optical spectroscopy (INDO/S). Splittings found for the X~4∑~- ground states of V_2~+ and VNb~+ using a CI treatment isolating essential correlation of the ground and isoconfigurational a~2∑~+ and b~2∑~- state wave functions agreed well with experiment. The size of the splitting for Nb_2~+ was predicted. In all three cases the a~2∑~+ and b~2∑~- states were found to be strongly coupled by the spin-orbit operator. Several perturbative models for predicting energies of interacting excited states based on measured splittings were analyzed by comparing to SOCI results for V_2, VNb, and Nb_2. Second-order perturbation theory, treating only the isoconfigurational states, and neglecting overlap and CI in computing couplings was the best choice of approximations due to cancellation of errors. An empirical model treating the isoconfigurational states of the cations was developed within these guidelines and agrees well with SOCI calculations for V_2~+. The empirical wave functions were divergent for Nb_2~+ due to similar energies of the doublet states. Analysis of correlation effects in the INDO/S model indicates that a charge-iterative method could be effective for systematically correlated semiempirical calculations on metal cluster ions.
机译：利用对光学光谱的微分重叠法（INDO / S）的中间忽略，利用自旋轨道配置相互作用（SOCI）计算研究了V_2〜+，VNb〜+和Nb_2〜+中的基态自旋轨道分裂。使用CI处理隔离V_2〜+和VNb〜+的X〜4∑〜-基态并分离基波基本相关性和等构型a〜2∑〜+和b〜2∑〜-状态波函数发现分裂与实验。预测了Nb_2〜+的分裂大小。在这三种情况下，a〜2∑〜+和b〜2∑〜-状态都被自旋轨道算子强耦合。通过比较V_2，VNb和Nb_2的SOCI结果，分析了几种基于测得的分裂预测相互作用的激发态能量的微扰模型。由于消除了误差，二阶微扰理论只考虑等构态，在计算耦合时忽略重叠和CI是最佳的近似选择。在这些指导原则内建立了处理阳离子同构态的经验模型，该模型与SOCI对V_2〜+的计算非常吻合。由于双重态的能量相似，Nb_2〜+的经验波函数发散。对INDO / S模型中相关效应的分析表明，电荷迭代法对于金属簇离子的系统相关半经验计算可能是有效的。

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