Tri-base synergy in sulfuric acid-base clusters

Hong Bin Xie; Jonas Elm

doi:10.3390/atmos12101260

Tri-base synergy in sulfuric acid-base clusters

Hong Bin Xie, Jonas Elm^*

^*Corresponding author for this work

Department of Chemistry
iCLIMATE Aarhus University Interdisciplinary Centre for Climate Change - iCLIMATE Aarhus University Interdisciplinary Centre for Climate Change, Langelandsgade

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

12 Citations (Scopus)

Abstract

Synergistic effects between different bases can greatly enhance atmospheric sulfuric acid (SA)-base cluster formation. However, only the synergy between two base components has previously been investigated. Here, we extend this concept to three bases by studying large atmospherically rel-evant (SA)₃ (base)₃ clusters, with the bases ammonia (A), methylamine (MA), dimethylamine (DMA), trimethylamine (TMA) and ethylenediamine (EDA). Using density functional theory—ωB97X-D/6-31++G(d,p)—we calculate the cluster structures and vibrational frequencies. The thermochemical parameters are calculated at 29,815 K and 1 atm, using the quasi-harmonic approximation. The binding energies of the clusters are calculated using high level DLPNO-CCSD(T₀ )/aug-cc-pVTZ. We find that the cluster stability in general depends on the basicity of the constituent bases, with some noteworthy additional guidelines: DMA enhances the cluster stability, TMA decreases the cluster stability and there is high synergy between DMA and EDA. Based on our calculations, we find it highly likely that three, or potentially more, different bases, are involved in the growth pathways of sulfuric acid-base clusters.

Original language	English
Article number	1260
Journal	Atmosphere
Volume	12
Issue	10
DOIs	https://doi.org/10.3390/atmos12101260
Publication status	Published - Oct 2021

Keywords

Aerosols
Atmospheric molecular clusters
New particle formation
Quantum chemistry

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10.3390/atmos12101260Licence: CC BY

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title = "Tri-base synergy in sulfuric acid-base clusters",

abstract = "Synergistic effects between different bases can greatly enhance atmospheric sulfuric acid (SA)-base cluster formation. However, only the synergy between two base components has previously been investigated. Here, we extend this concept to three bases by studying large atmospherically rel-evant (SA)3 (base)3 clusters, with the bases ammonia (A), methylamine (MA), dimethylamine (DMA), trimethylamine (TMA) and ethylenediamine (EDA). Using density functional theory—ωB97X-D/6-31++G(d,p)—we calculate the cluster structures and vibrational frequencies. The thermochemical parameters are calculated at 29,815 K and 1 atm, using the quasi-harmonic approximation. The binding energies of the clusters are calculated using high level DLPNO-CCSD(T0 )/aug-cc-pVTZ. We find that the cluster stability in general depends on the basicity of the constituent bases, with some noteworthy additional guidelines: DMA enhances the cluster stability, TMA decreases the cluster stability and there is high synergy between DMA and EDA. Based on our calculations, we find it highly likely that three, or potentially more, different bases, are involved in the growth pathways of sulfuric acid-base clusters.",

keywords = "Aerosols, Atmospheric molecular clusters, New particle formation, Quantum chemistry",

author = "Xie, {Hong Bin} and Jonas Elm",

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year = "2021",

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doi = "10.3390/atmos12101260",

language = "English",

volume = "12",

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T1 - Tri-base synergy in sulfuric acid-base clusters

AU - Xie, Hong Bin

AU - Elm, Jonas

PY - 2021/10

Y1 - 2021/10

N2 - Synergistic effects between different bases can greatly enhance atmospheric sulfuric acid (SA)-base cluster formation. However, only the synergy between two base components has previously been investigated. Here, we extend this concept to three bases by studying large atmospherically rel-evant (SA)3 (base)3 clusters, with the bases ammonia (A), methylamine (MA), dimethylamine (DMA), trimethylamine (TMA) and ethylenediamine (EDA). Using density functional theory—ωB97X-D/6-31++G(d,p)—we calculate the cluster structures and vibrational frequencies. The thermochemical parameters are calculated at 29,815 K and 1 atm, using the quasi-harmonic approximation. The binding energies of the clusters are calculated using high level DLPNO-CCSD(T0 )/aug-cc-pVTZ. We find that the cluster stability in general depends on the basicity of the constituent bases, with some noteworthy additional guidelines: DMA enhances the cluster stability, TMA decreases the cluster stability and there is high synergy between DMA and EDA. Based on our calculations, we find it highly likely that three, or potentially more, different bases, are involved in the growth pathways of sulfuric acid-base clusters.

AB - Synergistic effects between different bases can greatly enhance atmospheric sulfuric acid (SA)-base cluster formation. However, only the synergy between two base components has previously been investigated. Here, we extend this concept to three bases by studying large atmospherically rel-evant (SA)3 (base)3 clusters, with the bases ammonia (A), methylamine (MA), dimethylamine (DMA), trimethylamine (TMA) and ethylenediamine (EDA). Using density functional theory—ωB97X-D/6-31++G(d,p)—we calculate the cluster structures and vibrational frequencies. The thermochemical parameters are calculated at 29,815 K and 1 atm, using the quasi-harmonic approximation. The binding energies of the clusters are calculated using high level DLPNO-CCSD(T0 )/aug-cc-pVTZ. We find that the cluster stability in general depends on the basicity of the constituent bases, with some noteworthy additional guidelines: DMA enhances the cluster stability, TMA decreases the cluster stability and there is high synergy between DMA and EDA. Based on our calculations, we find it highly likely that three, or potentially more, different bases, are involved in the growth pathways of sulfuric acid-base clusters.

KW - Aerosols

KW - Atmospheric molecular clusters

KW - New particle formation

KW - Quantum chemistry

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DO - 10.3390/atmos12101260

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VL - 12

JO - Atmosphere

JF - Atmosphere

IS - 10

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ER -

Tri-base synergy in sulfuric acid-base clusters

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