论文标题
n $ _3^+$：全维势能表面，振动能级和基态动力学
N$_3^+$: Full-Dimensional Potential Energy Surface, Vibrational Energy Levels and Ground State Dynamics
论文作者
论文摘要
N $ _3^+$离子在其电子基态下的基本面和较高的振动激发态已从CCSD（T）-F12和MRCI+Q水平的3维势能表面（PESS）上的量子结合状态计算确定。振动基本原理在1130 cm $^{ - 1} $（$ν_1$，对称拉伸），807 cm $^{ - 1} $（$ν_3$，不对称拉伸）和406 cm $ $^{ - 1} $（$ ne）上（$ nment-feight）ccsd（$ n} $（$ν_2$，bend）在较高的表面上ccsd（$ν_2$，bend）。对于$ν_1$，计算接近实验的估计频率（1170 cm $^{ - 1} $）和以前的计算\ cite {Rosmus.n3：1994}，在1190 cm $ $^{ - 1} $中找到了它。 MRCI+Q PES上振动状态的计算与使用CCSD（T）-F12 PES的振动状态定性一致。 MRCI+Q计算的参考CASSCF波函数的分析提供了对PES的形状的进一步见解，并借给Hartree-Fock的可靠性作为耦合群集计算的参考波函数。据此，n $ _3^+$在其电子接地状态的所有低能区域（$^3 $ a $'''$）3D PES中主要具有单个参考字符。
The fundamentals and higher vibrationally excited states for the N$_3^+$ ion in its electronic ground state have been determined from quantum bound state calculations on 3-dimensional potential energy surfaces (PESs) at the CCSD(T)-F12 and MRCI+Q levels of theory. The vibrational fundamentals are at 1130 cm$^{-1}$ ($ν_1$, symmetric stretch), 807 cm$^{-1}$ ($ν_3$, asymmetric stretch), and 406 cm$^{-1}$ ($ν_2$, bend) on the higher-quality CCSD(T)-F12 surface. For $ν_1$, the calculations are close to the estimated frequency from experiment (1170 cm$^{-1}$) and previous calculations\cite{rosmus.n3:1994} which find it at 1190 cm$^{-1}$. Calculations of the vibrational states on the MRCI+Q PES are in qualitative agreement with those using the CCSD(T)-F12 PES. Analysis of the reference CASSCF wave function for the MRCI+Q calculations provides further insight into the shape of the PES and lends support for the reliability of Hartree-Fock as the reference wave function for the coupled cluster calculations. According to this, N$_3^+$ has mainly single reference character in all low-energy regions of its electronic ground state ($^3$A$''$) 3d PES.
