Quantum Dynamics Study On The Non-adiabatic Reactions Of Na（3p）+D₂/HD

Studying the non-adiabatic reactions of excited-state sodium atom with hydrogen molecule and its isotopic substitutions（D₂ and HD）has great significance.In this work,the state-to-state dynamics calculations are carried out for Na（3p）+D₂→NaD+D and Na（3p）+HD→NaH/NaD+D/H reactions by using time-dependent quantum wave packet method.The obtained dynamics information,such as reaction probabilities,integral cross sections（ICSs）and differential cross sections（DCSs）,is used to study reaction mechanisms of the two reactions in detail.The thesis contains following parts:（1）The time-dependent quantum wave packet calculations are carried out for the Na（3p）+D₂→NaD+D reaction and the reaction probabilities,state-to-state integral cross sections and differential cross sections are obtained.The obtained dynamics information of the Na（3p）+D₂→NaD+D reaction is compared with the Na（3p）+H₂→NaH+H reaction to study the isotopic effect when H₂ is replaced by D₂.The reaction threshold of the Na（3p）+D₂reaction is larger than that of the Na（3p）+H₂ reaction because of the zero-point energy effects.The integral cross sections reveal that the substitution of D₂ for H₂ reduces the reactivity of the reaction.The rotational state resolved ICSs show that the product of Na（3p）+D₂ reaction has wider rotational state distribution than Na（3p）+H₂ reaction at the same collision energy.The significant forward scattering peaks are observed in the differential cross sections of the two reactions,and the forward scattering becomes stronger as the collision energy increases.（2）The time-dependent quantum wave packet calculations are carried out for the Na（3p）+HD（v=0,1）→NaH/NaD+D/H reaction to obtain the dynamics information for both of two product channels.Regarding the v=0 reaction,the reaction prefers the NaD+H product channel and the products from two channels both have the maximum population at vibrationally cold but rotationally hot states.Significant forward scattering peaks are observed in DCSs for both of two product channels.The minimum energy reaction path reveals that the reaction prefers to proceed through an insertion route.Characteristics of product branching ratio and product state distribution are consistent with the insertion reaction mechanism.However,significant forward scattering peaks of the DCSs are inconsistent with the characteristic of insertion reaction mechanism.Therefore,the direct insertion reaction mechanism is put forward for this reaction,which could be described as the coming Na（3p）atom inserts into the HD molecule and then takes away the H or D atom directly.Regarding the v=1 reaction,the initial internal energy of HD as the supplement energy reduces the threshold of the reaction.The dominant product channel changes from NaD+H to NaH+D as the collision energy increases.