论文标题
n $ _ {3}^{+} $的光解离动力学
Photodissociation dynamics of N$_{3}^{+}$
论文作者
论文摘要
研究了N $ _3^+$的光电分解动力学从其$^3σ_ {\ rm g}^{ - } $接地到第一个激动的单元和三重态状态。 Three dimensional potential energy surfaces for the $^1$A$'$, $^1$A$''$, and $^3$A$'$ electronic states, correlating with the $^1 Δ_{\rm g}$ and $^3 Π_{\rm u}$ states in linear geometry, for N$_3^+$ are constructed using high level electronic structure calculations and represented as繁殖内核。参考{\ it i nibous}能量是在MRCI+Q/Aug-CC-PVTZ理论水平上计算得出的。为了遵循激发态的光解离动力，旋转和振动分布$ p（v'）$和$ p（j'）$的n $ _2 $产品是从垂直激发的基态分布确定的。由于基态的不同形状$^3 $ a $^{''} $ PES和激发状态，在双原子片段中生成了明显的角动量$ j'\ sim 60 $。激发态的寿命至少扩展到50 ps。值得注意的是，来自热集合的初始条件和基态波函数的wigner分布的结果是可比的。
The photodissociation dynamics of N$_3^+$ excited from its $^3 Σ_{\rm g}^{-}$ ground to the first excited singlet and triplet states is investigated. Three dimensional potential energy surfaces for the $^1$A$'$, $^1$A$''$, and $^3$A$'$ electronic states, correlating with the $^1 Δ_{\rm g}$ and $^3 Π_{\rm u}$ states in linear geometry, for N$_3^+$ are constructed using high level electronic structure calculations and represented as reproducing kernels. The reference {\it ab initio} energies are calculated at the MRCI+Q/aug-cc-pVTZ level of theory. For following the photodissociation dynamics in the excited states, rotational and vibrational distributions $P(v')$ and $P(j')$ for the N$_2$ product are determined from vertically excited ground state distributions. Due to the different shapes of the ground state $^3$A$^{''}$ PES and the excited states, appreciable angular momentum $j' \sim 60$ is generated in the diatomic fragments. The lifetimes in the excited states extend to at least 50 ps. Notably, results from sampling initial conditions from a thermal ensemble and from the Wigner distribution of the ground state wavefunction are comparable.
