Large ternary hydrogen-bonded pre-nucleation clusters in the Earth’s atmosphere

Herb, Jason; Nadykto, Alexey B.; Yu, Fangqun

doi:10.1016/j.cplett.2011.10.035

Cited by 77 publications

(92 citation statements)

References 38 publications

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“…Typically, OH bond lengths and O-O distances in (H2SO4)n(CH3NH2)m(H2O)k are a bit shorter than those in (H2SO4)n(NH3)m(H2O)k, being a sign of enhanced thermodynamic stability of (H2SO4)n(CH3NH2)m (H2O)k compared to (H2SO4)n(NH3)m(H2O)k. In the Supplementary Materials, an interested reader can find the complete data set (over 180 equilibrium geometries in total) for the Cartesian geometries of global and local minima located within ~3 kcal/mol of global minima, which cover the whole range of (H2SO4)n(CH3NH2)m(H2O)k, from (CH3NH2) molecules and (CH3NH2) hydrates to (H2SO4)2 (CH3NH2)2(H2O)5, respectively. The corresponding data sets for (H2SO4)n(NH3)m(H2O)k and (H2SO4)n(CH3)2NH)m(H2O)k are available in [26,61] and [22], respectively. Intrinsic statistical and entropic effects related to the difference between the Boltzmann-Gibbs average over the isomer mixture of a given composition and the energy of the global minimum of the same composition and to the difference in entropies between the global and minima do not exceed 0.1 kcal mol…”

Section: Methodsmentioning

confidence: 99%

“…Abbreviations NB, A, DMA and MA refer to no base, ammonia, dimethylamine and methylamine, respectively. The data for ammonia and dimethylamine were adopted from [26,61] and [22], respectively. The comparison of hydration free energies for clusters containing monomers and dimers of H2SO4 and bases such as ammonia, DMA and MA shown in Figure 2 indicates that the hydration of the MA is stronger than that of other common atmospheric bases, NH3 and DMA.…”

Section: Equilibrium Geometries and Cluster Propertiesmentioning

confidence: 99%

“…DMA and MA refer to dimethyl-and methylamine, respectively. The data for ammonia and dimethylamine were adopted from [26,61] and [22], respectively. Table 3 presents enthalpies, entropies and Gibbs free energy changes describing the formation of (H2SO4)n(CH3NH2)m(H2O)k clusters via the (H2SO4)n(CH3NH2)m−1(H2O)k+(CH3NH2) <=> (H2SO4)n(CH3NH2)m(H2O)k reaction.…”

Section: Hydrationmentioning

confidence: 99%

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Estimating the Lower Limit of the Impact of Amines on Nucleation in the Earth’s Atmosphere

Nadykto

Herb

et al. 2015

Entropy

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Amines, organic derivatives of NH3, are important common trace atmospheric species that can enhance new particle formation in the Earth's atmosphere under favorable conditions. While methylamine (MA), dimethylamine (DMA) and trimethylamine (TMA) all efficiently enhance binary nucleation, MA may represent the lower limit of the enhancing effect of amines on atmospheric nucleation. In the present paper, we report new thermochemical data concerning MA-enhanced nucleation, which were obtained using the DFT PW91PW91/6-311++G (3df, 3pd) method, and investigate the enhancement in production of stable pre-nucleation clusters due to the MA. We found that the MA ternary nucleation begins to dominate over ternary nucleation of sulfuric acid, water and ammonia. This means that under real atmospheric conditions ([MA] ~ 1 ppt, [NH3] ~ 1 ppb) the lower limit of the enhancement due to methylamines is either close to or higher than the typical effect of NH3. A very strong impact of the MA is observed at low RH; however it decreases quickly as the RH grows. Low RH and low ambient temperatures were found to be particularly favorable for the enhancement in production of stable sulfuric acid-water clusters due to the MA.

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Section: Methodsmentioning

confidence: 99%

Section: Equilibrium Geometries and Cluster Propertiesmentioning

confidence: 99%

Section: Hydrationmentioning

confidence: 99%

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Estimating the Lower Limit of the Impact of Amines on Nucleation in the Earth’s Atmosphere

Nadykto

Herb

et al. 2015

Entropy

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“…One of the important assumptions made is that the base-containing trimer and tetramer do not evaporate significantly. The data of Ortega et al (2012) suggest that the evaporation rates of the A 3 B 1 and the A 4 B 1 clusters are not negligible, even at temperatures at and below 248 K. However, the presence of further ammonia molecules in the trimer and tetramer can lower the evaporation rates and water should have a similar effect Herb et al, 2011). In contrast, the base-containing dimer (A 2 B) has a very small evaporation rate.…”

Section: Clustermentioning

confidence: 84%

“…Therefore, the Chen et al (2012) value can be regarded as a best estimate for the overall trimer evaporation rate for their experimental conditions. Herb et al (2011) also simulated the effect that one water molecule has on the acid evaporation rate from (H 2 SO 4 ) 3 (NH 3 ) 1 (H 2 O) 0,1 clusters. While the water molecule lowers the evaporation rate, the absolute evaporation rate is higher (2.9 × 10 4 s −1 at 300 K) than for the Ortega et al (2012) data.…”

Section: Acid-base Modelmentioning

confidence: 99%

Thermodynamics of the formation of sulfuric acid dimers in the binary (H2SO4–H2O) and ternary (H2SO4–H2O–NH3) system

Kürten¹,

Münch

Rondo

et al. 2015

Atmos. Chem. Phys.

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Abstract. Sulfuric acid is an important gas influencing atmospheric new particle formation (NPF). Both the binary (H 2 SO 4 -H 2 O) system and the ternary system involving ammonia (H 2 SO 4 -H 2 O-NH 3 ) may be important in the free troposphere. An essential step in the nucleation of aerosol particles from gas-phase precursors is the formation of a dimer, so an understanding of the thermodynamics of dimer formation over a wide range of atmospheric conditions is essential to describe NPF. We have used the CLOUD chamber to conduct nucleation experiments for these systems at temperatures from 208 to 248 K. Neutral monomer and dimer concentrations of sulfuric acid were measured using a chemical ionization mass spectrometer (CIMS). From these measurements, dimer evaporation rates in the binary system were derived for temperatures of 208 and 223 K. We compare these results to literature data from a previous study that was conducted at higher temperatures but is in good agreement with the present study. For the ternary system the formation of Published by Copernicus Publications on behalf of the European Geosciences Union. A. Kürten et al.: Thermodynamics of the formation of sulfuric acid dimersH 2 SO 4 q NH 3 is very likely an essential step in the formation of sulfuric acid dimers, which were measured at 210, 223, and 248 K. We estimate the thermodynamic properties (dH and dS) of the H 2 SO 4 q NH 3 cluster using a simple heuristic model and the measured data. Furthermore, we report the first measurements of large neutral sulfuric acid clusters containing as many as 10 sulfuric acid molecules for the binary system using chemical ionization-atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometry.

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Effect of methyl hydrogen sulfate on the formation of sulfuric acid‐ammonia clusters: A theoretical study

Gao

Wang

Zhang

et al. 2022

J Chinese Chemical Soc

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Methyl hydrogen sulfate (MHS) as a common nucleation precursor that has important effect on new particle formation (NPF). Liu et al. showed that MHS and sulfuric acid (SA) generation are competitive due to consumption of the common precursor SO 3 , and the nucleation ability of SA is better than MHS. Thus, MHS inhibits the SA-DMA-based clusters formation particularly in regions with high [MO] (methanol) (Liu et al., Proc. Natl. Acad. Sci. U.S.A. 2019, 116, 24,966). However, in regions where [H 2 O] is much higher than [MO] ([SA] > > [MHS]), the SO 3 consumed by the generation of less MHS will not significantly reduce the [SA], whether MHS still inhibits SA-A-based clusters formation and how MHS affects the growth pathways of MHS-SA-A-based clusters remains unclear. Hence, quantum chemistry calculations combining Atmospheric Cluster Dynamics Code (ACDC) are used to investigate the role of MHS in the SA-A-based system. Our conclusions show two different effects of MHS in NPF process: "inhibiting" in regions with high [MO] and "weakly facilitating" in regions with high [H 2 O] and low [MO]. The growth pathways show that with the increasing [MHS], the role of MHS in NPF gradually changes from "transporter" to "participator", and the contribution to the pathways increases from 7 to 85%. Our results contribute to understanding the NPF in low-temperature regions with different concentrations of MO and H 2 O. K E Y W O R D S ammonia (a), growth pathway, methyl hydrogen sulfate (MHS), new particle formation (NPF), sulfuric acid (SA)

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Large ternary hydrogen-bonded pre-nucleation clusters in the Earth’s atmosphere

Cited by 77 publications

References 38 publications

Estimating the Lower Limit of the Impact of Amines on Nucleation in the Earth’s Atmosphere

Estimating the Lower Limit of the Impact of Amines on Nucleation in the Earth’s Atmosphere

Thermodynamics of the formation of sulfuric acid dimers in the binary (H<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O) and ternary (H<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O–NH<sub>3</sub>) system

Effect of methyl hydrogen sulfate on the formation of sulfuric acid‐ammonia clusters: A theoretical study

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Large ternary hydrogen-bonded pre-nucleation clusters in the Earth’s atmosphere

Cited by 77 publications

References 38 publications

Estimating the Lower Limit of the Impact of Amines on Nucleation in the Earth’s Atmosphere

Estimating the Lower Limit of the Impact of Amines on Nucleation in the Earth’s Atmosphere

Thermodynamics of the formation of sulfuric acid dimers in the binary (H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt;–H&lt;sub&gt;2&lt;/sub&gt;O) and ternary (H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt;–H&lt;sub&gt;2&lt;/sub&gt;O–NH&lt;sub&gt;3&lt;/sub&gt;) system

Effect of methyl hydrogen sulfate on the formation of sulfuric acid‐ammonia clusters: A theoretical study

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Thermodynamics of the formation of sulfuric acid dimers in the binary (H<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O) and ternary (H<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O–NH<sub>3</sub>) system