I2+ A2Π(3/2,u)-X2Π(3/2,g) 体系的高分辨率观测与分析。

High-resolution observation and analysis of the I2+ A2Π(3/2,u)-X2Π(3/2,g) system.

机构信息

State Key Laboratory of Precision Spectroscopy, Department of Physics, East China Normal University, Shanghai 200062, China.

出版信息

J Chem Phys. 2012 Aug 7;137(5):054308. doi: 10.1063/1.4739466.

DOI:10.1063/1.4739466

PMID:22894349

Abstract

Rotationally resolved absorption spectra of I(2)(+) were recorded in 12,065-13,062 cm(-1) region by employing optical heterodyne velocity modulation absorption spectroscopy. In total, 4054 lines were assigned to 24 bands in the A(2)Π(3/2,u)-X(2)Π(3/2,g) system spanning the vibrational levels υ'' = 1-4 and υ(n)' = 11-19. The assigned lines were globally fitted and an error of 0.003 cm(-1) was obtained. Rotational constants, B(υ), were used to derive equilibrium parameters B(e)'' = 0.03977725(77) cm(-1), a(e)'' = 1.1819(24)×10(-4) cm(-1), r(e)'' = 2.584386(25) Å of the X(2)Π(3/2,g) state, and B(e)' = 0.0305787(37) cm(-1), a(e)' = 1.2353(23)×10(-4) cm(-1), r(e)' = 2.94758(18) Å of the A(2)Π(3/2,u) state. Vibrational energies were used to derive ω(e)'' = 239.0397(55) cm(-1), ω(e)x(e)'' = 0.64951(87) cm(-1) of the X(2)Π(3/2,g) state and ω(e)' = 138.103(11) cm(-1), ω(e)x(e)' = 0.45027(34) cm(-1) of the A(2)Π(3/2,u) state. The A(2)Π(3/2,u) (υ(n) = 13) state was found to be rotationally perturbed by the a(4)Σ(1/2,u)(-) (υ(n) = 17) state through second-order spin-orbit coupling.

摘要

采用光外差速度调制吸收光谱技术，在 12065-13062cm^(-1) 区域记录了 I(2)(+)的旋转分辨吸收光谱。总共将 4054 条谱线分配给 A(2)Π(3/2,u)-X(2)Π(3/2,g) 体系中的 24 个带，跨越 υ''=1-4 和 υ(n) '=11-19 的振动能级。分配的谱线进行了全局拟合，得到了 0.003cm^(-1) 的误差。通过旋转常数 B(υ)，推导出了平衡参数 B(e)''=0.03977725(77)cm^(-1)，a(e)''=1.1819(24)×10^(-4)cm^(-1)，r(e)''=2.584386(25)Å的 X(2)Π(3/2,g)态，以及 B(e) '=0.0305787(37)cm^(-1)，a(e) '=1.2353(23)×10^(-4)cm^(-1)，r(e) '=2.94758(18)Å的 A(2)Π(3/2,u)态。振动能用于推导出 X(2)Π(3/2,g)态的 ω(e)''=239.0397(55)cm^(-1)，ω(e)x(e)''=0.64951(87)cm^(-1)和 A(2)Π(3/2,u)态的 ω(e) '=138.103(11)cm^(-1)，ω(e)x(e) '=0.45027(34)cm^(-1)。通过二级自旋轨道耦合，发现 A(2)Π(3/2,u)(υ(n)=13)态被 a(4)Σ(1/2,u)(-) (υ(n)=17)态的旋转微扰。