We study the earliest steps in the radiolysis of a water pentamer in an intense, 800 nm, linearlypolarized fs laser field [I = (0.1 − 50) ∙ 10¹⁴ W/cm²] through a real-space, real-time implementation of time-dependent density functional theory nonadiabatically coupled to molecular dynamics. The ionization is enhanced with increasing laser intensity, resulting in the continuous emergence of higher charge states and an increase in the ionization ratio of the deepest levels. Two different reaction pathways of the water pentamer are presented by analyzing the degree of ionization, the level depletion, the probabilities of ionic states, the time-resolved electron density, the bond lengths, and the vibrational frequencies. Both pathways exhibit fluctuations and rearrangement dynamics of the hydrogen bonding network under irradiation. The cyclic structure of the pentamer formed via five oxygen ions is distorted and opened after ionization and tends to maintain a hydronium H₃O⁺ configuration. Proton transfer is accompanied by an oxygen–oxygen contraction and the first proton transfer rate ranges over 6–22 fs.

我们研究在激烈，800纳米，linearlypolarized飞秒激光场在水五聚体的辐最早步骤[我=（0 。 1 - 50）∙ 10 ¹⁴瓦/厘米²通过非绝热耦合到分子动力学的时变密度泛函理论的实时，实时实现。随着激光强度的增加，电离作用增强，导致更高电荷态的不断出现以及最深能级的电离率增加。通过分析电离程度，能级耗竭，离子态概率，时间分辨电子密度，键长和振动频率，提出了水五聚体的两种不同反应途径。两种途径在辐射下均表现出氢键网络的波动和重排动力学。由五个氧离子形成的五聚体的环状结构在电离后会变形并打开，并倾向于保持水合氢H ₃O ⁺配置。质子转移伴随着氧气-氧气的收缩，首次质子转移速率超过6-22 fs。