State-to-state Molecular Dynamics Study Of D~+/H~+ + HD System

The molecular reaction kinetics is a cutting-edge subject which mainly study molecular structure,the path of the whole reaction,the relationship between molecular structure and properties based on the molecular and atom level.Macroscopic kinetics and molecular reaction dynamics is complement to each other.Only studying the elementary reaction process clearly in the microscopic level can it provide the foundation explanation for the problem of macroscopic kinetics.After the molecular reaction dynamics was established,it has attracted lots of attention of scholars broadly since 1950s.H3+ is the simplest and stable molecule.It consists of three H atoms,which would trigger series of reaction as a proton donor.Due to its importance in the gas phase chemistry,scientists have done lots of researches on its spectral structure and isotopic ion-molecular reaction.However,there are still many unsolved problems in these studies.Thus,we plan to complete the studies and in this paper we used time-dependent quantum wave packet method to study the D+/H+ + HD reaction at the collision energy ranging from 0.01 to 0.8 eV.The main contents of the paper are summarized as follows:Chapter One will introduce the fundamental principle and development of molecular reaction dynamics,including experiment,theory method and researches of H3+ system.Chapter Two mainly introduce the time-dependent quantum wave packet method.In the next chapters,calculation results are presented.In Chapter Three,we used the wave packet method to study D+ + HD(v = 0,j= 0)reaction based on the non-adiabatic potential energy surface constructed by Kamisaka et al.at the collision energies ranging from 0.01 eV to 0.4 eV.Reaction probabilities,integral and differential cross sections are obtained.Due to the deep well in the PESs,resonance structures are obvious in the results of reaction probabilities and cross sections.The results showed that the Coriolis coupling effect plays a key role in the reaction and the magnitude of the reaction threshold energy is related to the centrifugal barrier.In addition,the non-strict symmetric structures in results of differential cross section indicate that the life-time of intermediate complex is not that long.In Chapter Four we did some researches on D+ + HD(v = 1,2,j = 0)reaction and also obtained reaction probabilities,state-to-state integral and differential cross sections.In this time,we studied the effects of the vibrational excitation of HD on the whole dynamics behavior of the reaction and compared them with the former results.The vibrational excitation of HD plays tiny role on the whole dynamics behavior.In Chapter Five,we used the same method to study H+ + HD(v = 0,j=0)reaction at the collision energies ranging from 0.01 eV to 0.8 eV and obtained reaction probabilities,integral and differential cross sections.Compared with previous system,we found the differential scattering cross sections of the two reaction channels also didn’t show a strict symmetric profile and inferred that the life time of intermediate complex for this reaction is also not that long.In addition,results of state-to-state integral cross sections show that the maximum J value which can reach for the H+ + HD channel is larger than of for the D++H2 channel.