Sharma Pramod, Das Soumitra, Vatsa Rajesh K
Chemistry Division, Bhabha Atomic Research Centre, Mumbai, 400 085, India.
Rapid Commun Mass Spectrom. 2015 Jan 15;29(1):45-53. doi: 10.1002/rcm.7085.
Clusters exhibit diverse photochemical behavior as a function of laser parameters, i.e. wavelength, pulse duration and intensity. One such aspect of cluster photochemistry is the generation of energetic multiply charged atomic ions, upon efficient interaction of clusters with intense laser pulses. In the present work, mass spectrometric investigations have been carried out on clusters of tetrahydrofuran (THF, C4 H8 O) - a saturated cyclic ether - subjected to nanosecond laser pulse (spanning from UV to IR wavelength range) with the aim of shedding light on the complex mechanism of laser-cluster interactions, which is still ambiguous.
THF clusters, generated via supersonic expansion of room-temperature THF vapours seeded in argon, were subjected to gigawatt intensity laser pulses (355, 532 and 1064 nm) obtained from a nanosecond Nd:YAG laser. The ions generated upon laser-cluster interaction were characterized using a time-of-flight mass spectrometer.
At 355 nm, THF clusters exhibit the usual multiphoton dissociation/ionization behavior while, at 532 nm, observation of multiply charged atomic ions of carbon (up to C ) and oxygen (up to O ) was ascribed to Coulomb explosion of THF clusters. For studies carried out at 1064 nm, multiply charged atomic ions of carbon up to C having an ionization energy of ~392 eV were observed, at a laser intensity of 10(10) W/cm(2) .
The observation of C atomic ions signifies efficient coupling of the laser energy with the cluster medium, using a nanosecond laser pulse. The results have been rationalized on the basis of a three-stage cluster ionization mechanism, suggesting the crucial role of the threshold laser intensity for initiating ionization within the cluster and generation of optimum charge centers for efficient extraction of energy from the laser pulse.
团簇表现出随激光参数(即波长、脉冲持续时间和强度)变化的多样光化学行为。团簇光化学的一个方面是,当团簇与强激光脉冲有效相互作用时,会产生高能多电荷原子离子。在本工作中,对四氢呋喃(THF,C₄H₈O)——一种饱和环醚——的团簇进行了质谱研究,这些团簇受到纳秒激光脉冲(波长范围从紫外到红外)作用,目的是阐明激光 - 团簇相互作用的复杂机制,该机制仍不明确。
通过在氩气中室温THF蒸气的超声速膨胀产生的THF团簇,受到从纳秒Nd:YAG激光获得的千兆瓦强度激光脉冲(355、532和1064纳米)作用。使用飞行时间质谱仪对激光 - 团簇相互作用产生的离子进行表征。
在355纳米处,THF团簇表现出常见的多光子解离/电离行为,而在532纳米处,观察到碳的多电荷原子离子(高达C)和氧的多电荷原子离子(高达O),这归因于THF团簇的库仑爆炸。对于在1064纳米处进行的研究,在激光强度为10(10) W/cm²时,观察到电离能约为392电子伏特的高达C的碳多电荷原子离子。
C原子离子的观察表明,使用纳秒激光脉冲时激光能量与团簇介质的有效耦合。基于三阶段团簇电离机制对结果进行了合理化解释,表明阈值激光强度对于启动团簇内的电离以及产生用于从激光脉冲有效提取能量的最佳电荷中心起着关键作用。