Chemistry Division, Bhabha Atomic Research Centre, Mumbai, 400 085, India.
Rapid Commun Mass Spectrom. 2011 Apr 30;25(8):1028-36. doi: 10.1002/rcm.4951. Epub 2011 Mar 29.
Using time-of-flight mass spectrometry (TOFMS), laser-induced photochemistry of ethyl bromide clusters has been investigated at three different wavelengths (viz. 266, 355 and 532 nm) utilizing nanosecond laser pulses of ~5 × 10(9) W/cm(2). An interesting finding of the present work is the observation of multiply charged atomic ions of carbon and bromine at 355 and 532 nm, arising from the Coulomb explosion of (C(2)H(5)Br)(n) clusters. At 266 nm, however, the (C(2)H(5)Br)(n) clusters were found to exhibit the usual multiphoton dissociation/ionization behaviour. The TOFMS studies are complemented by measuring the total charge density of the ionized volume at 266, 355 and 532 nm, using the parallel plate method, and the charge densities were found to be ~2 × 10(9), 6 × 10(9) and 2 × 10(11) charges/cm(3), respectively. The significantly higher charge density and the presence of energetic, multiply charged atomic ions at 532 nm are explained by the higher ponderomotive energy of the 532 nm photon, coupled with the Coulomb stability of the residual multiply charged ethyl bromide clusters generated upon laser irradiation, due to their larger effective cluster size at 532 nm than at 355 and 266 nm.
利用纳秒激光脉冲(约 5×10(9)W/cm(2)),在三个不同波长(即 266nm、355nm 和 532nm)下,使用飞行时间质谱(TOFMS)研究了溴乙烷团簇的激光光解。本工作的一个有趣发现是,在 355nm 和 532nm 处观察到了碳和溴的多电荷原子离子,这是(C(2)H(5)Br)(n)团簇的库仑爆炸产生的。然而,在 266nm 时,(C(2)H(5)Br)(n)团簇表现出通常的多光子解离/电离行为。TOFMS 研究通过使用平行板法在 266nm、355nm 和 532nm 下测量电离体积的总电荷密度得到补充,发现电荷密度分别约为 2×10(9)、6×10(9)和 2×10(11)电荷/cm(3)。在 532nm 时,电荷密度显著增加,存在高能、多电荷原子离子,这是由于 532nm 光子的 ponderomotive 能量更高,再加上激光辐照后生成的残余多电荷乙基溴团簇的库仑稳定性,这是由于它们在 532nm 时比在 355nm 和 266nm 时具有更大的有效团簇尺寸。