Quantum chemical modeling of organic enhanced atmospheric nucleation: A critical review

Wiley Interdisciplinary Reviews Computational Molecular Science, Journal Year: 2023, Volume and Issue: 13(5)

Published: May 9, 2023

Abstract Aerosol particles are important for our global climate, but the mechanisms and especially relative importance of various vapors new formation (NPF) remain uncertain. Quantum chemical (QC) studies on organic enhanced nucleation has past couple decades attracted immense attention, very little remains known about exact compounds that potentially NPF. Here we comprehensively review QC literature atmospheric cluster involving compounds. We outline potential systems should be further investigated. Cluster complex multi‐functional accretion products warrant investigations, such out reach with currently applied methodologies. suggest a “cluster functional groups” approach to address this issue, which will allow identification structure involved in This article is categorized under: Theoretical Physical Chemistry > Reaction Dynamics Kinetics Software Thermochemistry Molecular Statistical Mechanics Interactions

Language: Английский

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Atmospheric Sulfuric Acid–Multi-Base New Particle Formation Revealed through Quantum Chemistry Enhanced by Machine Learning

The Journal of Physical Chemistry A, Journal Year: 2023, Volume and Issue: 127(9), P. 2091 - 2103

Published: Feb. 22, 2023

The formation of molecular clusters and secondary aerosols in the atmosphere has a significant impact on climate. Studies typically focus new particle (NPF) sulfuric acid (SA) with single base molecule (e.g., dimethylamine or ammonia). In this work, we examine combinations synergy several bases. Specifically, used computational quantum chemistry to perform configurational sampling (CS) (SA)0-4(base)0-4 five different types bases: ammonia (AM), methylamine (MA), (DMA), trimethylamine (TMA), ethylenediamine (EDA). Overall, studied 316 clusters. We traditional multilevel funnelling approach augmented by machine-learning (ML) step. ML made CS these possible significantly enhancing speed quality search for lowest free energy configurations. Subsequently, cluster thermodynamics properties were evaluated at DLPNO-CCSD(T0)/aug-cc-pVTZ//ωB97X-D/6-31++G(d,p) level theory. calculated binding energies evaluate stabilities population dynamics simulations. resultant SA-driven NPF rates synergies bases are presented show that DMA EDA act as nucleators (although becomes weak large clusters), TMA acts catalyzer, AM/MA is often overshadowed strong

Language: Английский

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Clusteromics V: Organic Enhanced Atmospheric Cluster Formation

ACS Omega, Journal Year: 2023, Volume and Issue: 8(10), P. 9621 - 9629

Published: Feb. 28, 2023

Formic acid (FA) is a prominent candidate for organic enhanced nucleation due to its high abundance and stabilizing effect on smaller clusters. Its role in new particle formation studied through the use of state-of-the-art quantum chemical methods cluster systems (acid)1–2(FA)1(base)1–2 with acids being sulfuric (SA)/methanesulfonic (MSA) bases consisting ammonia (A), methylamine (MA), dimethylamine (DMA), trimethylamine (TMA), ethylenediamine (EDA). A funneling approach used determine structures initial configurations generated ABCluster program, followed by semiempirical PM7 ωB97X-D/6-31++G(d,p) calculations. The final binding free energy calculated at DLPNO-CCSD(T0)/aug-cc-pVTZ//ωB97X-D/6-31++G(d,p) level theory using quasi-harmonic approximation. Cluster dynamics simulations show that FA has minuscule or negligible MSA–FA–base as well most SA–FA–base systems. SA–FA–DMA system shows highest influence from an enhancement 21%, compared non-FA counterpart.

Language: Английский

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Role of Methanesulfonic Acid in Sulfuric Acid–Amine and Ammonia New Particle Formation

ACS Earth and Space Chemistry, Journal Year: 2023, Volume and Issue: 7(3), P. 653 - 660

Published: March 7, 2023

Aerosol nucleation accounts for over half of all seed particles cloud droplet formation. In the atmosphere, sulfuric acid (SA) nucleates with ammonia, amines, oxidized organics, and many more compounds to form particles. Studies have also shown that methanesulfonic (MSA) independently amines ammonia. MSA SA are produced simultaneously via dimethyl sulfide oxidation in marine atmosphere. However, limited knowledge exists on how nucleate together presence various atmospherically relevant base compounds, which is critical predicting rates accurately. This work provides experimental evidence react SA-MSA-base has different reaction pathways than SA-base nucleation. Specifically, formation SA-MSA heterodimer creates energetically favorable SA-MSA-methylamine an enhancement rates. SA-trimethylamine suppressed by MSA, likely due steric hindrance trimethylamine. These results display importance including reactions between SA, predict particle

Language: Английский

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Massive Assessment of the Binding Energies of Atmospheric Molecular Clusters

Journal of Chemical Theory and Computation, Journal Year: 2022, Volume and Issue: 18(12), P. 7373 - 7383

Published: Nov. 23, 2022

Quantum chemical studies of the formation and growth atmospheric molecular clusters are important for understanding aerosol particle formation. However, search lowest free-energy cluster configuration is extremely time consuming. This makes high-level benchmark data sets valuable in quest global minimum as it allows identification cost-efficient computational methodologies, well development machine learning (ML) models. Herein, we present a highly versatile quantum set comprising total 11 749 (acid)1–2(base)1–2 configurations, containing up to 44 atoms. Utilizing LUMI supercomputer, calculated accurate PNO-CCSD(F12*)(T)/cc-pVDZ-F12 binding energies full configurations leading an unprecedented both regard sheer size with respect level theory. We employ constructed assess performance various semiempirical density functional theory methods. In particular, find that r2-SCAN-3c method shows excellent across related accuracy CPU time, making promising during configurational sampling. Furthermore, applying sets, construct ML models based on Δ-learning provide recommendations future application

Language: Английский

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Clusteromics IV: The Role of Nitric Acid in Atmospheric Cluster Formation

ACS Omega, Journal Year: 2022, Volume and Issue: 7(35), P. 31551 - 31560

Published: Aug. 23, 2022

Nitric acid (NA) has previously been shown to affect atmospheric new particle formation; however, its role still remains highly uncertain. Through the employment of state-of-the-art quantum chemical methods, we study (acid)1-2(base)1-2 and (acid)3(base)2 clusters containing at least one nitric sulfuric (SA) or methanesulfonic (MSA) with bases ammonia (A), methylamine (MA), dimethylamine (DMA), trimethylamine (TMA), ethylenediamine (EDA). The initial cluster configurations are generated using ABCluster program. PM7 ωB97X-D/6-31++G(d,p) calculations used reduce number relevant configurations. thermochemical parameters calculated level theory quasi-harmonic approximation, final single-point energies high-level DLPNO-CCSD(T0)/aug-cc-pVTZ calculations. enhancing effect from presence on formation is studied data dynamics simulations. We find that when NA in excess compared other acids, it a substantial potential.

Language: Английский

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Quantum chemical modeling of atmospheric molecular clusters involving inorganic acids and methanesulfonic acid

Chemical Physics Reviews, Journal Year: 2023, Volume and Issue: 4(3)

Published: Sept. 1, 2023

Atmospheric molecular cluster formation is the first stage toward aerosol particle formation. Despite intensive progress in recent years, relative role of different vapors and mechanisms for forming clusters still not well-understood. Quantum chemical (QC) methods can give insight into thereby yield information about potentially relevant compounds. Here, we summarize QC literature on clustering involving species such as sulfuric acid, methanesulfonic nitric acid. The importance iodine iodous acid (HIO2) iodic (HIO3) atmospheric an emerging topic, critically review our view how to future. We outline machine learning (ML) be used enhance configurational sampling, leading a massive increase compositions that modeled. In future, ML-boosted could allow us comprehensively understand complex with multiple pathways, one step closer implementing accurate models.

Language: Английский

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Atmospheric Gas-Phase Formation of Methanesulfonic Acid

Environmental Science & Technology, Journal Year: 2023, Volume and Issue: 57(50), P. 21168 - 21177

Published: Dec. 5, 2023

Despite its impact on the climate, mechanism of methanesulfonic acid (MSA) formation in oxidation dimethyl sulfide (DMS) remains unclear. The DMS + OH reaction is known to form methanesulfinic (MSIA), methane sulfenic (MSEA), methylthio radical (CH3S), and hydroperoxymethyl thioformate (HPMTF). Among them, HPMTF reacts further SO2 OCS, while other three CH3SO2 radical. Based theoretical calculations, we find that can add O2 CH3S(O)2OO, which react MSA. branching ratio highly temperature sensitive, MSA yield increases with decreasing temperature. In warmer regions, dominant product oxidation, colder large amounts form. Global modeling indicates proposed temperature-sensitive leads a substantial increase simulated global atmospheric burden.

Language: Английский

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Clusterome: A Comprehensive Data Set of Atmospheric Molecular Clusters for Machine Learning Applications

ACS Omega, Journal Year: 2023, Volume and Issue: 8(28), P. 25155 - 25164

Published: June 30, 2023

Formation and growth of atmospheric molecular clusters into aerosol particles impact the global climate contribute to high uncertainty in modern models. Cluster formation is usually studied using quantum chemical methods, which quickly becomes computationally expensive when system sizes grow. In this work, we present a large database ∼250k relevant cluster structures, can be applied for developing machine learning (ML) The used train ML model kernel ridge regression (KRR) with FCHL19 representation. We test ability extrapolate from smaller larger clusters, between different molecules, equilibrium structures out-of-equilibrium transferability onto systems new interactions. show that KRR models transfer acid base interactions mean absolute errors below 1 kcal/mol. suggest introducing an iterative step configurational sampling processes, reduce computational expense. Such approach would allow us study significantly more at higher accuracy than previously possible thereby cover much part compounds.

Language: Английский

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Nitric Acid and Organic Acids Suppress the Role of Methanesulfonic Acid in Atmospheric New Particle Formation

The Journal of Physical Chemistry A, Journal Year: 2023, Volume and Issue: 127(36), P. 7568 - 7578

Published: Aug. 31, 2023

Multicomponent atmospheric molecular clusters, typically comprising a combination of acids and bases, play pivotal role in our climate system contribute to the perplexing uncertainties embedded modern models. Our understanding cluster formation is limited by lack studies on complex mixed-acid-mixed-base systems. Here, we investigate multicomponent clusters consisting mixtures several acid base molecules: sulfuric (SA), methanesulfonic (MSA), nitric (NA), formic (FA), along with methylamine (MA), dimethylamine (DMA), trimethylamine (TMA). We calculated binding free energies comprehensive set 252 at DLPNO-CCSD(T0)/aug-cc-pVTZ//ωB97X-D/6-31++G(d,p) level theory. Combined existing datasets, simulated new particle (NPF) rates using Atmospheric Cluster Dynamics Code (ACDC). find that presence NA FA had substantial impact, increasing NPF rate 60% realistic conditions. Intriguingly, suppress MSA NPF. These findings suggest even high concentration has impact polluted regions NA. outline method for generating lookup table could potentially be used models sufficiently incorporates all required chemistry. By unraveling mechanisms get one step closer comprehending their implications global system.

Language: Английский

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