Born-Oppenheimer Molecular Dynamics Research Articles

When catchers meet - a computational study on the dimerization of the Buckycatcher.

We study the dimerization of the buckycatcher in gas phase and in toluene. We created an extensive library of 36 different complexes, which were characterized at semi-empirical and DFT levels. Semi-empirical geometries and dimerization energies compare well against reference data or Density Functional Theory calculations we performed. Born-Oppenheimer molecular dynamics was used to understand what happens when two molecules of the buckycatcher meet, allowing us to infer on the lack of kinetic barriers when dimers form. Thermodynamically, it is possible that room temperature solutions contain dimerized buckycatcher. Using a very simple exchange model, it is shown, however, that dimerization cannot compete thermodynamically against complexation with fullerenes, which accounts for experimental observations.

Strong carbon - noble gas covalent bond and fluxionality in hypercoordinate compounds.

Thermodynamic, kinetic, and chemical bonding analysis at the coupled cluster level has been carried out for a series of hypercoordinated carbon compounds with formula CH4Ng2+ (Ng = He-Rn). Results show that these compounds could be stable at room temperature and Born-Oppenheimer molecular dynamics simulations (BOMD) in conjunction with activation energies indicate high kinetic stability. In addition, all chemical bonding descriptors agree with a strong C-Ng covalent bond and a bonding pattern similar to that of CH5+. Finally, BOMD simulations showed that these compounds are fluxional, with a continuous formation/breaking of H-H and C-H bonds. To the best of the authors' knowledge, these results represent the first series of fluxional compounds possessing a covalent bond between a main group element and a noble gas atom.

Vibrational spectra of human tissues: Experimental data and density functional theory calculations comparison

Biophotonics techniques enabling molecular sensing of tissues and biological samples of had been widely applied to biomedical problems. Vibrational spectroscopy technologies like Fourier-Transform Infrared (FTIR) spectroscopy is a well-reported example. However, the correct interpretation of measured vibrational spectra of macromolecules and tissues emerging from the complexity of structures is a challenge. Computer simulations can be used as a strategic method to understand interactions between specific parts of a macromolecule. Here we present two implementations of vibrational calculations based on diagonalization of Hessian matrix obtained via Density Functional Theory calculations using Car-Parrinello Molecular Dynamics (CPMD package), Born-Oppenheimer Molecular Dynamics quickstep GPW (CP2K package), and a molecular dynamics calculations based on tight binding (CP2K-TB) was also employed to obtain FTIR spectra via electric dipole correlation function. These calculations were proposed to capture vibrational pieces of information related to FTIR of the human oral mucosa. Eleven models of peptide which represents collagen type I macromolecule including confined water molecules (ranging from 0 to 8 waters), were tested. CPMD and CP2K methods presented an excellent agreement of vibrational bands positions and maximum intensity to experimental data (goodness-of-fit R2 ∼ 0.90). On the other hand, this agreement was very poor for the CP2K-TB case in spite of the correct overall relative spectral intensity with respect to experimental data. We found that the peptide model enclosing eight waters (labeled C8) in CPMD calculations presented the highest value of R2 = 0.99. The CPMD method, despite some limitations, outperformed the CP2K calculation in our case. Here we only used a collagen cutout and confined water, but it is possible to add other molecules such as proteoglycans to investigate and characterize a tissue. The short collagen mimetic peptide has implications for the conformational behavior of native collagen. The method itself can be used for other macromolecules. Furthermore, we assignment of vibrational modes in the high-wavenumber region ( > 2, 000▒cm−1) is also presented.

Understanding the thermal stability of a 3d, 4d, and 5d element doped aluminium nanocluster through BOMD simulations

ABSTRACT Endohedrally doped atomic clusters have generated considerable interest among computational chemists on account of their tunable chemical properties that mimic a super atom. Such endohedrally doped clusters have also been experimentally realised in the more recent past. The present work explores the practical existence of 3d, 4d and 5d doped aluminium clusters, more specifically doped cluster, by evaluating systematically their structural stability through the first principle molecular dynamical simulations. Born–Oppenheimer Molecular Dynamics (BOMD) simulations have been carried out on atomic clusters where X = Ti, V, Fe, Co, Ni, Cu, Zn, Y, Mo, Ru, Rh and W are in endohedral position. The thermal stability of such endohedrally doped clusters is quantified through parameters such as , MSD and . Electronic structure calculations reveal that endohedral doping of only Rh, Cu and Zn is preferred in the cluster. Other dopants prefer to remain on the surface positions. However, finite temperature calculations reveal that the Zn cluster undergoes surface modifications from 300K leading to a distorted icosahedral structure. Cu cluster in quartet spin state is the only thermally stable cluster with Cu remaining in the endohedral position and structure retaining icosahedral confirmation till 700K.

Trapping the Transition State in a [2,3]-Sigmatropic Rearrangement by Applying Pressure.

Transition states are of central importance in chemistry. While they are, by definition, transient species, it has been shown before that it is possible to "trap" transition states by applying stretching forces. We here demonstrate that the task of transforming the transition state of a chemical reaction into a minimum on the potential energy surface can be achieved using hydrostatic pressure. We apply the computational extended hydrostatic compression force field (X-HCFF) approach to the educt of a [2,3]-sigmatropic rearrangement in both static and dynamic calculations and find that the five-membered cyclic transition state of this reaction becomes a minimum at pressures in the range between 100 and 150 GPa. Born-Oppenheimer molecular dynamics (BOMD) simulations suggest that slow decompression leads to a 70:30 mix of the product and the educt of the sigmatropic rearrangement. Our findings are discussed in terms of geometric parameters and electronic rearrangements throughout the reaction. To provide reference data for experimental investigations, we simulated the IR, Raman, and time-resolved UV/vis absorption spectra for the educt, transition state, and product. We speculate that the trapping of transition states by using pressure is generally possible if the transition state of a chemical reaction has a more condensed geometry than both the educt and the product, which paves the way for new ways of initiating chemical reactions.

Uncovering the Electrolyte-Dependent Transport Mechanism of LiO2 in Lithium-Oxygen Batteries.

Lithium-oxygen batteries (LOBs) offer extremely high theoretical energy density and are therefore strong contenders for bringing conventional batteries into the next generation. To avoid deactivation and passivation of the electrode due to the gradual covering of the surface by discharge products, electrolytes with high donor number (DN) are becoming increasingly popular in LOBs. However, the mechanism of this electrolyte-assisted discharge process remains unclear in many aspects, including the lithium superoxide (LiO2) intermediate transportation mechanism and stability at both electrode/electrolyte interfaces and in bulk electrolytes. Here, we performed a systematic Born-Oppenheimer molecular dynamics (BOMD)-level investigation of the LiO2 solvation reactions at two interfaces with high- or low-DN electrolytes (dimethyl sulfoxide (DMSO) or acetonitrile (CH3CN), respectively), followed by examinations of stability and condensation once the LiO2 monomers are solvated. Release of partial discharge product LiO2 is found to be energetically favorable into DMSO from the Co3O4 cathode with a small energy barrier. However, in the presence of CH3CN electrolyte, the release of LiO2 from the electrode surface is found to be energetically unfavorable. Dissolved LiO2(sol) clusters in bulk DMSO solvents are found to be more favorable to dimerize and agglomerate into a toroidal shape rather than to decompose, which avoids the emergence of strong oxidant ions (O2-) and preserves the system stability. This study provides two complete molecular-level pathways (solution and surface) from first-principles understanding of LOBs, offering guidance for future selection and design of electrode catalysts and solvents.

Ab Initio Study of H-Bond Dynamics in Three-Component Crystals Comprising (DABCOH+ )n Polycationic Chains.

In this work, the dynamic character of hydrogen-bond (H-bond) networks in two three-component crystals comprising polycationic chains was described. The first studied system was 1,4-diazabicyclo[2.2.2]octan-1-ium (DABCOH+ ) sulfamate monohydrate, known for its large negative linear compressibility. The second analyzed material was the newly obtained polar salt co-crystal: 1,4-diazabicyclo[2.2.2]octan-1-ium sulfamate urea. X-ray diffraction measurements enabled us to study the H-bond systems in both crystals using the graph set analysis. Obtained structures served as the initial models for Born-Oppenheimer molecular dynamics computations. A detailed study of intermolecular interactions and power spectra was conducted. The analysis of time and space correlations between the changes in H-bonds enabled the detection of proton transfer occurring in both systems at 300 K. Further study of those dynamic phenomena was done using the Energy Decomposition Analysis for selected trajectory fragments. Our work should improve the understanding of dielectric and ferroelectric properties of hybrid organic-inorganic materials.

Flexibility and Regularity of the Hydration Structures of Ions by an Example of Na+: Nonempirical Insight

The stationary nonempirical simulations of [Na(H2O)n]+ clusters with n in the range of 28-51 carried out at the density functional level with a hybrid B3LYP functional and the Born-Oppenheimer molecular dynamics modeling of the size-selected clusters reveal the interrelated structural and energetic peculiarities of the sodium ion hydration structures. Surface, bulk, and transient structures are distinguished by different locations of the sodium nucleus (close to either the spatial center of the structure or one of its side faces) and a consistently changing coordination number (which typically equals five or six). The differences and correlations between the stationary and averaged dynamically changing configurations are quantified. The ⟨rNaO⟩, mean Na-O distances for the first-shell water molecules, are found to depend both on the spatial character of the structure and the local coordination of sodium. The ⟨rNaO⟩ values are compared to different experimental estimates, and the virtual discrepancy of the latter is explained based on the results of cluster simulations. Different coordination neighborhoods of the sodium ion are predicted depending on its local fraction in actual specimens.

Calculation of Mass Spectra with the QCxMS Method for Negatively and Multiply Charged Molecules.

Analysis and validation of a mass spectrometry (MS) experiment are usually performed by comparison to reference spectra. However, if references are missing, measured spectra cannot be properly matched. To close this gap, the Quantum Chemical Mass Spectrometry (QCxMS) program has been developed. It enables fully automatic calculations of electron ionization (EI) and positive ion collision-induced dissociation (CID) mass spectra of singly charged molecular ions. In this work, the extension to negative and multiple ion charge for the CID run mode is presented. QCxMS is now capable of calculating structures carrying any charge, without the need for pretabulated fragmentation pathways or machine learning of database spectra. Mass spectra of four single negatively charged and two multiple positively charged organic ions with molecular sizes from 12 to 92 atoms were computed and compared to reference spectra. The underlying Born-Oppenheimer molecular dynamics (MD) calculations were conducted using the semiempirical quantum mechanical GFN2-xTB method, while for some small molecules, ab initio DFT-based MD simulations were performed. Detailed insights into the fragmentation pathways were gained, and the effects of the computed charge assignments on the resulting spectrum are discussed. Especially for the negative ion mode, the influence of the deprotonation site to create the anion was found to be substantial. Doubly charged fragments could successfully be calculated fully automatically for the first time, while higher charged structures introduced severe assignment problems. Overall, this extension of the QCxMS program further enhances its applicability and underlines its value as a sophisticated toolkit for CID-based tandem MS structure elucidation.

Promoted Activity of Surface Hydroxyls on γ-Al2O3 Mineral Dust with the Coexistence of SO2 and NH3.

Sulfate and ammonium formed on mineral dust can be mutually accelerated through the heterogeneous reactions of coexisting SO2 and NH3. However, little is known about the underlying mechanism, especially the pivotal reactive sites. Using combined Born-Oppenheimer molecular dynamics simulations and density functional theory calculations, the results show that, compared to that of SO2 or NH3 alone on the γ-Al2O3 surface, the increased level of formation of sulfate and ammonium can be attributed to the promoted activity of the surface-bridged hydroxyl with the coexistence of SO2 and NH3. In the specific mechanism, the O and H of the surface-bridged hydroxyl group are attacked by the adjacent SO2 and NH3, respectively, which directly enhances the formation of absorbed sulfite and ammonium, and indirectly facilitates the production of sulfate by oxidation of atmospheric O2. The proposed mechanisms can be broadly applied to other aluminum-based suspended dust particles, such as kaolinite, montmorillonite, and clay dust.

Evidence of Formation of Monolayer Hydrated Salts in Nanopores.

Despite much effort being devoted to the study of ionic aqueous solutions at the nanoscale, our fundamental understanding of the microscopic kinetic and thermodynamic behaviors in these systems remains largely incomplete. Herein, we reported the first 10 μs molecular dynamics simulation, providing evidence of the spontaneous formation of monolayer hexagonal honeycomb hydrated salts of XCl2·6H2O (X = Ba, Sr, Ca, and Mg) from electrolyte aqueous solutions confined in an angstrom-scale slit under ambient conditions. By using both the classical molecular dynamics simulations and the first-principles Born-Oppenheimer molecular dynamics simulations, we further demonstrated that the hydrated salts were stable not only at ambient temperature but also at elevated temperatures. This phenomenon of formation of hydrated salt in water is contrary to the conventional view. The free energy calculations and dehydration analyses indicated that the spontaneous formation of hydrated salts can be attributed to the interplay between ion hydration and Coulombic attractions in the highly confined water. In addition to providing molecular-level insights into the novel behavior of ionic aqueous solutions at the nanoscale, our findings may have implications for the future exploration of potential existence of water molecules in the saline deposits on hot planets.

The Effect of Surface Composition on the Selective Capture of Atmospheric CO2 by ZIF Nanoparticles: The Case of ZIF-8.

We performed theoretical studies of CO2 capture in atmospheric conditions by the zeolitic imidazolate framework-8 (ZIF-8) via classical Monte Carlo (MC) simulations with Metropolis sampling and classical molecular dynamics (MD) simulations in the NVT and NPT ensembles and different thermodynamic conditions. The ZIF-8 framework was described by varying unit cell dimensions in the presence of pure gases of CO2, N2, O2, Ar, and H2O steam as well as binary mixtures of CO2:N2 and CO2:H2O in s 1:1 concentration. Different chemical compositions of the framework surface was considered to provide an accurate treatment of charge and charge distribution in the nanoparticle. Hence, surface groups were represented as unsaturated zinc atom (Zn+2), 2-methylimidazole (mImH), and deprotonated 2-methylimidazole (mIm-). Force field reparameterization of the surface sites was required to reproduce the interactions of the gas molecules with the ZIF-8 surface consistent with quantum mechanics (QM) calculations and Born-Oppenheimer molecular dynamics (BOMD). It was observed that ZIF-8 selectively captures CO2 due to the negligible concentrations of N2, O2, Ar, and H2O. These molecules spontaneously migrate to the inner pores of the framework. At the surface, there is a competitive interaction between H2O, CO2, and N2, for the positively charged ZIF-8 nanoparticle with a large binding energy advantage for water molecules (on average -62, -15, and -8 kcal/mol respectively). For the neutral ZIF-8 nanoparticle, the water molecules dominate the interactions due to the occurrence of hydrogen bond with the imidazolate groups at the surface. Simulations of binary mixtures of CO2/water steam and CO2/N2 were performed to investigate binding competition between these molecules for the framework positively charged and neutral surfaces. It was found that water molecules drastically block the interaction between CO2 molecules and the framework surface, decreasing CO2 capture in the central pore, and CO2 molecules fully block the interaction between N2 molecules and the framework. These findings show that CO2 capture by ZIF-8 is possible in atmospheric environments only upon dehydration of the atmospheric gas. It further shows that ZIF-8 capture of CO2 from the atmospheric environment is dependent on thermodynamic conditions and can be increased by decreasing temperature and/or increasing pressure.

Born-Oppenheimer molecular dynamics and electronic properties of liquid H2S: The importance of a non-local approach to dispersion interactions

The dynamics and electronic properties of liquid H2S were investigated by Born–Oppenheimer molecular dynamics (BOMD). The Vydrov and Van Voorhis VV10 exchange–correlation functional [J. Chem. Phys. 133 (2010) 244103] that includes non-local correlation was adopted for generating the dynamics. This functional predicts the binding energy of the (H2S)2 dimer in very good agreement with experiment. Emphasis was placed on the structure, polarisation effects, and electronic absorption in liquid phase. The dipole moment in liquid H2S increases by 0.2D relative to the gas phase. A very small change (∼0.1 eV) in the position of the first maximum of the electronic absorption spectrum is observed when we compare liquid H2S and the isolated molecule. This is in contrast to liquid water where a [0.4-0.7] eV blue shift in the first peak of the absorption spectrum relative to the gas phase is observed. Exciton binding energies of H2S are calculated and compared with results for water. Their importance for explaining the difference between the blue-shift in H2S and water is discussed. The results indicate that although the (H2S)2 dimer is HB, some specific features characterising the structure and electronic properties of other HB liquids are not observed in liquid H2S. The interest of a non-local treatment of van der Waals interactions in liquid H2S is stressed.

OH Group Orientation Leads to Organosulfate Formation at the Liquid Aerosol Surface.

Organosulfates (OSs) are well-known and ubiquitous constituents of atmospheric aerosol particles and have been used as secondary organic aerosol markers in many field studies. Hence, it is imperative to understand the formation of OS species in the atmosphere. Recently, hydroxy acids (HAs) and hydroxy acid sulfates have been extensively detected in the atmospheric environment. However, the reaction mechanism of HAs to form OSs is much less understood. In this work, we have mainly investigated the reaction of typical α-HAs, including glycolic acid (GA) and lactic acid (LA), and SO3 at the liquid aerosol surface using quantum chemistry calculations and Born-Oppenheimer molecular dynamics simulations. The OH group orientation of α-HAs at the air-water interface is found to exert a significant impact on the formation of OSs. The OH group pointing to the gas phase is obviously beneficial to the formation of OSs. Two key factors are discovered important to the reaction of α-HAs adsorbed on the liquid surface with SO3: (a) the exposure position of the active site to the gas phase and (b) the reactivity of the exposed site to the attracted SO3 molecule. Moreover, we found that the air-water interface exerts a significant influence on the physicochemical behaviors of GA and LA, especially on their OH group orientation, and thus leads to their different properties for the SO3 colliding reaction. The presented reaction mechanism provides a new feasible pathway for the production of OSs at the liquid aerosol surface, which may have important impacts on the formation of organic aerosols.

Resolution of Identity in Gas-Phase Dissociations of Mono- and Diprotonated DNA Trinucleotide Codons by 15N-Labeling and Computational Structure Analysis.

Dissociations of DNA trinucleotide codons as gas-phase singly and doubly protonated ions were studied by tandem mass spectrometry using 15N-labeling to resolve identity in the nucleobase loss and backbone cleavages. The monocations showed different distributions of nucleobase loss from the 5'-, middle, and 3'-positions depending on the nucleobase, favoring cytosine over guanine, adenine, and thymine in an ensemble-averaged 62:27:11:<1 ratio. The distribution for the loss of the 5'-, middle, and 3'-nucleobase was 49:18:33, favoring the 5'-nucleobase, but also depending on its nature. The formation of sequence w2+ ions was unambiguously established for all codon mono- and dications. Structures of low-Gibbs-energy protomers and conformers of dAAA+, dGGG+, dCCC+, dTTT+, dACA+, and dATC+ were established by Born-Oppenheimer molecular dynamics and density functional theory calculations. Monocations containing guanine favored classical structures protonated at guanine N7. Structures containing adenine and cytosine produced classical nucleobase-protonated isomers as well as zwitterions in which two protonated bases were combined with a phosphate anion. Protonation at thymine was disfavored. Low threshold energies for nucleobase loss allowed extensive proton migration to occur prior to dissociation. Loss of the nucleobase from monocations was assisted by neighboring group participation in nucleophilic addition or proton abstraction, as well as allosteric proton migrations remote from the reaction center. The optimized structures of diprotonated isomers for dAAA2+ and dACA2+ revealed combinations of classical and zwitterionic structures. The threshold and transition-state energies for nucleobase-ion loss from dications were low, resulting in facile dissociations involving cytosine, guanine, and adenine.

Si6C18: A bispentalene derivative with two planar tetracoordinate carbons

AbstractHere we show that substituting the ten protons in the dianion of a bispentalene derivative (C18H102−) by six Si2+ dications produces a minimum energy structure with two planar tetracoordinate carbons (ptC). In Si6C18, the ptCs are embedded in the terminal C5 pentagonal rings and participate in a three‐center, two‐electron (3c‐2e) Si‐ptC‐Si σ‐bond. Our exploration of the potential energy surface identifies a triphenylene derivative as the putative global minimum. Nevertheless, robustness to Born–Oppenheimer molecular dynamics (BOMD) simulations at 900 and 1500 K supports bispentalene derivative kinetic stability. Chemical bonding analysis reveals ten delocalized π‐bonds, which, according to Hückel's 4n + 2 π‐electron rule, would classify it as an aromatic system. Magnetically induced current density analysis reveals the presence of intense local paratropic currents and a weakly global diatropic current, the latter agreeing with the possible global aromatic character of this specie.

The hydrogen bond interaction dynamics in polyvinylphenol: Studied by Born-Oppenheimer molecular dynamics

In this letter, we present the results of the study of the hydrogen bond network of Poly(4-vinylphenol) (PVPh) by using Born-Oppenheimer molecular dynamics. The polymeric structure and IR spectra of PVPh result from the presence of hydrogen bonds between the hydroxyl group. The presented study focuses on the analysis of changes in the network of conjugated hydrogen bonds observed in Poly(4-vinylphenol). The hydroxyl groups form conjugated hydrogen bonds in separate domains. The ab initio molecular dynamics gave us a possibility to understand the stabilization role of the hydrogen bond in the polymer material. Additionally, the quantization of nuclear motion has been performed.

Local intermolecular structure, hydrogen bonding and related dynamics in the liquid cis/trans N-methylformamide mixture: A density functional theory based Born-Oppenheimer molecular dynamics study

The local intermolecular structure and related dynamics in the liquid cis/trans N-methylformamide mixture at ambient temperature and density conditions have been systematically studied by employing Born-Oppenheimer molecular dynamics simulation techniques. Particular attention has been paid to the local structure around the cis- and trans- conformers and the formation and dynamics of hydrogen bonds with their closest neighbors. The calculated atom–atom radial distribution functions are in very good agreement with available experimental data and reveal the existence of different types of hydrogen bonding intermolecular interactions. The average number of hydrogen bonds formed by the cis- conformers is higher in comparison with the one corresponding to the trans- conformers. Moreover, the lifetimes of the hydrogen bonds formed in the liquid are longer when the cis- conformers participate in the bond formation, either as donors or acceptors. These findings clearly indicate that the local structural network around the cis- conformers in the liquid is more cohesive. The latter finding is also reflected in the slower reorientational dynamics of the cis- conformers and the low- and high-frequency region of the spectral densities of the atomic velocity time correlation functions. Finally, the calculated average dipole moments of the trans- and cis- conformers are significantly higher than their corresponding gas-phase values, signifying the importance of polarization effects in this particular polar liquid solvent.

ULYSSES: An Efficient and Easy to Use Semiempirical Library for C+.

We introduce ULYSSES, a user-friendly and robust C++ library for semiempirical quantum chemical calculations. In its current version, ULYSSES is equipped with a large set of different semiempirical models, most of which are based on the Neglect of Diatomic Differential Overlap (NDDO) approximation. Empirical corrections for dispersion and hydrogen bonding are available for most methods, so that higher quality is achieved in the calculation of energies of nonbonded complexes. The library is furthermore equipped with geometry optimization, as well as modules for calculating molecular properties of general interest. Ideal gas thermodynamics is available and allows single structure as well as conformer (multistructure) averaged properties to be calculated. We offer the possibility to use several vibrational partition functions according to the nature of interactions being studied: for covalent systems, the traditional harmonic oscillator approximation is available; for nonbonded complexes, we systematically extended the partition function proposed by Grimme for all thermodynamic functions. The library is also capable of running Born-Oppenheimer molecular dynamics.

Methanediol CH2(OH)2 and hydroxymethyl CH2OH+: key organic intermediates on the path to complex organic molecules

Context. Ab initio molecular dynamics simulations were carried out to study the formation pathways to complex organic molecules when a OH+ projectile hit an interstellar dust grain covered only by methanol molecules. The selected target material is a methanol cluster formed by ten units (CH3OH)10. Aims. The focus of this paper is the process where methanediol CH2(OH)2 and hydroxymethyl CH2OH+, both key organic intermediate molecules, were involved in the formation mechanisms of stable complex organic molecules (COMs). Methods. We performed Born-Oppenheimer (ab initio) molecular dynamics (BOMD) simulations under the hybrid functional of Head-Gordon ωB97X-D. We used the initial kinetic impact energy of 10, 12, 15, 18, 20, and 22 eV. Results. We corroborate that CH2(OH)2 and CH2OH+ are the main precursors to form molecules such as methoxymethanol CH3OCH2OH, the formyl radical HCO, the Criegee biradical CH2OO, and formaldehyde H2Co and its elusive HCOH isomer. We discuss the mechanism formation of these complex organic molecules. We compare the formation pathways with previous theoretical results where both key intermediates are present. The pathways in some cases go through CH2(OH)2 or undergo by CH2OH+. Conclusions. We confirm that CH2(OH)2 and CH2OH+ play a key role on the path to the formation of abundant H2CO. These mechanisms can give insight into alternative pathways relevant to understanding experimental processes with key steps within those precursors.