N₂的3Πᵤ态的耦合通道模型：3σgF₃ 3Πᵤ和3πᵤG₃ 3Πᵤ里德堡态的结构与相互作用

A coupled-channel model of the 3Pi(u) states of N2: structure and interactions of the 3ssigma(g)F3 3Pi(u) and 3ppi(u)G3 3Pi(u) Rydberg states.

作者信息

Lewis B R, Heays A N, Gibson S T, Lefebvre-Brion H, Lefebvre R

机构信息

Research School of Physical Sciences and Engineering, The Australian National University, Canberra, Australian Capital Territory 0200, Australia.

出版信息

J Chem Phys. 2008 Oct 28;129(16):164306. doi: 10.1063/1.2990656.

DOI:10.1063/1.2990656

PMID:19045265

Abstract

New and existing spectroscopic data on N(2), obtained using a wide variety of experimental techniques, are interpreted using a coupled-channel Schrodinger-equation (CSE) model of the structure and predissociation dynamics for the interacting Rydberg and valence states of (3)Pi(u) symmetry. As a result, v>0 levels of the 3ppi(u)G(3) (3)Pi(u) Rydberg state are assigned correctly for the first time, leading to the identification of very strong perturbations in the G(3)-state vibrational structure. A four-channel CSE model, which includes the 3ssigma(g)F(3) (3)Pi(u) and 3ppi(u)G(3) (3)Pi(u) Rydberg states and the C(') (3)Pi(u) and C (3)Pi(u) valence states, indicates strong Rydberg-Rydberg coupling between the F(3) and G(3) states, strong Rydberg-valence coupling between the G(3) and C(') states, and weaker coupling between the F(3) and C(') states.

摘要

利用多种实验技术获得的关于N₂的新的和现有的光谱数据，采用耦合通道薛定谔方程（CSE）模型对³Πᵤ对称的相互作用里德堡态和价态的结构及预解离动力学进行了解释。结果，首次正确地归属了³ΠᵤG₃（³Πᵤ）里德堡态的v>0能级，从而识别出G₃态振动结构中非常强的微扰。一个四通道CSE模型，包括³σgF₃（³Πᵤ）和³ΠᵤG₃（³Πᵤ）里德堡态以及C′（³Πᵤ）和C（³Πᵤ）价态，表明F₃和G₃态之间存在强的里德堡-里德堡耦合，G₃和C′态之间存在强的里德堡-价态耦合，而F₃和C′态之间的耦合较弱。