Wadsworth Center, New York State Department of Health and Department of Environmental Health Sciences, State University of New York, Albany, New York 12201-0509, USA.
J Phys Chem A. 2010 Feb 25;114(7):2561-8. doi: 10.1021/jp909867a.
We have studied the photolysis of nitric acid (HNO(3)) in the gas phase at 253 and 295 K, on aluminum surfaces at 253 and 295 K, and on ice films at 253 K, by using 308 nm excimer laser photolysis combined with cavity ring-down spectroscopy. We monitored both the ground-state NO(2) and the electronically excited NO(2), NO(2), produced from the HNO(3) photolysis. NO(2) + OH is a predominant photolysis pathway (if not the only photolysis pathway) from the gas-phase photolysis of HNO(3) at 308 nm. The NO(2)* quantum yields from the HNO(3) photolysis on aluminum surfaces are 0.80 +/- 0.15 at 295 K and 0.92 +/- 0.26 at 253 K, where errors quoted represent 2sigma measurement uncertainty. The corresponding NO(2)* quantum yield from the HNO(3) photolysis on ice films is 0.60 +/- 0.34 at 253 K. The 308 nm absorption cross sections of HNO(3) on Al surfaces and on ice films have been directly measured. Absorption cross sections of HNO(3) on Al surface at 308 nm are (4.19 +/- 0.17) x 10(-18) and (4.23 +/- 0.45) x 10(-18) cm(2)/molecule at 253 and at 295 K, whereas the corresponding absorption cross section of HNO(3) on ice films is (1.21 +/- 0.31) x 10(-18) cm(2)/molecule at 253 K (errors quoted represent 2sigma measurement uncertainty). Atmospheric implications of the results are discussed.
我们使用 308nm 准分子激光光解结合腔衰荡光谱法,在 253 和 295K 下研究了气相中、253 和 295K 下的铝表面以及 253K 下的冰膜中硝酸(HNO(3))的光解。我们监测了由 HNO(3)光解产生的基态 NO(2)和电子激发态 NO(2),NO(2)。NO(2) + OH 是 308nm 下气相中 HNO(3)光解的主要光解途径(如果不是唯一的光解途径)。在 295K 下,HNO(3)在铝表面光解的 NO(2)*量子产率为 0.80 +/- 0.15,在 253K 下为 0.92 +/- 0.26,其中给出的误差表示 2sigma 测量不确定度。在 253K 下,HNO(3)在冰膜上光解的 NO(2)*量子产率为 0.60 +/- 0.34。我们直接测量了 HNO(3)在 Al 表面和冰膜上的 308nm 吸收截面。在 308nm 下,HNO(3)在 Al 表面上的吸收截面在 253 和 295K 下分别为(4.19 +/- 0.17)x 10(-18)和(4.23 +/- 0.45)x 10(-18)cm(2)/molecule,而在 253K 下,HNO(3)在冰膜上的相应吸收截面为(1.21 +/- 0.31)x 10(-18)cm(2)/molecule(给出的误差表示 2sigma 测量不确定度)。讨论了结果对大气的影响。