Rotationally resolved spectroscopy and dynamics of the 3p(x) (1)A(2) Rydberg state of formaldehyde.
Rotationally resolved spectroscopy and dynamics of the 3p(x) (1)A(2) Rydberg state of formaldehyde.
复制标题
甲醛 3p(x) (1)A(2) Rydberg 态的旋转分辨光谱和动力学。
DOI：
--
复制
发表时间：
2010
期刊：
影响因子：
--
通讯作者：
Peter Radi
中科院分区：
文献类型：
--
作者：
M. Meisinger;A. M. Schulenburg;F. Merkt;Peter Radi
用双共振三光子电离光谱研究了甲醛的3p(X) (1)A(2)里德堡态最低三个振动能级(0(0)，6(1)和4(1))的转动结构。在面内摇摆(ν(6))和面外弯曲(ν(4))模之间强烈的a型科里奥利相互作用导致观察到振动禁戒跃迁从中间的(1)A(2)(2(1)4(3))能级。振子跃迁到4(1)态的半最大宽度比振动基态和6(1)能级大得多。带原点(T(0)=67 728.939(82)cm(-1))，刚性转子转动常数(A=9.006(19)cm(-1)，B=1.331(20)cm(-1)，C=1.135(22)cm(-1))，测定了3p(X)ξ(1)A(2)里德堡态的科里奥利耦合常数( =8.86(89)cm(-1))和两种振动模式(v[结束波](6)=808.88(25)cm(-1)和v[结束波](4)=984.92(26)cm(-1))的扰动基波数。利用双共振技术产生的偏振效应来探测科里奥利相互作用，并研究它对预解离动力学的影响。
The rotational structure of the lowest three vibrational levels (0(0), 6(1) and 4(1)) of the 3p(x) (1)A(2) Rydberg state of formaldehyde has been studied by doubly-resonant three-photon ionization spectroscopy. A strong a-type Coriolis interaction between the in-plane rocking (ν(6)) and out-of-plane bending (ν(4)) modes results in the observation of vibronically forbidden transitions to the 6(1) level from the intermediate Ã(1)A(2) (2(1) 4(3)) level. The full widths at half maximum of the rovibronic transitions to the 4(1) state are considerably larger than to the vibrational ground state and the 6(1) level. The band origin (T(0) = 67 728.939(82) cm(-1)), the rigid rotor rotational constants (A = 9.006(19) cm(-1), B = 1.331(20) cm(-1), and C = 1.135(22) cm(-1)), the Coriolis coupling constant (ξ = 8.86(89) cm(-1)) and the deperturbed fundamental wave numbers of both vibrational modes (v[combining tilde](6) = 808.88(25) cm(-1) and v[combining tilde](4) = 984.92(26) cm(-1)) have been determined for the 3p(x) (1)A(2) Rydberg state. Polarization effects originating from the double-resonance technique have been exploited to detect the Coriolis interaction and investigate how it affects the predissociation dynamics.