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• Chinese Journal of Chemical Physics
• Vol. 33, Issue 5, 05000507 (2020)
Mou Li-hui1、2、3, Jiang Gui-duo1、2、3, Li Zi-yu1、3、*, and He Sheng-gui1、2、3、*
Author Affiliations
• 1State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
• 2University of Chinese Academy of Sciences, Beijing 100049, China
• 3Beijing National Laboratory for Molecular Sciences and CAS Research/Education Center of Excellence in Molecular Sciences, Beijing 100190, China
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Abstract

Reactions of gas-phase species with small molecules are being actively studied to understand the elementary steps and mechanistic details of related condensed-phase processes. Activation of the very inert N$\equiv$N triple bond of dinitrogen molecule by isolated gas-phase species has attracted considerable interest in the past few decades. Apart from molecular adsorption and dissociative adsorption, interesting processes such as C-N coupling and degenerate ligand exchange were discovered. The present review focuses on the recent progress on adsorption, activation, and functionalization of N2 by gas-phase species (particularly metal cluster ions) using mass spectrometry, infrared photo-dissociation spectroscopy, anion photoelectron spectroscopy, and quantum chemical calculations including density functional theory and high-level ab initio calculations. Recent advances including characterization of adsorption products, dependence of clusters' reactivity on their sizes and structures, and mechanisms of N$\equiv$N weakening and splitting have been emphasized and prospects have been discussed.

Ⅰ INTRODUCTION

Gas-phase reactions can be studied under isolated and well-controlled conditions. Gas-phase species, particularly the atomic clusters with limited number of atoms and well-defined structures, are often used as ideal models of active sites in complex catalytic processes. The investigations on the reactions of gas-phase species with small molecules are thus of great importance and are being actively studied to understand the mechanisms of activation and transformation of chemical bonds, particularly the very inert bonds such as RC-H [1-10], OC = O [11-17], H-H [18-23], and N$\equiv$N [24-35]. The gas-phase reactions involving organic (such as CH4, C2H6, C2H4, CH3OH, etc.) and inorganic (such as H2, H2O, SO2, CO, CO2, etc.) molecules have been extensively investigated and reviewed in literatures [36-52]. In recent years, activation of small molecules related to energy and environment, such as N2 [24-35], has heightened concerns in this field.