TY - JOUR
T1 - Nitric Acid-Amine Chemistry in the Gas Phase and at the Air-Water Interface
AU - Kumar, Manoj
AU - Li, Hao
AU - Zhang, Xiuhui
AU - Zeng, Xiao Cheng
AU - Francisco, Joseph S.
N1 - Publication details (e.g. title, author(s), publication statuses and dates) are captured on an “AS IS” and “AS AVAILABLE” basis at the time of record harvesting from the data source. Suggestions for further amendments or supplementary information can be sent to [email protected].
PY - 2018/5/23
Y1 - 2018/5/23
N2 - Gas-phase simulations of nitric acid-amine chemistry suggest that the fundamental acid-base interaction between HNO3 and NH3 results in a variety of HNO3-NH3-based complexes, such as (HNO3)3·(NH3)2, (HNO3)3·(NH3)3, and (HNO3)4·(NH3)3, that can be formed. The formation of these complexes in the gas phase follow different growth mechanisms under different relative humidity conditions. On the other hand, at the air-water interface, Born-Oppenheimer molecular dynamics simulations suggest that the formation of the fundamental NO3-··(R1)(R2)NH2+ [for NH3, R1 = R2 = H; CH3NH2, R1 = H, R2 = CH3; and (CH3)2NH, R1 = R2 = CH3] ion pairs require the formation of the HNO3··(R1)(R2)NH complexes in the gas-phase prior to their adsorption on the water surface. Ion-pair formation at the water surface involves proton transfer from HNO3 to (R1)(R2)NH and occurs within a few femtoseconds of the simulation. The NO3-··(R1)(R2)NH2+ ion pairs preferentially remain at the interface over the picosecond time scale, where they are stabilized via hydrogen bonding with surface water molecules. This offers a novel chemical framework for understanding gas-to-particle partitioning in the atmosphere. These results not only improve our understanding of the formation of nitrate particulates in polluted urban environments, but also provide useful guidelines for understanding particle formation in forested or coastal environments, in which organic acids and organosulfates are present in significant quantities and their exact role in particle formation remains elusive.
AB - Gas-phase simulations of nitric acid-amine chemistry suggest that the fundamental acid-base interaction between HNO3 and NH3 results in a variety of HNO3-NH3-based complexes, such as (HNO3)3·(NH3)2, (HNO3)3·(NH3)3, and (HNO3)4·(NH3)3, that can be formed. The formation of these complexes in the gas phase follow different growth mechanisms under different relative humidity conditions. On the other hand, at the air-water interface, Born-Oppenheimer molecular dynamics simulations suggest that the formation of the fundamental NO3-··(R1)(R2)NH2+ [for NH3, R1 = R2 = H; CH3NH2, R1 = H, R2 = CH3; and (CH3)2NH, R1 = R2 = CH3] ion pairs require the formation of the HNO3··(R1)(R2)NH complexes in the gas-phase prior to their adsorption on the water surface. Ion-pair formation at the water surface involves proton transfer from HNO3 to (R1)(R2)NH and occurs within a few femtoseconds of the simulation. The NO3-··(R1)(R2)NH2+ ion pairs preferentially remain at the interface over the picosecond time scale, where they are stabilized via hydrogen bonding with surface water molecules. This offers a novel chemical framework for understanding gas-to-particle partitioning in the atmosphere. These results not only improve our understanding of the formation of nitrate particulates in polluted urban environments, but also provide useful guidelines for understanding particle formation in forested or coastal environments, in which organic acids and organosulfates are present in significant quantities and their exact role in particle formation remains elusive.
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U2 - 10.1021/jacs.8b03300
DO - 10.1021/jacs.8b03300
M3 - RGC 21 - Publication in refereed journal
C2 - 29689155
SN - 0002-7863
VL - 140
SP - 6456
EP - 6466
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 20
ER -
