Critical Role of Iodous Acid in Neutral Iodine Oxoacid Nucleation

Rongjie Zhang; Hong Bin Xie; Fangfang Ma; Jingwen Chen; Siddharth Iyer; Mario Simon; Martin Heinritzi; Jiali Shen; Yee Jun Tham; Theo Kurtén; Douglas R. Worsnop; Jasper Kirkby; Joachim Curtius; Mikko Sipilä; Markku Kulmala; Xu Cheng He

doi:10.1021/acs.est.2c04328

Critical Role of Iodous Acid in Neutral Iodine Oxoacid Nucleation

Rongjie Zhang, Hong Bin Xie, Fangfang Ma, Jingwen Chen, Siddharth Iyer, Mario Simon, Martin Heinritzi, Jiali Shen, Yee Jun Tham, Theo Kurtén, Douglas R. Worsnop, Jasper Kirkby, Joachim Curtius, Mikko Sipilä, Markku Kulmala, Xu Cheng He

Fysiikka

Tutkimustuotos: Artikkeli › Tieteellinen › vertaisarvioitu

26 Sitaatiot (Scopus)

10 Lataukset (Pure)

Abstrakti

Nucleation of neutral iodine particles has recently been found to involve both iodic acid (HIO₃) and iodous acid (HIO₂). However, the precise role of HIO₂in iodine oxoacid nucleation remains unclear. Herein, we probe such a role by investigating the cluster formation mechanisms and kinetics of (HIO₃)_m(HIO₂)_n(m = 0-4, n = 0-4) clusters with quantum chemical calculations and atmospheric cluster dynamics modeling. When compared with HIO₃, we find that HIO₂binds more strongly with HIO₃and also more strongly with HIO₂. After accounting for ambient vapor concentrations, the fastest nucleation rate is predicted for mixed HIO₃-HIO₂clusters rather than for pure HIO₃or HIO₂ones. Our calculations reveal that the strong binding results from HIO₂exhibiting a base behavior (accepting a proton from HIO₃) and forming stronger halogen bonds. Moreover, the binding energies of (HIO₃)_m(HIO₂)_nclusters show a far more tolerant choice of growth paths when compared with the strict stoichiometry required for sulfuric acid-base nucleation. Our predicted cluster formation rates and dimer concentrations are acceptably consistent with those measured by the Cosmic Leaving Outdoor Droplets (CLOUD) experiment. This study suggests that HIO₂could facilitate the nucleation of other acids beyond HIO₃in regions where base vapors such as ammonia or amines are scarce.

Alkuperäiskieli	Englanti
Sivut	14166-14177
Sivumäärä	12
Julkaisu	Environmental Science and Technology
Vuosikerta	56
Numero	19
DOI - pysyväislinkit	https://doi.org/10.1021/acs.est.2c04328
Tila	Julkaistu - 2022
OKM-julkaisutyyppi	A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

Julkaisufoorumi-taso

Jufo-taso 2

!!ASJC Scopus subject areas

Yleinen kemia
Environmental Chemistry

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10.1021/acs.est.2c04328Lisenssi: CC BY

acs.est.2c04328Final published version, 5,21 MBLisenssi: CC BY

https://urn.fi/URN:NBN:fi:tuni-202211078208Lisenssi: CC BY

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@article{3f6474f2ff7f4cb0ae785598e9cd01c7,

title = "Critical Role of Iodous Acid in Neutral Iodine Oxoacid Nucleation",

abstract = "Nucleation of neutral iodine particles has recently been found to involve both iodic acid (HIO3) and iodous acid (HIO2). However, the precise role of HIO2in iodine oxoacid nucleation remains unclear. Herein, we probe such a role by investigating the cluster formation mechanisms and kinetics of (HIO3)m(HIO2)n(m = 0-4, n = 0-4) clusters with quantum chemical calculations and atmospheric cluster dynamics modeling. When compared with HIO3, we find that HIO2binds more strongly with HIO3and also more strongly with HIO2. After accounting for ambient vapor concentrations, the fastest nucleation rate is predicted for mixed HIO3-HIO2clusters rather than for pure HIO3or HIO2ones. Our calculations reveal that the strong binding results from HIO2exhibiting a base behavior (accepting a proton from HIO3) and forming stronger halogen bonds. Moreover, the binding energies of (HIO3)m(HIO2)nclusters show a far more tolerant choice of growth paths when compared with the strict stoichiometry required for sulfuric acid-base nucleation. Our predicted cluster formation rates and dimer concentrations are acceptably consistent with those measured by the Cosmic Leaving Outdoor Droplets (CLOUD) experiment. This study suggests that HIO2could facilitate the nucleation of other acids beyond HIO3in regions where base vapors such as ammonia or amines are scarce.",

keywords = "atmospheric cluster dynamics simulation, iodic acid, iodine oxoacid nucleation, iodous acid, particle formation, quantum chemical calculation",

author = "Rongjie Zhang and Xie, {Hong Bin} and Fangfang Ma and Jingwen Chen and Siddharth Iyer and Mario Simon and Martin Heinritzi and Jiali Shen and Tham, {Yee Jun} and Theo Kurt{\'e}n and Worsnop, {Douglas R.} and Jasper Kirkby and Joachim Curtius and Mikko Sipil{\"a} and Markku Kulmala and He, {Xu Cheng}",

note = "Funding Information: This research has received support from the National Natural Science Foundation of China (22236004, 21876024, 22176022, 42175118); the Major International (Regional) Joint Research Project (21661142001); the Academy of Finland (296628, 316114, 1315600 and 1346369); the European Research Council under the European Union{\textquoteright}s Horizon 2020 research and innovation program under Grant No. 101002728 (ERC Consolidator Grant Project ADAPT); the German Federal Ministry of Education and Research, CLOUD-12 (01LK1222A) and CLOUD-16 (01LK1601A); the European Commission Seventh Framework Programme and European Union Horizon 2020 program (Marie Sk{\l}odowska Curie ITNs no. 316662 “CLOUD-TRAIN”, no. 764991 “CLOUD-MOTION”, MSCA-IF no. 656994 “nano-CAVa”, and MC-COFUND grant no. 600377); CLOUD-Motion H2020-MSCA-ITN-2017 no. 764991 and the German Ministry of Science and Education (CLOUD-16, 01LK1601A); the European Research Council (GASPARCON, 714621); the ACCC Flagship funded by the Academy of Finland (grant no. 337549); the European Research Council (ERC) project ATM-GTP (grant no. 742206); and the Supercomputing Center of the Dalian University of Technology. We thank the Jenny and Antti Wihuri Foundation for providing funding for this research. Publisher Copyright: {\textcopyright} 2022 The Author.",

year = "2022",

doi = "10.1021/acs.est.2c04328",

language = "English",

volume = "56",

pages = "14166--14177",

journal = "Environmental Science and Technology",

issn = "0013-936X",

publisher = "American Chemical Society",

number = "19",

}

TY - JOUR

T1 - Critical Role of Iodous Acid in Neutral Iodine Oxoacid Nucleation

AU - Zhang, Rongjie

AU - Xie, Hong Bin

AU - Ma, Fangfang

AU - Chen, Jingwen

AU - Iyer, Siddharth

AU - Simon, Mario

AU - Heinritzi, Martin

AU - Shen, Jiali

AU - Tham, Yee Jun

AU - Kurtén, Theo

AU - Worsnop, Douglas R.

AU - Kirkby, Jasper

AU - Curtius, Joachim

AU - Sipilä, Mikko

AU - Kulmala, Markku

AU - He, Xu Cheng

N1 - Funding Information: This research has received support from the National Natural Science Foundation of China (22236004, 21876024, 22176022, 42175118); the Major International (Regional) Joint Research Project (21661142001); the Academy of Finland (296628, 316114, 1315600 and 1346369); the European Research Council under the European Union’s Horizon 2020 research and innovation program under Grant No. 101002728 (ERC Consolidator Grant Project ADAPT); the German Federal Ministry of Education and Research, CLOUD-12 (01LK1222A) and CLOUD-16 (01LK1601A); the European Commission Seventh Framework Programme and European Union Horizon 2020 program (Marie Skłodowska Curie ITNs no. 316662 “CLOUD-TRAIN”, no. 764991 “CLOUD-MOTION”, MSCA-IF no. 656994 “nano-CAVa”, and MC-COFUND grant no. 600377); CLOUD-Motion H2020-MSCA-ITN-2017 no. 764991 and the German Ministry of Science and Education (CLOUD-16, 01LK1601A); the European Research Council (GASPARCON, 714621); the ACCC Flagship funded by the Academy of Finland (grant no. 337549); the European Research Council (ERC) project ATM-GTP (grant no. 742206); and the Supercomputing Center of the Dalian University of Technology. We thank the Jenny and Antti Wihuri Foundation for providing funding for this research. Publisher Copyright: © 2022 The Author.

PY - 2022

Y1 - 2022

N2 - Nucleation of neutral iodine particles has recently been found to involve both iodic acid (HIO3) and iodous acid (HIO2). However, the precise role of HIO2in iodine oxoacid nucleation remains unclear. Herein, we probe such a role by investigating the cluster formation mechanisms and kinetics of (HIO3)m(HIO2)n(m = 0-4, n = 0-4) clusters with quantum chemical calculations and atmospheric cluster dynamics modeling. When compared with HIO3, we find that HIO2binds more strongly with HIO3and also more strongly with HIO2. After accounting for ambient vapor concentrations, the fastest nucleation rate is predicted for mixed HIO3-HIO2clusters rather than for pure HIO3or HIO2ones. Our calculations reveal that the strong binding results from HIO2exhibiting a base behavior (accepting a proton from HIO3) and forming stronger halogen bonds. Moreover, the binding energies of (HIO3)m(HIO2)nclusters show a far more tolerant choice of growth paths when compared with the strict stoichiometry required for sulfuric acid-base nucleation. Our predicted cluster formation rates and dimer concentrations are acceptably consistent with those measured by the Cosmic Leaving Outdoor Droplets (CLOUD) experiment. This study suggests that HIO2could facilitate the nucleation of other acids beyond HIO3in regions where base vapors such as ammonia or amines are scarce.

AB - Nucleation of neutral iodine particles has recently been found to involve both iodic acid (HIO3) and iodous acid (HIO2). However, the precise role of HIO2in iodine oxoacid nucleation remains unclear. Herein, we probe such a role by investigating the cluster formation mechanisms and kinetics of (HIO3)m(HIO2)n(m = 0-4, n = 0-4) clusters with quantum chemical calculations and atmospheric cluster dynamics modeling. When compared with HIO3, we find that HIO2binds more strongly with HIO3and also more strongly with HIO2. After accounting for ambient vapor concentrations, the fastest nucleation rate is predicted for mixed HIO3-HIO2clusters rather than for pure HIO3or HIO2ones. Our calculations reveal that the strong binding results from HIO2exhibiting a base behavior (accepting a proton from HIO3) and forming stronger halogen bonds. Moreover, the binding energies of (HIO3)m(HIO2)nclusters show a far more tolerant choice of growth paths when compared with the strict stoichiometry required for sulfuric acid-base nucleation. Our predicted cluster formation rates and dimer concentrations are acceptably consistent with those measured by the Cosmic Leaving Outdoor Droplets (CLOUD) experiment. This study suggests that HIO2could facilitate the nucleation of other acids beyond HIO3in regions where base vapors such as ammonia or amines are scarce.

KW - atmospheric cluster dynamics simulation

KW - iodic acid

KW - iodine oxoacid nucleation

KW - iodous acid

KW - particle formation

KW - quantum chemical calculation

U2 - 10.1021/acs.est.2c04328

DO - 10.1021/acs.est.2c04328

M3 - Article

C2 - 36126141

AN - SCOPUS:85138975733

SN - 0013-936X

VL - 56

SP - 14166

EP - 14177

JO - Environmental Science and Technology

JF - Environmental Science and Technology

IS - 19

ER -

Critical Role of Iodous Acid in Neutral Iodine Oxoacid Nucleation

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