Born-Oppenheimer Molecular Dynamics Simulations Research Articles

Dual structural fluxionality in the copper borozene complex Cu3B8-: A two-layered molecular rotor.

Doubly aromatic B82-, a borozene analog of benzene (C6H6) due to their similar π bonding, can be considered an ideal base for multi-layered molecular rotors. Here, we theoretically constructed the copper borozene complex Cu3B8- to investigate its stability and structural fluxionality. The lowest energy isomers consist of two-layered configurations: a B8 molecular wheel and a triangular Cu3 motif that either stands upright or lies flat above the B8 wheel. Both configurations exhibit structural fluxionality, as indicated by the free rotation of Cu3 with respect to the B8 molecular wheel, confirmed by Born-Oppenheimer molecular dynamics simulations even at low temperatures. This fluxional behavior is associated with an ultra-soft vibrational mode of Cu3 (less than 10.0cm-1) and a negligible rotational barrier of 0.01 kcal/mol. Notably, high simulated temperatures cause irregular interconversion between the standing and lying orientations of Cu3 without regularity. Chemical bonding analysis confirmed that charge transfer from Cu3 to the B8 wheel renders Cu3B8- a typical copper borozene complex, [Cu3+][B82-], where B82- has six delocalized π and σ electrons. This electron delocalization contributes to a dilute and continuous electron cloud that underpins the dynamic behavior of the Cu3 trimer.

Molecular Association and Reactivity of the Pyridine Dimer Cation.

A recent experimental report has identified the formation of the C-N hemibonded pyridine dimer cation following vacuum ultraviolet near-threshold photoionization [J. Phys. Chem. Lett., 2021, 12, 4936-4943]. Herein, the dynamics and consequent reactivity of the pyridine dimer cation were investigated employing Born-Oppenheimer molecular dynamics (BOMD) simulations. An antiparallel π-stacked pyridine dimer in the neutral ground state is transformed into a noncovalently interacting C-H···N hydrogen-bonded structure which can lead to proton transfer in the cationic state. Additionally, C-N- and N-N-bonded adducts were formed in the cationic state. Further, metastable C-H···H-C-bonded cationic species was observed, which rearranged to an N-N bonded adduct. In contrast to the experimental observation, migration of the proton to the α position was not observed in the C-N bonded adduct owing to a high barrier of about 2 eV. The observed trends in the molecular association, proton transfer, and the formation of C-N and N-N bonded adducts are a consequence of the roaming dynamics of one pyridine moiety over the other in the cationic state.

Probing the Role of Solvent Configurations and Local Electric Fields on HX (X = F, Cl, Br and I) Dissociation in Water Clusters.

The acidity of hydrohalic acids increases down the group, with HF and HI being the weakest and strongest acids. Electronic structure calculations suggest that the critical electric fields required for the dissociation of HF, HCl, HBr, and HI are 347, 193, 163, and 153 MV cm-1, respectively, which are proportional to their corresponding pKa values and emphasize that in these systems the bond dissociation energy determines the pKa. The solvent configuration plays a significant role in the acid dissociation process, which is illustrated by a particular configuration of three water molecules around HX and favors dissociation of only HBr, even though the critical electric field required for the dissociation of HI is lower than that of HBr, as depicted in the graphical abstract. Further, the Born-Oppenheimer molecular dynamics (BOMD) simulations suggest that the spontaneity of HX dissociation depends on both the solvent configuration and thermal fluctuations, which hold higher significance in the case of weaker acids. In general, it was observed that the solvent electric field required for the acid dissociation process is marginally lower at higher temperatures.

CB11S3+: A Triangular Boron-Based Cluster with One Planar Tetracoordinate Carbon at Its Edge.

Boron-based clusters containing planar tetracoordinate carbon (ptC) are unique and scarce. Isoelectronic-replacing after proper vulcanization is an effective strategy to obtain the ptC based on the B12 cluster. Herein we report computational evidence for a ternary CB11S3+ (C2v, 1A1) cluster, which possesses a concentric double-triangle structure containing one ptC atom at the peripheral edge. The unbiased structural explorations of potential energy surfaces and high-level CCSD(T) calculations indicate that the ptC CB11S3+ cluster is a true global minimum. Born-Oppenheimer molecular dynamics (BOMD) simulations reveal that it is dynamically stable against isomerization and decomposition. Chemical bonding analysis reveals that three delocalized π bonds endow the π aromaticity to the CB11 unit of CB11S3+. In addition, the strong S → B π back-bonding is also conducive to the stability of CB11S3+. The current findings offer opportunities for further boron-based ptC clusters.

A first principles study of stability, electronic and thermoelectric characteristics of novel high temperature half- heusler alloys ScAgX (X=Si,Ge,Sn)

To meet the ever-increasing renewable energy demand Half- Heusler (HH) materials can be a potential candidate. Heusler materials are seeking popularity as efficient high-temperature thermoelectric materials. Here we systematically investigated the structural, electronic, mechanical and thermoelectric properties of novel HH compounds ScAgX (X = Si,Ge,Sn) in the framework of the first principles approach. These materials are found to be chemically, mechanically and dynamically stable. Born-Oppenheimer molecular dynamics simulations (BOMD) verify the thermal stability of these materials from 300 K to 1100 K. The semiconducting nature of these materials is confirmed by the electronic band structure. ScAgX (X = Si,Ge,Sn) have an indirect band gap of 0.37 eV, 0.42 eV and 0.38 eV respectively. A high value of Seebeck coefficient of 6351 μV/K, 6955 μV/K and 6558 μV/K has been obtained at room temperature. ScAgSi shows a high value of electrical conductivity (∼106 S/m) among these compounds at room temperature. The calculated value of the figure of merit (ZT) of ScAgX (X = Si,Ge,Sn) is 0.12, 0.08 and 0.16 at 1100 K respectively. Our present investigation shows that these materials can be a potential candidate for high-temperature thermoelectric power generation.

Insights into the catalytic effect of atmospheric organic trace species on the hydration of Criegee intermediates

The bimolecular reactions between Criegee intermediates (CIs) and atmospheric trace species have been extensively investigated, with a particular focus on the reaction with water, while the catalytic role of atmospheric organic compounds in hydration reactions was often neglected. In this study, we employed quantum chemical calculations and Born-Oppenheimer molecular dynamics (BOMD) simulations to investigate the catalytic effects of atmospheric organic amines, organic acids, and alcohols on the hydration reactions of CIs in the gas phase and at the gas-liquid interface. The catalytic reactions were found to follow a cyclic catalytic structure and a stepwise reaction mechanism. Gas-phase studies revealed that organic acids exhibited stronger catalytic effects compared to amines and alcohols, and the catalytic efficiency of amines and alcohols was similar to those of single water molecule. In addition, the catalytic reaction barriers of organic acids and alcohols were positively correlated with their gas-phase acidity (R2 = 0.94 to 0.97). A negative correlation was observed between the catalytic reaction barrier of amines and their gas-phase basicity (R2 = 0.84 to 0.90) and proton affinity (R2 = 0.84 to 0.92). At the gas-liquid interface, organic acids promoted the formation of hydroxyethyl hydroperoxide (HEHP, CH3CH(OH)(OOH)), organic acid ions, and H3O+, whereas the catalytic hydration of CIs by organic amines resulted in the formation of CH3CH(OH)OO and amine ions. Both HEHP and CH3CH(OH)OO can be further decomposed to form OH and HO2, or participate in new particles formation as precursors. This study complements the research gap on the reaction of CIs with water, providing valuable insights into the atmospheric sources of HEHP and HOx as well as the formation of secondary organic aerosols (SOAs).

Relaxation of the 2a1 ionized water dimer: An interplay of intermolecular Coulombic decay (ICD) and proton transfer processes.

This article investigates the relaxation dynamics of the ionized 2a1 state of a water molecule within a water dimer. The study was motivated by findings from two previous pieces of research that focused on the relaxation behaviors of the inner-valence ionized water dimer. The present study discloses an observation indicating that water dimers display specific fragmentation patterns following inner-valence ionization, depending on the position of the vacancy. Vacancies were created in the 2a1 state of the proton-donating water molecule (PDWM) and proton-accepting water molecule (PAWM). Utilizing Born-Oppenheimer molecular dynamics simulations, the propagation of the 2a1 ionized state was carried out for both scenarios. The results revealed proton transfer occurred when the vacancy resided in the PDWM, accompanied by the closing of decay channels for O-H bond distance (RO-H) > 1.187Å (matching Richter et al.'s findings). Conversely, when vacancy was on PAWM, we observed no closing of decay channels (aligning with Jahnke et al.'s findings). This difference translates to distinct fragmentation pathways. In PDWM cases, 2a1 state ionization leads to H3O+ -OH• formation. In contrast, PAWM vacancies result in decay pathways leading to H2O+-H2O+ products.

Restriction on molecular fluxionality by substitution: A case study for the 1,10-dicyanobullvalene.

We show herein that 1,10-dicyano substitution restricts the paragon fluxionality of bullvalene to just 14 isomers which isomerize along a single cycle. The restricted fluxionality of 1,10-dicyanobullvalene (DCB) is investigated by means of: (i) Bonding analyses of the isomer structures using the adaptive natural density partitioning (AdNDP). (ii) Quantum dynamical simulations of the isomerizations along the cyclic intrinsic reaction coordinate of the potential energy surface (PES). The PES possesses 14 equivalent potential wells supporting 14 isomers which are separated by 14 equivalent potential barriers supporting 14 transition states. Accordingly, at low temperatures, DCB appears as a hindered molecular rotor, without any delocalization of the wavefunction in the 14 potential wells, without any nuclear spin isomers, and with completely negligible tunneling. These results are compared and found to differ from those for molecular boron rotors. (iii) Born-Oppenheimer molecular dynamics (BOMD) simulations of thermally activated isomerizations. (iv) Calculations of the rate constants in the frame of transition state theory (TST) with reasonable agreement achieved with the BOMD results. (v) Simulations of the equilibration dynamics using rate equations for the isomerizations with TST rate coefficients. Accordingly, in the long-time limit, isomerizations of the 14 isomers, each with Cs symmetry, approach the "14 Cs → C7v" thermally averaged structure. This is a superposition of the 14 equally populated isomer structures with an overall C7v symmetry. By extrapolation, the results for DCB yield working hypotheses for so far un-explored properties e.g. for the equilibration dynamics of C10H10.

Formation pathways of formic acid (HCOOH) in regions with methanol ices

We modeled the collisions between OH^+ projectiles with kinetic energies ranging from 10 to 22 eV and an amorphous cold (CH3OH)_10 substrate using Born-Oppenheimer molecular dynamics (BOMD) simulations. We conducted the simulations for a collision time of 400 femtoseconds (fs), during which we followed multiple bond-forming and breaking reactions. Here, we report four new pathways for the formation of formic acid HCOOH . We find new precursors such as CH3(OH)2+ HC(OH)2^+ CH2OH^+ and CH2(OH)2 which are essential in these pathways for the formation of formic acid. The methanodiol CH2(OH)2 and hydroxymethyl CH2OH^+ cations have previously been identified as key precursors of formaldehyde. These pathways suggest new ways to form formic acid in methanol ice mantles on dust grains, offering alternative mechanisms leading to the formation of complex organic molecules (COMs) in space.

Molecular mechanisms and atmospheric implications of the simplest criegee intermediate and hydrochloric acid chemistry in the gas phase and at the aqueous interfaces

The atmospheric chemistry of Criegee Intermediates has become a frontier research point in environmental pollution in recent years. In this work, quantum chemical calculations and Born-Oppenheimer Molecular Dynamics (BOMD) simulations were employed to explore the gas phase and aqueous interface behavior of the simplest Criegee Intermediate (sCI, CH2OO) and hydrochloric acid (HCl) reaction. Quantum chemical calculations have revealed that the product of ClCH2OOH (CMHP) formation from the CH2OO + HCl reaction without and with water molecule undergoes a barrierless or near barrierless process in the gas phase. The results of the rate coefficients calculated by the master equation indicate that the gas-phase CMHP formation from the reaction of CH2OO + HCl could compete with the hydrolysis of CH2OO with (H2O)2 at the altitude of 15 km. BOMD simulations at the aqueous interfaces show that the CH2OO + HCl reaction occurs through stepwise mechanisms that are distinct from those in the gas phase. Three different interfacial reaction channels were identified: i) CMHP direct formation, ii) water-mediated CMHP formation, and iii) HCl-mediated hydroxymethyl hydroperoxide (HMHP) formation, and completed in picosecond time scales. Considering the harsh reaction conditions between CH2OO and HCl at the interface (i.e., the two molecules must be sufficiently close to form the CH2OO-HCl complex), the route of HMHP formation via the hydrolysis of CH2OO remains the main atmospheric loss pathway of CH2OO at the aqueous interfaces. Interestingly, molecular dynamic simulations in nanosecond time scales reveal that the formed CMHP in the gas phase has a tendency to aggregate with sulfuric acids, ammonia, and water molecules to form stable clusters within 213–278 K. The present results for the CMHP and HMHP formations from the sCI-HCl chemistry in the atmosphere will enhance our comprehension of the atmospheric behavior of Criegee intermediates in urban and marine pollution areas.

Adsorption behaviors of ethyltriethoxysilane on the calcium silicate hydrate surface: Effect of Ca/Si ratio and adsorption sites

Silane coupling agents (SCAs) are utilized to enhance the impermeability of concrete surfaces, whose adhesion force is affected by the interfacial interactions in between that remain unclear. In this study, we probe the adsorption tendencies of ethyltriethoxysilane (ETES) onto C-S-H surfaces by employing density functional theory (DFT) calculations and Born-Oppenheimer molecular dynamics (BOMD) simulations. Results suggest that significant chemisorption occurs at the CaOH(1.5), SiOH(1.0), Ca(1.0) sites C-S-H surfaces. Electronic structures analysis proved that the chemisorption of hydroxyl sites arises from the overlap of H and O atomic orbitals, resulting in the formation of hydrogen bonds. The chemisorption of the Ca(1.0) site is caused by electrostatic adsorption between calcium and oxygen. Adsorption energy results show: ECaOH(1.5) > ECa(1.0) > ESiOH(1.0). Moreover, ETES remains transverse adsorption on low Ca/Si C-S-H surfaces, while displaying longitudinal adsorption on high. Interaction analysis illustrates the configuration discrepancy arising from the absence of bridge silicon-oxygen tetrahedrons which possess vdW interactions with ethyl. Notably, transverse adsorption covers a wider area on the C-S-H surface thereby enhancing the hydrophobic effect. In summary, the utilization of ETES presents notable advantages within the context of low Ca/Si ratio cement. This study contributes valuable insights into the design and application of silane coatings.

Reaction of SO3 with H2SO4 and its implications for aerosol particle formation in the gas phase and at the air–water interface

Abstract. The reactions between SO3 and atmospheric acids are indispensable in improving the formation of aerosol particles. However, relative to those of SO3 with organic acids, the reaction of SO3 with inorganic acids has not received much attention. Here, we explore the atmospheric reaction between SO3 and H2SO4, a typical inorganic acid, in the gas phase and at the air–water interface using quantum chemical (QC) calculations and Born–Oppenheimer molecular dynamics simulations. We also report the effect of H2S2O7, the product of the reaction between SO3 and H2SO4, on new particle formation (NPF) in various environments using the Atmospheric Cluster Dynamics Code (ACDC) kinetic model and QC calculations. The present findings show that the gas-phase reactions of SO3 + H2SO4 without and with water molecules are both low-energy-barrier processes. With the involvement of interfacial water molecules, H2O induced the formation of the S2O72-⋯H3O+ ion pair, HSO4- mediated the formation of the HSO4-⋯H3O+ ion pair, and the deprotonation of H2S2O7 was observed and proceeded on the picosecond timescale. The present findings suggest the potential contribution of the SO3–H2SO4 reaction to NPF and aerosol particle growth, showing that (i) although H2S2O7 is easily hydrolyzed with water to form H2SO4, it can directly participate in H2SO4–NH3-based cluster formation and can present a more obvious enhancement effect on SA–A-based cluster formation, and (ii) the formed interfacial S2O72- can attract candidate species from the gas phase to the water surface and, thus, accelerate particle growth.

Full Dynamical and Ab Initio Investigation of the Electron Transfer-Mediated Decay Mechanism of He+ in the Presence of Heavier Alkali Dimers.

We have studied the electron transfer-mediated decay (ETMD) process for the 1s ionized state of the He atom in the presence of a heavier alkali homonuclear dimer (Na2, K2, and Rb2) as well as heteronuclear dimer (LiNa, NaK, and KRb). In our computation, we have considered all the alkali dimers being in the singlet electronic ground state. The electron transfer from the alkali dimer to He (1s-1) leads to the emission of another electron from the alkali dimer into the continuum. We have investigated the impact of the distance of the He atom from the center of mass of the alkali dimer on the ETMD decay width. We also performed the Born-Oppenheimer molecular dynamics simulation to understand the impact of nuclear dynamics on the ETMD process.

XB2Bi2 (X = Si, Ge, Sn, Pb): Penta-Atomic Planar Tetracoordinate Si/Ge/Sn/Pb Clusters with 20 Valence Electrons.

Planar tetracoordinate silicon, germanium, tin, and lead (ptSi/Ge/Sn/Pb) species are scarce and exotic. Here, we report a series of penta-atomic ptSi/Ge/Sn/Pb XB2Bi2 (X = Si, Ge, Sn, Pb) clusters with 20 valence electrons (VEs). Ternary XB2Bi2 (X = Si, Ge, Sn, Pb) clusters possess beautiful fan-shaped structures, with a Bi-B-B-Bi chain surrounding the central X core. The unbiased density functional theory (DFT) searches and high-level CCSD(T) calculations reveal that these ptSi/Ge/Sn/Pb species are the global minima on their potential energy surfaces. Born-Oppenheimer molecular dynamics (BOMD) simulations indicate that XB2Bi2 (X = Si, Ge, Sn, Pb) clusters are robust. Bonding analyses indicate that 20 VEs are perfect for the ptX XB2Bi2 (X = Si, Ge, Sn, Pb): two lone pairs of Bi atoms; one 5c-2e π, and three σ bonds (two Bi-X 2c-2e and one B-X-B 3c-2e bonds) between the ligands and X atom; three 2c-2e σ bonds and one delocalized 4c-2e π bond between the ligands. The ptSi/Ge/Sn/Pb XB2Bi2 (X = Si, Ge, Sn, Pb) clusters possess 2π/2σ double aromaticity, according to the (4n + 2) Hückel rule.

Enticing a Proton using Single Ammonia Molecule as Bait.

In microhydrated acid-solvent clusters, deprotonation of an acid is assisted by a critical number of solvent molecules and a solvent electric field. Born-Oppenheimer molecular dynamics simulations reveal that trifluoroacetic acid undergoes spontaneous proton transfer in water clusters, with the critical number being five. Acetic acid and phenol, on the other hand, do not dissociate even in the presence of a large number of water molecules (in excess of 40). The addition of a single ammonia molecule to the water cluster, which interacts directly with the protic group, lowers the critical number of solvent water molecules required for proton transfer to three and seven in the case of acetic acid and phenol, respectively. The population of the undissociated and the proton-transferred structures get dispersed to form separate islands on the electric field versus the O-H distance representation with the cusp representing the critical values. The critical electric fields for the spontaneous proton transfer are around 254, 237, and 318 MV cm-1 for trifluoroacetic acid, acetic acid, and phenol, respectively. In the case of phenol, the free energy profiles suggest that proton transfer to the ammonia moiety embedded in water promotes proton transfer efficiently due to the higher basicity of ammonia and enhanced hydrogen bonding network of solvent water, vis-à-vis phenol-ammonia clusters.

Surface electronic structure and photo activity of double perovskite Ba[formula omitted]PrBiO[formula omitted]: First-principles investigations

Double perovskite Ba2PrBiO6 exhibits photo catalytic activity in the visible light range with the observed optical band gap of ∼1.0 eV. On the other hand, density functional theory (DFT) calculations predict a larger bulk band gap of 2.0 eV even with the standard Perdew–Burke–Ernzerhof (PBE) functional, which is known to underestimate the band gap of semiconductors. Much larger bulk band gap of 3.13 eV is predicted with a hybrid functional treatment for the exchange–correlation, which generally gives better descriptions for them. This discrepancy between experiment and theory implies the presence of unknown mechanism which effectively reduces the band gap of Ba2PrBiO6 and thereby gains the sensitivity to the visible light. The first finding is that the surface band gaps of Ba2PrBiO6 calculated using an appropriate hybrid functional are smaller than the bulk band gaps and are 2.49 eV and 2.85 eV for the Pr–Bi and Ba–O polar surfaces, respectively. We also find that work function is quite sensitive to the surface structures and its accurate calculations are essential to show that the reduction and oxidation levels are fit to the gap region. When a substitutional defect PrBi, in which Bi is substituted by Pr, is introduced into the Pr–Bi polar surface, surface band gap is further reduced to 0.93 eV, being very close to the experimental value. For the Ba–O polar surface, similar reduction to 1.59 eV is found but not substantial as compared to the Pr–Bi polar surface. These narrow surface band gaps may be the origin of the photo activity of Ba2PrBiO6 in the visible light region. We also performed Born–Oppenheimer molecular dynamics simulations to clarify the reactivity of the polar surfaces to water. We find that two hydroxyl groups were created in the adsorption of a single H2O molecule. The decomposition of water molecule in the adsorption indicates that the polar surfaces provide a promising stage for the photo catalytic activity. Further adsorption of H2O molecules leads to their diffusion on the surface.

The reaction mechanism of SO3 with the multifunctional compound ethanolamine and its atmospheric implications.

SO3 is an important reactive species in sulfur cycle and sulfuric acid formation processes and its reactions with some functional group substances, such as H2O, NH3, CH3OH, and organic and inorganic acids, have been extensively studied. However, its loss mechanism with multifunctional species is still lacking in detail. Herein, the reaction mechanism between SO3 and monoethanolamide (MEA) was investigated in the gas phase and on water droplets. The quantum chemical calculations indicate that the gas-phase reactions of SO3 with the OH and NH2 moieties of MEA hardly occur as their reaction energy barriers are up to 21.9-29.4 kcal mol-1. When a single water molecule is added into the SO3 + MEA reaction, it not only decreases the reaction barrier by at least 15.0 kcal mol-1 and thus enhances the rate obviously, but can also lead to the main product changing from HOCH2CH2NHSO3H to NH2CH2CH2OSO3H. The Born Oppenheimer molecular dynamics simulations on a water droplet show that the routes of the NH2CH2CH2OSO3-⋯H3O+ ion pair, HSO4- and HOCH2CH2NH3+ ions and zwitterionic formations of HOCH2CH2NH2+-SO3- and SO3--OCH2CH2NH3+ occur through a loop-structure route or chain reaction process, and can be finished within several picoseconds. Interestingly, the nucleation simulations show that the products of HOCH2CH2NHSO3H and NH2CH2CH2OSO3H have a potential ability to participate in the formation of new particles as they can form larger clusters with H2SO4, NH3 and H2O molecules within 20 ns. Thus, the present study will not only give new insight into the reaction between SO3 and multifunctional compounds, but also provide a new potential formation mechanism for particles resulting from the loss of SO3.

Planar tetracoordinate beryllium compounds with a partially covalent Be-Ng bond.

An analysis of the thermodynamic and kinetic stability and the nature of the chemical bond in hypercoordinated compounds with the formula BeH3Ng+ (Ng = He-Rn) through high-level calculations is presented in this work. Thermochemical calculations show that, for the heavier noble gases (Ar-Rn), these systems are thermodynamically stable at room temperature; however, this stability decreases due to a weakening of the Be-H2 interaction, while the Be-Ng bond strengthens going down the periodic table. These results are complemented by Born Oppenheimer molecular dynamics simulations, in which the increasing tendency to dissociate the Be-H2 bond is evidenced. The nature of the chemical bonding depends on the analysis performed. On the one hand, the interacting quantum atoms method indicates that the covalent contribution is around 25 to 30%. On the other hand, the electron density topology indicates a covalent nature for compounds with Kr-Rn, while Hirshfeld population analysis in conjunction with Mayer's bond order establishes polar covalent behavior. The geometrical parameters and natural energy decomposition analysis (NEDA) indicate a covalent nature, allowing us to consider that the Be-Ng bond has a partially covalent character.

Dissociation of H2O2 on water surfaces (ice and water droplets).

OH radicals are an important constituent of the atmosphere. Therefore, all reactions that act as a source of OH radicals are important. It is known that photo-dissociation of H2O2 is an important source of OH radicals in the atmosphere. In the present study, using Born-Oppenheimer molecular dynamics simulations, we have shown that the H2O2 molecule can dissociate thermally on water droplets, as well as on the surface of ice, to form OH radicals. Furthermore, the dissociation of H2O2 was found to be very fast (less than 50 fs) on the ice surface compared with on the water droplets. We believe this route for the formation of OH radicals could be more critical than photo-dissociation, as it can take place both during the day and at night, but further studies with more sophisticated theoretical approaches or experiments are required to confirm this hypothesis.

Barrierless reactions of C2 Criegee intermediates with H2SO4 and their implication to oligomers and new particle formation

The formation of oligomeric hydrogen peroxide triggered by Criegee intermediate maybe contributes significantly to the formation and growth of secondary organic aerosol (SOA). However, to date, the reactivity of C2 Criegee intermediates (CH3CHOO) in areas contaminated with acidic gas remains poorly understood. Herein, high-level quantum chemical calculations and Born-Oppenheimer molecular dynamics (BOMD) simulations are used to explore the reaction of CH3CHOO and H2SO4 both in the gas phase and at the air-water interface. In the gas phase, the addition reaction of CH3CHOO with H2SO4 to generate CH3HC(OOH)OSO3H (HPES) is near-barrierless, regardless of the presence of water molecules. BOMD simulations show that the reaction at the air-water interface is even faster than that in the gas phase. Further calculations reveal that the HPES has a tendency to aggregate with sulfuric acids, ammonias, and water molecules to form stable clusters, meanwhile the oligomerization reaction of CH3CHOO with HPES in the gas phase is both thermochemically and kinetically favored. Also, it is noted that the interfacial HPES− ion can attract H2SO4, NH3, (COOH)2 and HNO3 for particle formation from the gas phase to the water surface. Thus, the results of this work not only elucidate the high atmospheric reactivity of C2 Criegee intermediates in polluted regions, but also deepen our understanding of the formation process of atmospheric SOA induced by Criegee intermediates.