H+Br2→HBr+Br反应的态-态量子动力学研究
State-to-State Quantum Dynamical Study of H+Br2→HBr+Br Reaction
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摘要: H原子与卤素气体(F2,Cl2,Br2)的反应是典型的轻-重-重原子-双原子反应. 对于研究化学激光的基本反应途径十分重要. 之前所有的实验结果都表明,H+Br2→HBr+Br反应的势垒高度很小,甚至是负值. 本文基于11698个UCCSD(T)/CBS水平的从头算能量点,用FI-NN方法构建了HBr2体系的精确全维全域势能面,还包括了Br原子2P3/2轨道的自旋-轨道耦合. 势能面有一个下沉的势垒(-0.351 kcal/mol),放热(ΔH0=-41.265 kcal/mol) 和实验值吻合的很好,在这个势能面上应用含时波包方法计算了H+Br2→HBr+Br反应的态-态积分和微分截面. 对初始基态反应,产物HBr(v'=2,3,4)态在所考虑的整个能量范围内占主导地位,说明HBr是振动态布居反转的. 温度300 K时,计算的产物振动分布在v'=3有最大值,在v'=0,1的分布可以忽略不计,这与Setser及合作者和Polanyi及合作者的实验结果相一致. 超过一半的总可用能量进入到产物的内部运动中,这其中大部分进入到振动中. 计算表明,反应物Br2的初始转动激发对产物振转态分布和微分截面影响很小,而初始振动激发则有一定影响. 在低能区域,初始振动激发到v0=5态很明显的增强了产物的振动激发. 在初始基态和初始转动激发态下,碰撞能量到0.5 eV的微分截面在后向达到峰值,但随着碰撞能量的增加,角分布的宽度显著增加. 对于初始振动激发态,产物微分截面的结构较为复杂,对高振动激发态产物有很强的前向散射峰.Abstract: The time-dependent wave packet method has been employed to calculate the state-to-state integral cross sections and differential cross sections (DCSs) for three initial states of the title reaction on the recently constructed neural network potential energy surface. It is found that the product HBr( v' = 2, 3, 4) states have the dominated population in the entire energy region considered here, indicating an inverted HBr vibrational state distribution. More than half of the available energy ends up as product internal motion, and most of which goes into the vibrational motion. Our calculations show that initial rotational excitation of Br _2 has little effect on the product ro-vibrational state distributions and DCSs of the reaction. While the initial vibrational excitation has some influences. The initial vibrational excitation to v_0 = 5 obviously enhance the product vibrational excitation in the low energy region. The DCSs for collision energy up to 0.5 eV at the ground and rotationally excited state are peaked in the backward direction, but the width of the angular distribution increases considerably with the increase of collision energy. For the vibrationally excited state, the DCSs are rather complicated with some strong forward scattering peaks for highly vibrationally excited products.