Reactive quenching of electronically excited NO2∗ and NO3∗ by H2O as potential sources of atmospheric HOx radicals
Reactive quenching of electronically excited NO2∗ and NO3∗ by H2O as potential sources of atmospheric HOx radicals
复制标题
作为大气 HOx 自由基的潜在来源，H2O 对电子激发的 NO2* 和 NO3* 进行反应猝灭
DOI：
10.5194/acp-18-14005-2018
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发表时间：
2018
影响因子：
6.3
通讯作者：
J. Crowley
中科院分区：
文献类型：
--
作者：
T. Dillon;J. Crowley
抽象的。脉冲
激光激发NO_2(532-647 nm)或NO_3
(623-662 nm)在水存在下被用来引发
气相反应NO2∗+H2O → 产物
(R5反应)和N3∗+H2O → 产物
(R12反应)。没有证据表明反应中会产生OH(R5)或
(R12)已观察到
和K5b/K5<；1×10-5和
K12B/K12&Lt；0.03。K5b/K5的上限
使这一反应作为大气中的一个氢氧源而变得微不足道
扩展了研究(Crowley和Carl，1997；Carr等人，2009；Amedro et
Al.，2011)，这表明先前报道的大的OH产率通过
Li等人(2008)是错误的。K12B/K12的上限表明，非反应能量转移是主要的机制
不过，对于反应(R12)
产生少量但数量可观的大气
不能排除HOX和HONO的可能性。在这个过程中
总去除NO3-∗的功、速率系数
氮气(反应R10)和水(反应R12)是
测定：K10=(2.1±0.1)×10-11 cm~3 分子−1 S−1和K12=(1.6±0.3)×10-10 cm~3 分子−1 S−1
K12比之前的单项小4倍还多
报告的价值。
Abstract. Pulsed
laser excitation of NO2 (532–647 nm) or NO3
(623–662 nm) in the presence of H2O was used to initiate the
gas-phase reaction NO2∗+H2O → products
(Reaction R5) and NO3∗+H2O → products
(Reaction R12). No evidence for OH production in Reactions (R5) or
(R12) was observed
and upper limits for OH production of k5b/k5<1×10-5 and
k12b/k12<0.03 were assigned. The upper limit for k5b∕k5
renders this reaction insignificant as a source of OH in the atmosphere and
extends the studies (Crowley and Carl, 1997; Carr et al., 2009; Amedro et
al., 2011) which demonstrate that the previously reported large OH yield by
Li et al. (2008) was erroneous. The upper limit obtained for k12b∕k12 indicates that non-reactive energy transfer is the dominant mechanism
for Reaction (R12), though
generation of small but significant amounts of atmospheric
HOx and HONO cannot be ruled out. In the course of this
work, rate coefficients for overall removal of NO3∗ by
N2 (Reaction R10) and by H2O (Reaction R12) were
determined: k10=(2.1±0.1)×10-11 cm3 molecule−1 s−1 and k12=(1.6±0.3)×10-10 cm3 molecule−1 s−1. Our value of
k12 is more than a factor of 4 smaller than the single previously
reported value.
影响因子：
56.9
作者：
Xin Li;F. Rohrer;A. Hofzumahaus;T. Brauers;R. Häseler;B. Bohn;S. Broch;H. Fuchs;S. Gomm;F. Holland;J. Jäger;J. Kaiser;F. Keutsch;I. Lohse;K. Lu;R. Tillmann;R. Wegener;G. Wolfe;T. Mentel;A. Kiendler‐Scharr;A. Wahner
通讯作者：
Xin Li;F. Rohrer;A. Hofzumahaus;T. Brauers;R. Häseler;B. Bohn;S. Broch;H. Fuchs;S. Gomm;F. Holland;J. Jäger;J. Kaiser;F. Keutsch;I. Lohse;K. Lu;R. Tillmann;R. Wegener;G. Wolfe;T. Mentel;A. Kiendler‐Scharr;A. Wahner