Ma Tongmei, Gengler Jamie, Wang Zhong, Wang Hailing, Steimle Timothy C
Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287-1604, USA.
J Chem Phys. 2007 Jun 28;126(24):244312. doi: 10.1063/1.2742386.
The optical Stark effect in the Q(1) and R(0) lines of the [15.1]1-X (1)Sigma+ (1,0) band of rhodium mononitride (RhN) were recorded and analyzed to determine the permanent electric dipole moments mu for the X (1)Sigma+(upsilon=0) and [15.1]1(upsilon=1) states to be 2.43(5) and 1.75(1) D, respectively. The determined dipole moments are compared to predicted values obtained from density functional theory [Stevens et al., Chem. Phys. Lett. 421, 281 (2006)] and an all-electron ab initio calculation [Shim et al., J. Mol. Struct. THEOCHEM 393, 127 (1997)]. A simple single configuration molecular orbital correlation diagram is used to rationalize the relative values of mu for the 4d mononitrides and RhO. An electronic configuration for the [15.1]1 state is proposed based on the interpretation of the (103)Rh and (14)N magnetic hyperfine interactions.
记录并分析了一氮化铑（RhN）的[15.1]1-X (1)Σ+(1,0)带的Q(1)和R(0)线中的光学斯塔克效应，以确定X (1)Σ+(υ=0)和[15.1]1(υ=1)态的永久电偶极矩μ，分别为2.43(5) D和1.75(1) D。将确定的偶极矩与从密度泛函理论[史蒂文斯等人，《化学物理快报》421, 281 (2006)]和全电子从头算计算[沈等人，《分子结构：理论化学》393, 127 (1997)]获得的预测值进行比较。使用一个简单的单组态分子轨道相关图来解释4d单氮化物和RhO的μ的相对值。基于对(103)Rh和(14)N磁超精细相互作用的解释，提出了[15.1]1态的电子组态。
