Simulation Verification of Barrierless HONO Formation from the Oxidation Reaction System of NO, Cl, and Water in the Atmosphere

Zhao, Xianwei; Shi, Xiangli; Ma, Xiaoliang; Wang, Junjie; Xu, Fei; Zhang, Qingzhu; Liu, Ying; Teng, Zhuochao; Han, Yanan; Wang, Qiao; Wang, Wenxing

doi:10.1021/acs.est.1c01773

Cited by 8 publications

(5 citation statements)

References 61 publications

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“…Another ab initio MD method, known as Born–Oppenheimer molecular dynamics (BOMD), includes electronic structure calculations in MD simulations by reducing the electronic structure component by solving the time-independent Schrodinger equation (i.e., QM), while classical MD treats fixed nuclear positions. BOMD simulations determined the heterogeneous reaction for nitrous acid formation from nitric oxide, •Cl radicals, and water on a droplet surface . It was found that the formation of nitrous acid for a dihydrate vs a monohydrate system is energetically more favorable, as evidenced by the absence of a free-energy barrier.…”

Section: Computational Chemistry Methodsmentioning

confidence: 99%

“…BOMD simulations determined the heterogeneous reaction for nitrous acid formation from nitric oxide, •Cl radicals, and water on a droplet surface. 299 It was found that the formation of nitrous acid for a dihydrate vs a monohydrate system is energetically more favorable, as evidenced by the absence of a free-energy barrier. The reaction was studied on the surface of a water droplet by BODM and showed that bond breaking in nitric oxide and •Cl radicals occurs only in water molecules for both monohydrate and dihydrate systems.…”

Section: Acs Esandt Engineeringmentioning

confidence: 99%

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Computational Chemistry as Applied in Environmental Research: Opportunities and Challenges

Sandoval-Pauker,

Yin,

Castillo

et al. 2023

ACS EST Eng.

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The constant development of computer systems and infrastructure has allowed computational chemistry to become an important component of environmental chemistry research. In the past decade, the application of quantum and classical mechanical calculations to model and understand environmental systems has increased exponentially. In this review, we highlight various applications of computational chemistry techniques in areas of environmental chemistry research (e.g., wastewater/air treatment, sensing, biodegradation). We briefly describe each computational approach, starting with quantum chemistry principle methods followed by molecular mechanics (MM), molecular dynamics (MD), and hybrid QM/MM methods. The recent introduction of artificial intelligence and machine learning techniques and their potential to disrupt the field are also discussed. Challenges and current and future directions to address them are presented.

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Section: Computational Chemistry Methodsmentioning

confidence: 99%

Section: Acs Esandt Engineeringmentioning

confidence: 99%

Computational Chemistry as Applied in Environmental Research: Opportunities and Challenges

Sandoval-Pauker,

Yin,

Castillo

et al. 2023

ACS EST Eng.

View full text Add to dashboard Cite

show abstract

“…Heterogeneous transformations of chemical pollutants were conventionally investigated using molecular dynamics methods, such as ab initio molecular dynamics (AIMD) and hybrid quantum-mechanical/molecular-mechanical molecular dynamics simulations. − These methods were limited to reactions with low energy barriers (typically <2 kcal·mol –1 ), as reactions with higher energy barriers require an extremely long time to reach transition states …”

Section: Potential Applications In Environmental Chemistrymentioning

confidence: 99%

Potential Application of Machine-Learning-Based Quantum Chemical Methods in Environmental Chemistry

Xia

Chen

et al. 2022

Environ. Sci. Technol.

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It is an important topic in environmental sciences to understand the behavior and toxicology of chemical pollutants. Quantum chemical methodologies have served as useful tools for probing behavior and toxicology of chemical pollutants in recent decades. In recent years, machine learning (ML) techniques have brought revolutionary developments to the field of quantum chemistry, which may be beneficial for investigating environmental behavior and toxicology of chemical pollutants. However, the ML-based quantum chemical methods (ML-QCMs) have only scarcely been used in environmental chemical studies so far. To promote applications of the promising methods, this Perspective summarizes recent progress in the ML-QCMs and focuses on their potential applications in environmental chemical studies that could hardly be achieved by the conventional quantum chemical methods. Potential applications and challenges of the ML-QCMs in predicting degradation networks of chemical pollutants, searching global minima for atmospheric nanoclusters, discovering heterogeneous or photochemical transformation pathways of pollutants, as well as predicting environmentally relevant end points with wave functions as descriptors are introduced and discussed.

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“…Both laboratory and field studies found that photolysis of adsorbed HNO 3 and particulate nitrate (NO − 3 ) could produce HONO (Ye et al, 2016(Ye et al, , 2017Zhou et al, 2003Zhou et al, , 2002bZhou et al, , 2011, which might be an important HONO source, at least in remote areas and polar regions. Evidence of other new pathways and mechanisms has also been found and their atmospheric relevance discussed (Ge et al, 2019;Wang et al, 2016;Xu et al, 2019;Xia et al, 2021;Zhao et al, 2021;Gen et al, 2021).…”

Section: Introductionmentioning

confidence: 95%

Budget of nitrous acid (HONO) at an urban site in the fall season of Guangzhou, China

Cheng

et al. 2022

Atmos. Chem. Phys.

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Abstract. High concentrations of nitrous acid (HONO) have been observed in the Pearl River Delta (PRD) region of China in recent years, contributing to an elevated atmospheric oxidation capacity due to the production of OH through HONO photolysis. We investigated the budget of HONO at an urban site in Guangzhou from 27 September to 9 November 2018 using data from a comprehensive atmospheric observation campaign. During this period, measured concentrations of HONO were 0.02 to 4.43 ppbv, with an average of 0.74 ± 0.70 ppbv. An emission ratio (HONO/NOx) of 0.9 ± 0.4 % was derived from 11 fresh plumes. The primary emission rate of HONO at night was calculated to be between 0.04 ± 0.02 and 0.30 ± 0.15 ppbv h−1 based on a high-resolution NOx emission inventory. Heterogeneous conversion of NO2 on the ground surface (0.27 ± 0.13 ppbv h−1), primary emissions from vehicle exhaust (between 0.04 ± 0.02 and 0.30 ± 0.15 ppbv h−1, with a middle value of 0.16 ± 0.07 ppbv h−1), and the homogeneous reaction of NO + OH (0.14 ± 0.30 ppbv h−1) were found to be the three largest sources of HONO at night. Heterogeneous NO2 conversion on aerosol surfaces (0.03 ± 0.02 ppbv h−1) and soil emission (0.019 ± 0.009 ppbv h−1) were two other minor sources. Correlation analysis shows that NH3 and the relative humidity (RH) may have participated in the heterogeneous transformation of NO2 to HONO at night. Dry deposition (0.41 ± 0.31 ppbv h−1) was the main removal process of HONO at night, followed by dilution (0.18 ± 0.16 ppbv h−1), while HONO loss at aerosol surfaces was much slower (0.008 ± 0.006 ppbv h−1). In the daytime, the average primary emission Pemis was 0.12 ± 0.02 ppbv h−1, and the homogeneous reaction POH+NO was 0.79 ± 0.61 ppbv h−1, larger than the unknown source PUnknown (0.65 ± 0.46 ppbv h−1). Similar to previous studies, PUnknown appeared to be related to the photo-enhanced conversion of NO2. Our results show that primary emissions and the reaction of NO + OH can significantly affect HONO at a site with intensive emissions during both the daytime and nighttime. Uncertainty in parameter values assumed in the calculation of HONO sources can have a strong impact on the relative importance of HONO sources at night, and could be reduced by improving knowledge of key parameters such as the NO2 uptake coefficient. The uncertainty in the estimated direct emission can be reduced by using emission data with higher resolution and quality. Our study highlights the importance of better constraining both conventional and novel HONO sources by reducing uncertainties in their key parameters for advancing our knowledge of this important source of atmospheric OH.

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Simulation Verification of Barrierless HONO Formation from the Oxidation Reaction System of NO, Cl, and Water in the Atmosphere

Cited by 8 publications

References 61 publications

Computational Chemistry as Applied in Environmental Research: Opportunities and Challenges

Computational Chemistry as Applied in Environmental Research: Opportunities and Challenges

Potential Application of Machine-Learning-Based Quantum Chemical Methods in Environmental Chemistry

Budget of nitrous acid (HONO) at an urban site in the fall season of Guangzhou, China

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