Pietanza Lucia Daniela, Colonna Gianpiero, Capitelli Mario
P.Las.M.I. Lab, CNR-Nanotec, Bari, Italy.
Front Chem. 2019 Mar 29;7:163. doi: 10.3389/fchem.2019.00163. eCollection 2019.
Non-equilibrium vibrational distributions and electron energy distributions of CO in nanosecond repetitively pulsed (NRP) discharges and afterglows have been determined from a coupled solution of the time dependent Boltzmann equation for the electron energy distribution function (eedf) of free electrons and the master equations for the vibrational distribution function (vdf) of CO and the electronic excited states of CO and O and C atoms. Emphasis is given to the role of dissociative electron attachment (DEA) from vibrationally excited states in affecting the eedf and vdf under extreme conditions, i.e., an optically thick plasma with quenching processes involving the electronic excited states, populated by a sequence of discharge pulses and corresponding afterglows. In particular, the quenching process of the aΠ electronic state of CO determines a pumping of vibrational quanta in the ground state, which in turn largely modifies the CO vdf promoting the activation of DEA process. DEA rate coefficients have been obtained by using a complete set of vibrational (v) dependent cross sections through the ( Π) channel and by using the experimental = 0 cross section of Rapp and Briglia, which should include the contribution of other resonant states. The importance of the last contribution has been also estimated by using a scaling law to extend the = 0 cross section over all the vibrational ladder of CO. In particular, this mechanism becomes competitive with the other reactive channels for very short inter-pulse delay times, i.e., the = 1 μ, being less important for longer inter-pulse delay times, i.e., the = 25 μ.
通过求解自由电子的电子能量分布函数(eedf)的含时玻尔兹曼方程以及CO、CO和O及C原子的电子激发态的振动分布函数(vdf)的主方程的耦合解,确定了纳秒重复脉冲(NRP)放电及余辉中CO的非平衡振动分布和电子能量分布。重点研究了在极端条件下,即由一系列放电脉冲和相应余辉产生的、存在涉及电子激发态的猝灭过程的光学厚等离子体中,振动激发态的解离电子附着(DEA)对eedf和vdf的影响。特别地,CO的aΠ电子态的猝灭过程决定了基态振动量子的泵浦,这反过来又极大地改变了CO的vdf,促进了DEA过程的激活。通过使用穿过(Π)通道的完整的与振动(v)相关的截面集,并使用Rapp和Briglia的实验 = 0截面,获得了DEA速率系数,该截面应包括其他 共振态的贡献。还通过使用标度律将 = 0截面扩展到CO的所有振动阶梯上,估计了最后一项贡献的重要性。特别地,对于非常短的脉冲间延迟时间,即 = 1 μ,这种机制与其他反应通道具有竞争力,而对于较长的脉冲间延迟时间,即 = 25 μ,则不太重要。