Growth of atmospheric freshly nucleated particles: a semi-empirical molecular dynamics study DOI Creative Commons
Yosef Knattrup, Ivo Neefjes, Jakub Kubečka

et al.

Aerosol Research, Journal Year: 2025, Volume and Issue: 3(1), P. 237 - 251

Published: May 19, 2025

Abstract. When simulating new particle formation rates, collisions in the system are approximated as hard spheres without long-range interactions. This simplification may lead to an underestimation of actual rate. In this study, we employ semi-empirical molecular dynamics (SEMD) at GFN1-xTB level theory probe sticking process monomers sulfuric acid (SA), methanesulfonic (MSA), nitric (NA), formic (FA), ammonia (AM), methylamine (MA), dimethylamine (DMA), and trimethylamine (TMA) onto freshly nucleated particles (FNPs). The FNPs considered (SA)10(AM)10, (SA)10(MA)10, (SA)10(DMA)10, (SA)10(TMA)10. general, find that hard-sphere kinetic approximation, which neglects interactions, significantly underestimates number leading sticking. By calculating coefficient from SEMD simulations, obtain enhancement factors 2.3 1.5 for SA + (SA)10(AM)10 AM collisions, respectively. A comparison with OPLS (optimized potentials liquid simulations) all-atom force field simulations shows similar 2.4 1.6 Compared exhibits a more isotropic behavior, probability remaining near unity small offsets before rapidly dropping 0 % beyond certain offset. contrast, show gradual decline due orientations still largest discrepancy between two methods occurs lower collision velocities – below 200 m s−1 400 where even head-on predict low or zero probability. has previously been attributed periodic repulsions rotating partners caused by fluctuations their charge distributions. do not exhibit behavior. Since these populated our both yield factors. However, systems larger effective masses, such prevalent, would expect diverge.

Language: Английский

Significant contributions of trimethylamine to sulfuric acid nucleation in polluted environments DOI Creative Commons
Runlong Cai, Rujing Yin, Xue Li

et al.

npj Climate and Atmospheric Science, Journal Year: 2023, Volume and Issue: 6(1)

Published: June 27, 2023

Abstract As one of the least understood aerosol processes, nucleation can be a dominant source atmospheric aerosols. Sulfuric acid (SA)-amine binary with dimethylamine (DMA) has been recognized as governing mechanism in polluted continental boundary layer. Here we demonstrate importance trimethylamine (TMA) for complex atmosphere and propose molecular-level SA-DMA-TMA ternary an improvement upon conventional mechanism. Using proposed mechanism, could connect gaseous amines to SA-amine cluster signals measured urban Beijing. Results show that TMA accelerate SA-DMA-based new particle formation Beijing by 50–100%. Considering global abundance DMA, our findings imply comparable DMA layer, probably higher contributions from rural environments future controlled emissions.

Language: Английский

Citations

32
Quantum chemical modeling of organic enhanced atmospheric nucleation: A critical review DOI Creative Commons
Jonas Elm, Daniel Ayoubi, Morten Engsvang

et al.

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

Citations

27
Atmospheric Sulfuric Acid–Multi-Base New Particle Formation Revealed through Quantum Chemistry Enhanced by Machine Learning DOI
Jakub Kubečka, Ivo Neefjes, Vitus Besel

et al.

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

Citations

26
Clusteromics V: Organic Enhanced Atmospheric Cluster Formation DOI Creative Commons
Daniel Ayoubi, Yosef Knattrup, Jonas Elm

et al.

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

Citations

24
Clusteromics II: Methanesulfonic Acid–Base Cluster Formation DOI Creative Commons
Jonas Elm

ACS Omega, Journal Year: 2021, Volume and Issue: 6(26), P. 17035 - 17044

Published: June 23, 2021

The role of methanesulfonic acid (MSA) in atmospheric new particle formation remains highly uncertain. Using state-of-the-art computational methods, we study the electrically neutral

Language: Английский

Citations

55
Clusteromics III: Acid Synergy in Sulfuric Acid–Methanesulfonic Acid–Base Cluster Formation DOI Creative Commons
Jonas Elm

ACS Omega, Journal Year: 2022, Volume and Issue: 7(17), P. 15206 - 15214

Published: April 20, 2022

Acid-base molecular clusters are an important stage in atmospheric new particle formation. While such most likely multicomponent nature, there very few reports on consisting of multiple acid molecules and base molecules. By applying state-of-the-art quantum chemical methods, we herein study electrically neutral (SA)1(MSA)1(base)0-2 with = ammonia (A), methylamine (MA), dimethylamine (DMA), trimethylamine (TMA) ethylenediamine (EDA). The cluster structures obtained using a funneling approach employing the ABCluster program, semiempirical PM7 calculations ωB97X-D/6-31++G(d,p) calculations. final binding free energies calculated at DLPNO-CCSD(T0)/aug-cc-pVTZ//ωB97X-D/6-31++G(d,p) level theory quasi-harmonic approximation. Based geometries thermochemistry (at 298.15 K 1 atm), find that mixed (SA)1(MSA)1(base)1-2 more resemble (SA)2(base)1-2 compared to (MSA)2(base)1-2 clusters. Hence, some steric hindrance lack hydrogen bond capacity previously observed is diminished corresponding Cluster kinetics simulations reveal presence MSA molecule enhances formation potential by up factor 20. We SA-MSA-DMA have highest potential, thus, this system should be further extended larger sizes future studies.

Language: Английский

Citations

36
A new advance in the pollution profile, transformation process, and contribution to aerosol formation and aging of atmospheric amines DOI Creative Commons

Xinlin Shen,

Jiangyao Chen, Guiying Li

et al.

Environmental Science Atmospheres, Journal Year: 2023, Volume and Issue: 3(3), P. 444 - 473

Published: Jan. 1, 2023

Atmospheric amines from various sources undergo a variety of homogeneous and heterogeneous reactions to contribute the overall process aerosol particle formation further affect climate.

Language: Английский

Citations

22
Intermolecular hydrogen bond interactions in water clusters of zwitterionic glycine: DFT, MESP, AIM, RDG, and molecular dynamics analysis DOI
Natarajan Sathiyamoorthy Venkataramanan, Ambigapathy Suvitha,

Sirajunnisa Abdul Rahim

et al.

Journal of Molecular Liquids, Journal Year: 2024, Volume and Issue: 396, P. 123932 - 123932

Published: Jan. 11, 2024

Language: Английский

Citations

9
Massive Assessment of the Binding Energies of Atmospheric Molecular Clusters DOI
Andreas Buchgraitz Jensen, Jakub Kubečka, Gunnar Alexander Schmitz

et al.

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

Citations

29
Quantum Machine Learning Approach for Studying Atmospheric Cluster Formation DOI
Jakub Kubečka, Anders S. Christensen, Freja Rydahl Rasmussen

et al.

Environmental Science & Technology Letters, Journal Year: 2022, Volume and Issue: 9(3), P. 239 - 244

Published: Jan. 31, 2022

Quantum chemical (QC) calculations can yield direct insight into an atmospheric cluster formation mechanism and rates. However, such are extremely computationally demanding as more than millions of configurations might exist need to be computed. We present efficient approach produce high quality QC data sets for applications in studies how train accurate quantum machine learning model on the generated data. Using two-component sulfuric acid─water system a proof concept, we demonstrate that kernel ridge regression with Δ-learning trained accurately predict binding energies equilibrium mean absolute errors below 0.5 kcal mol–1. Additionally, enlarge training set nonequilibrium show possibility predicting new structures clusters several molecules larger those set. Applying leads drastic reduction number relevant explicitly evaluated by methods. The presented is directly transferable arbitrary composition will lead faster exploration configurational space systems.

Language: Английский

Citations

27