Inverted Vibrational and Rotational Excitation of CN(B2Σ+) Produced through Superexcited Ion-Pair States of MCN (M = Na, K, Rb),The Journal of Physical Chemistry A

当前位置： X-MOL 学术 › J. Phys. Chem. A › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Inverted Vibrational and Rotational Excitation of CN(B2Σ+) Produced through Superexcited Ion-Pair States of MCN (M = Na, K, Rb)
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2020-03-30 , DOI: 10.1021/acs.jpca.9b11634
Hisato Yasumatsu ₁ , Gwang-Hi Jeung ₂

Affiliation

This paper reports an energy-partition mechanism in dissociative excitation of alkali cyanide molecules, MCN (M = Rb, K, Na), to produce CN(B²Σ⁺) and M(ns²S) (n = 5, 4, and 3 for Rb, K, and Na, respectively) in collision with Kr metastable atoms, Kr^m(³P_2,0). Both the vibrational and rotational distributions of CN(B²Σ⁺) produced in the reactions of RbCN and KCN were inverted as being peaked at v′ = 1 and N′ = 35, respectively, where v′ and N′ are the vibrational and the rotational quantum numbers of CN(B²Σ⁺), respectively. According to a state crossing model, it was derived that CN(B²Σ⁺) is produced by predissociation through a superexcited ion-pair state, CN^–(3¹Σ⁺)·M⁺(¹S), followed by an adiabatic transition to a repulsive state correlating to the dissociation limit of CN(B²Σ⁺) + M(ns²S). The inverted distributions are driven by structural changes during the excitation and the adiabatic transition. The maximum vibrational population at v′ = 1 originates from a large Franck–Condon overlap between the vibrational wavefunctions of CN^–(3¹Σ⁺) and CN(B²Σ⁺) at v′ = 1. The rotational excitation of the CN(B²Σ⁺) product is explained with changing from a T-shape geometry of MCN in the ground state to a linear one in the superexcited ion-pair state.

中文翻译：

倒振动和CN的转动激发（B ² Σ ⁺）通过MCN的超激发离子对国家（M =钠，钾，铷）生产的

本文报道在碱金属氰化物分子，MCN（M = RB，K，Na）的，以产生CN（B的离解激发能量分隔机构² Σ ⁺）和M（Ñ小号² S）（Ñ = 5,4 ，与Rb，K和Na分别为3和3）与Kr亚稳原子Kr ^m（³ P _2,0）碰撞。两个CN（B的振动和转动分布² Σ ⁺在RBCN和KCN的反应产生的）倒置作为被锐化V' = 1和Ñ分别'= 35，其中v '和Ñ'是振动和CN（B的旋转量子数² Σ ⁺）表示。据的状态下交叉模型，它是得出，CN（B ² Σ ⁺）是由预离解产生通过超激发离子对状态，CN ^-（3 ¹ Σ ⁺）·男⁺（^1个S），接着是绝热过渡到排斥状态相关，以CN（B的解离极限² Σ ⁺）+ M（ñ小号² S）。反向分布是由激发和绝热过渡过程中的结构变化驱动的。最大振动人口在v '=从CN的振动波函数之间的大的弗兰克-康登重叠1个始发^-（3 ¹ Σ ⁺）和CN（B ² Σ ⁺）在v '= 1，CN（B的旋转激励² Σ ⁺用基态MCN的T形几何形状转变为超激发离子对态的线性MCN解释了产物。

更新日期：2020-03-30

点击分享查看原文

点击收藏

阅读更多本刊最新论文