Sliced velocity mapping ion imaging technique was employed to investigate the dynamics of the hydroxyl elimination channel in the photodissociaiton of nitric acid in the ultraviolet region. The OH product was detected...Sliced velocity mapping ion imaging technique was employed to investigate the dynamics of the hydroxyl elimination channel in the photodissociaiton of nitric acid in the ultraviolet region. The OH product was detected by （2＋1） resonance enhanced multiphoton ionization via the D^2∑^- electronic state. The total kinetic energy spectra of the OH＋NO2 channel from the photolysis of HONO2 show that both ：NO2（X2A1） and NO2（A2B2） channels are present, suggesting that both 1^1A″ and 2^1A″ excited electronic states of HONO2 are involved in the excitation. The parallel angular distributions suggest that the dissociation of the nitric acid is a fast process in comparison with the rotational period of the HNO3 molecule. The anisotropy parameter β for the hydroxyl elimination channel is found to be dependent on the OH product rotational state as well as the photolysis energy.展开更多
Nitrous acid （HONO）, as a primary precursor of OH radicals, has been considered one of the most important nitrogencontaining species in the atmosphere. Up to 30% of primary OH radical production is attributed to the...Nitrous acid （HONO）, as a primary precursor of OH radicals, has been considered one of the most important nitrogencontaining species in the atmosphere. Up to 30% of primary OH radical production is attributed to the photolysis of HONO. However, the major HONO formation mechanisms are still under discussion. During the Campaigns of Air Quality Research in Beijing and Surrounding Region （CAREBeijing2006） campaign, comprehensive measurements were carried out in the megacity Beijing, where the chemical budget of HONO was fully constrained. The average diurnal HONO concentration varied from 0.33 to 1.2 ppbv. The net OH production rate from HONO, Pon（HONO）net, was on average （from 05：00 to 19：00） 7.1 × 10^6 molecule/（cm^3 s）, 2.7 times higher than from 03 photolysis. This production rate demonstrates the important role of HONO in the atmospheric chemistry of megacity Beijing. An unknown HONO source （Punknown） with an average of 7.3 × 10^6 molecule/（cm^3 s） was derived from the budget analysis during daytime. Punknown provided four times more HONO than the reaction of NO with OH did. The diurnal variation of Punknown showed an apparent photo-enhanced feature with a maximum around 12：00, which was consistent with previous studies at forest and rural sites. Laboratory studies proposed new mechanisms to recruit NO2 and J（NO2） in order to explain a photo-enhancement of of Puknown. In this study, these mechanisms were validated against the observation-constraint Punknown. The reaction of exited NO2 accounted for only 6% of Puknown, and Punk poorly correlated with [NO2] （R = 0.26） and J（NO2）[NO2] （R = 0.35）. These results challenged the role of NO2 as a major precursor of the missing HONO source.展开更多
基金Ⅴ. ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China, the Ministry of Sciences and Technology, and the Chinese Academy of Sciences.
文摘Sliced velocity mapping ion imaging technique was employed to investigate the dynamics of the hydroxyl elimination channel in the photodissociaiton of nitric acid in the ultraviolet region. The OH product was detected by （2＋1） resonance enhanced multiphoton ionization via the D^2∑^- electronic state. The total kinetic energy spectra of the OH＋NO2 channel from the photolysis of HONO2 show that both ：NO2（X2A1） and NO2（A2B2） channels are present, suggesting that both 1^1A″ and 2^1A″ excited electronic states of HONO2 are involved in the excitation. The parallel angular distributions suggest that the dissociation of the nitric acid is a fast process in comparison with the rotational period of the HNO3 molecule. The anisotropy parameter β for the hydroxyl elimination channel is found to be dependent on the OH product rotational state as well as the photolysis energy.
基金supported by the National Natural Science Foundation of China(21190052,40675072,41121004)the Ministry of Science and Technology of China(2002CB410801)the Beijing Council of Science and Technology(HB200504-6,HB200504-2)
文摘Nitrous acid （HONO）, as a primary precursor of OH radicals, has been considered one of the most important nitrogencontaining species in the atmosphere. Up to 30% of primary OH radical production is attributed to the photolysis of HONO. However, the major HONO formation mechanisms are still under discussion. During the Campaigns of Air Quality Research in Beijing and Surrounding Region （CAREBeijing2006） campaign, comprehensive measurements were carried out in the megacity Beijing, where the chemical budget of HONO was fully constrained. The average diurnal HONO concentration varied from 0.33 to 1.2 ppbv. The net OH production rate from HONO, Pon（HONO）net, was on average （from 05：00 to 19：00） 7.1 × 10^6 molecule/（cm^3 s）, 2.7 times higher than from 03 photolysis. This production rate demonstrates the important role of HONO in the atmospheric chemistry of megacity Beijing. An unknown HONO source （Punknown） with an average of 7.3 × 10^6 molecule/（cm^3 s） was derived from the budget analysis during daytime. Punknown provided four times more HONO than the reaction of NO with OH did. The diurnal variation of Punknown showed an apparent photo-enhanced feature with a maximum around 12：00, which was consistent with previous studies at forest and rural sites. Laboratory studies proposed new mechanisms to recruit NO2 and J（NO2） in order to explain a photo-enhancement of of Puknown. In this study, these mechanisms were validated against the observation-constraint Punknown. The reaction of exited NO2 accounted for only 6% of Puknown, and Punk poorly correlated with [NO2] （R = 0.26） and J（NO2）[NO2] （R = 0.35）. These results challenged the role of NO2 as a major precursor of the missing HONO source.
