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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Impact of functional groups on the electrocatalytic hydrogenation of aromatic carbonyls to alcohols

We report that electrocatalytic hydrogenation (ECH) of biomass-derived feedstocks has a critical dependence on the molecular structure of the organic and its adsorption on the electrode surface. In this study, we investigated the role of functional groups in the adsorption of the organic molecule on the charged Pd (111) surface and its subsequent effect on organic reduction in electrochemical hydrogenation of organic molecules. With three aromatic carbonyls of benzaldehyde (BZD), acetophenone (ACE), and vanillin (VAN), we rationalize molecular-scale adsorption and interfacial charge transfer processes by employing density-functional-theory based ab initio molecular dynamics simulations. We observe that the functional group and electrode charge strongly affect the proximity of organic molecule to the Pd (111) surface, where distances of aromatic ring and carbonyl group of the organic on the electrode change distinctively with functional groups and charge state of electrode, which strongly impact reduction of organics on the surface. Calculations of differential electron density show the strongest reduction with benzaldehyde via interfacial electron transfer from the charged Pd surface. We also observe that the interaction between the functional groups and solvent (VAN > BZD > ACE) significantly influence the organic interaction with the charged electrode (BZD > VAN > ACE), resulting in the net interaction energy between the organic and the electrode in the order of BZD > ACE > VAN. Experimental measurement of ECH rate also show the same trend of the net interaction energy. These results demonstrate the significance of solvent effect on the reducibility of organic molecules on electrodes.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Probing surface-adsorbate interactions through active particle dynamics

Adsorbate molecules present in a reaction mixture may bind to and block catalytic sites. Measurement of the surface coverage of these molecules via adsorption isotherms is critical for modeling and design of catalytic reactions on surfaces. However, it is challenging to measure isotherms in solution in a way that is directly relevant to catalytic activity under reaction conditions, particularly since adsorbates may bind with an enormous range of surface affinity parameters. Here we used the motion of self-propelled catalytic Janus particles, which employ the decomposition of hydrogen peroxide fuel as a propulsion mechanism, to determine the effective surface coverage of thioglycerol, furfural, and ethanol on a platinum surface as a function of concentration in aqueous solution by measuring the decrease in active motion due to the blocking of active sites. For strongly adsorbing thioglycerol, this effective coverage was compared and contrasted to the total adsorbed amount measured using inductively-coupled plasma analysis. Demonstrating the broad applicability of this approach, the surface affinity of the three adsorbates spanned more than four orders of magnitude. For each species, the adsorbate-mediated attenuation of active motion occurred over a wide concentration range and was well-described by a Langmuir isotherm. The strongly interacting thioglycerol had the highest affinity towards the surface (K a = 15.5 ± 4.3 mM –1 ) and fully deactivated the active particle motion at surface saturation. Furfural had an intermediate affinity (K a = 0.42 ± 0.07 mM –1 ) but did not fully block H 2 O 2 access to the surface at apparent saturation, consistent with a maximum fractional surface coverage of θ max = 0.67. Ethanol exhibited even lower affinity (K a = 0.0025 ± 2x10 -4 mM –1 ) and its coverage saturated at only θ max = 0.38. Analysis of isotherms at elevated temperatures enabled direct extraction of the enthalpies of adsorption. The degree of surface coverage at adsorbate saturation appeared to correlate with the relative energies of adsorption for the different adsorbate species and was consistent with adsorbate saturation of one of multiple active site populations towards H 2 O 2 decomposition. Furthermore, computational investigations into solvent effects on furfural adsorption showed good quantitative agreement with the experimental results. This work leverages unique properties of active particles to explore fundamental catalysis questions and demonstrates a novel paradigm for significant and experimentally accessible multidisciplinary research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2003

Dissociative Ionization of Aromatic and Heterocyclic Molecules

Space radiation poses a major health hazard to humans in space flight. The high-energy charged particles in space radiation ranging from protons to high atomic number, high-energy (HZE) particles, and the secondary species they produce, attack DNA, cells, and tissues. Of the potential hazards, long-term health effects such as carcinogenesis are likely linked to the DNA lesions caused by secondary electrons in the 1 - 30 eV range. Dissociative ionization (DI) is one of the electron collision processes that can damage the DNA, either directly by causing a DNA lesion, or indirectly by producing radicals and cations that attack the DNA. To understand this process, we have developed a theoretical model for DI. Our model makes use of the fact that electron motion is much faster than nuclear motion and assumes DI proceeds through a two-step process. The first step is electron-impact ionization resulting in a particular state of the molecular ion in the geometry of the neutral molecule. In the second step the ion undergoes unimolecular dissociation. Thus the DI cross section sigma(sup DI)(sub a) for channel a is given by sigma(sup DI)(sub a) = sigma(sup I)(sub a) P(sub D) with sigma(sup I)(sub a) the ionization cross section of channel a and P(sub D) the dissociation probability. This model has been applied to study the DI of H2O, NH3, and CH4, with results in good agreement with experiment. The ionization cross section sigma(sup I)(sub a) was calculated using the improved binary encounter-dipole model and the unimolecular dissociation probability P(sub D) obtained by following the minimum energy path determined by the gradients and Hessians of the electronic energy with respect to the nuclear coordinates of the ion. This model is used to study the DI from the low-lying channels of benzene and pyridine to understand the different product formation in aromatic and heterocyclic molecules. DI study of the DNA base thymine is underway. Solvent effects will also be discussed.

Huo, Winifred M.↗
DOE OSTI2025

Automatic Generation of Chemical Mechanisms for Electrochemical Systems: Solid Electrolyte Interphase Formation in Lithium Batteries

Electrolytes in many lithium ion batteries decompose at the low potentials near the anode. The decomposition products form a layer termed the solid electrolyte interphase (SEI). The composition and growth of the SEI layer significantly affect both the capacity fade and safety of lithium ion batteries. However, SEI formation and growth kinetics are not well understood. In this work, we present an extension of the Reaction Mechanism Generator (RMG) software to automatically generate mechanisms for SEI formation. We extend RMG’s solvation correction framework to account for kinetic solvent effects and demonstrate the accuracy of our technique. We calculate thermochemical parameters for 252 species and rate coefficients for 69 reactions, most with associated solvation corrections. This and additional quantum chemistry data are used to extend RMG’s thermodynamic group additivity and solute parameter estimation schemes to handle lithiated species and add 14 new reaction families to RMG. RMG is additionally extended to simulate electrocatalytic systems. Lastly, we demonstrate RMG on the decomposition of acetonitrile and ethylene carbonate near a battery anode. Furthermore, while this framework does not yet resolve individual ions, as appropriate thermochemistry estimators are not available, and thus, cannot yet resolve more complex electrochemical pathways, RMG is able to generate reasonable pathways for SEI formation that match literature pathways and products. In particular, RMG identifies a new important reaction pathway that is not present in literature.

Chemical reactions↗
DOE OSTI2021

Transition state stabilization depends on solvent identity, pore size, and hydrophilicity for epoxidations in zeolites

Ti-silicates activate H 2 O 2 to form Ti-hydroperoxo and Ti-peroxo intermediates that can react with alkenes to form epoxide products. Comparisons of kinetics for 1-octene epoxidation with H 2 O 2 on Ti-BEA and Ti-MFI catalysts with different hydrophilicities in methanol (CH 3 OH) or acetonitrile (CH 3 CN) solvents show the significance of the solvent for stabilizing catalytically-relevant species and the complex interdependencies between solvent, catalyst topology, and hydrophilicity. Epoxidation turnover rates are higher in CH 3 CN than CH 3 OH for Ti-BEA, but the opposite trend is observed for Ti-MFI. Ti-silicates with greater silanol densities, however, give greater epoxidation turnover rates than their hydrophobic counterparts in both solvents. Kinetic, spectroscopic, and thermodynamic analyses show that differences in turnover rates mainly arise from changes in the stabilization of reactive surface species by solvent mediated interactions, because the mechanism of the reaction and stability of the fluid-phase reactants remain similar in CH 3 CN and CH 3 OH. Specifically, apparent activation free energy values ($ΔG^{‡}_{App}$) indicate that surface intermediates responsible for alkene epoxidation are stabilized to a greater extent in CH 3 CN on Ti-BEA and in CH 3 OH on Ti-MFI. Hydrophilic Ti-silicates present lower ($ΔG^{‡}_{App}$) values regardless of solvent identity, which suggests that these differences correspond to the number of hydrogen-bonding solvent molecules found near reactive species bound to Ti active sites. Finally, taken together, these findings demonstrate the role of solvent molecules in allowing reactive intermediates to recognize the properties of active sites beyond the length-scale of covalent bonds, which carry implications for epoxidation but also other reactions within solvent-filled pores of microporous materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

An ab initio free energy study of the reaction mechanism and rate-limiting steps of CO 2 capture by aqueous glycine

Aqueous amino acids are promising absorbents for direct air capture (DAC) of CO 2 . Herein, we investigate the possibility of kinetic control of CO 2 absorption with aqueous anionic glycine (GLY - ) by employing extensive ab initio molecular dynamics simulations, free energy analysis, and reaction rate theory. We find that first GLY - binds to CO 2 by overcoming a barrier (7.4 kcal/mol) to form a zwitterion intermediate, which then releases a proton by overcoming a similar barrier. Despite the similarity in the barrier, zwitterion formation appears to be the rate-limiting step because it is two orders of magnitude slower (microseconds) than the proton release step. This is predominantly due to stronger nonequilibrium solvent effects for the former that cause many barrier-recrossing events and effectively slow down the reaction rate. Such a detailed fundamental understanding of the amino acid-based CO 2 -absorption mechanism and rates is key to improving the kinetic efficiency of DAC technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Solvent-Induced Swelling Behaviors of Microphase-Separated Polystyrene- block -Poly(ethylene oxide) Thin Films Investigated Using In Situ Spectroscopic Ellipsometry and Single-Molecule Fluorescence Microscopy

Block copolymers have attracted considerable interest in the fields of nanoscience and nanotechnology, because these polymers afford well-defined nanostructures via self-assembly. An in-depth understanding of solvent effects on the physicochemical properties of these microdomains is crucial for their preparation and utilization. Herein, we employed in situ spectroscopic ellipsometry and single-molecule fluorescence techniques to gain detailed insights into microdomain properties in polystyrene-block-poly(ethylene oxide) (PS-b-PEO) films exposed to ethanol- and water-saturated N 2 . We observed a quick increase and a subsequent gradual decrease in the ellipsometric thickness of PS-b-PEO films upon exposure to ethanol-saturated N 2 . This observation was unexpected because ethanol-saturated N 2 induced negligible thickness change for PS and PEO homopolymer films. The similarity in maximum thickness gain observed under ethanol- and water-saturated N 2 implied the swelling of PEO microdomains. Ethanol vapor permeation through the PEO microdomains was supported by the red-shift of the ensemble and single-molecule fluorescence emission of Nile red in PS-b-PEO films. Single-molecule tracking data showed the initial enhancement and subsequent reduction of the diffusion of hydrophilic sulforhodamine B molecules in PS-b-PEO films upon exposure to ethanol-saturated N 2 , consistent with the spectroscopic ellipsometry results. Furthermore, the higher ethanol susceptibility of the PEO microdomains was attributable to their amorphous nature, as shown by FTIR data.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Molecular Level Understanding of Polyethylene Terephthalate (PET) Depolymerization in Base/Alcohol Hybrid Systems

Polyethylene terephthalate (PET) depolymerization in base/alcohol hybrid systems represents a promising low-energy approach for chemically recycling PET waste into valuable monomers. This study investigates the mechanistic pathways of PET depolymerization in NaOH/alcohol solutions, emphasizing the competing roles of hydroxide and alkoxide species. Utilizing a combination of experimental techniques, density functional theory (DFT) calculations, and molecular dynamics (MD) simulations, we explore how factors such as base concentration, alcohol chain length, and pKa values of alcohols influence PET depolymerization efficiency and pathways. Our findings indicate that alkoxide ions (RO⁻) exhibit notably higher reactivity than hydroxide ions (HO⁻), favoring an alcoholysis pathway in the base/alcohol hybrid system. Experimental results across a series of C1 to C5 alcohols show that longer-chain alcohols, particularly 1-butanol, achieve higher PET conversion, although this does not align solely with simple nucleophilicity trends of alkoxides. While DFT calculations reveal comparable activation energies for various alkoxides in PET depolymerization, MD simulations underscore the significant role of alcohol chain length, with longer-chain alcohols forming more stable or frequent interactions with PET. Additionally, the alkoxide concentration, influenced by the alcohol’s pK a , directly impacts PET conversion. These suggest that PET depolymerization is governed by a balance between alkoxide concentration and alkoxide-PET interactions, rather than activation energies or nucleophilicity alone. From a practical perspective, incorporating long-chain alcohols as cosolvents may enhance process efficiency but increases raw material costs by approximately 30%. However, long-chain alcohols present a safer and more sustainable alternative to hazardous cosolvents such as dichloromethane. This work offers a molecular-level understanding of PET depolymerization in base/alcohol systems and provides insights into optimizing these systems for more efficient and sustainable PET recycling processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Electrolyte Organization Leads to Potential-Dependence in Thermochemical Catalysis of Nonpolar Reactions

Electrochemical polarization is now known to play a key role in thermochemical catalysis at solid–liquid interfaces. However, existing frameworks cannot account for why even nonpolar, nonfaradaic reactions are sensitive to interfacial polarization. In order to uncover the molecular basis of this phenomenon, we herein study the potential-dependent reaction kinetics of ethylene and trans-2-butene hydrogenation at Pt–liquid interfaces. Measurements were performed in aqueous and ortho-difluorobenzene (o-DFB) solutions, spontaneously polarizing the Pt–liquid interfaces by, respectively, varying the pH or dissolving distinct metallocene redox buffers into solution. Here, we find that at comparable mechanistic regimes, the rates of both ethylene and trans-2-butene hydrogenation are maximized near the same electrochemical potential, E. Moreover, the potential-dependence, defined as $\frac{∂ln 𝑟}{∂𝐸}$, of trans-2-butene hydrogenation is approximately 2.2× greater than that of ethylene hydrogenation across the full potential range studied. These observations are all consistent with a model in which polarization of the Pt surface away from the local potential of zero free charge (E PZFC ) induces electrostatic organization of the polar solvent and charged ions near the interface, which impedes olefin adsorption and surface reaction because these surface reactions induce electrolyte displacement. Accordingly, interfacial polarization alters the free energy landscape and thus the rate of nonpolar heterogeneous catalysis by controlling the degree of electrostatic organization of polar and charged spectators at the interface, which do not in general need to be specifically chemisorbed onto the surface but could simply be close enough to the surface to be perturbed by the olefin adsorption. These results point toward electrochemical design handles, namely, the electrolyte, catalyst potential, and local E PZFC of the catalyst, with which to tune interfacial catalysis of thermochemical organic transformations.

adsorption↗
DOE OSTI2025

Systematic improvement of redox potential calculation of Fe(III)/Fe(II) complexes using a three-layer micro-solvation model

Electrochemical transformations of metal ions in aqueous media are challenging to model accurately due to the dynamic solvation structure surrounding ions at different charge states. Predictive modeling at the atomistic scale is essential for understanding these solvation architectures but is often computationally prohibitive. In this contribution, we present a simple, fast, and accurate three-layer micro-solvation model to evaluate the redox potential of metal ions in aqueous solutions. Our model, developed and validated for Fe 3+ /Fe 2+ redox potentials, combines the DFT-based geometry optimizations of the octahedral Fe complex with two layers of explicit water molecules to capture solute–solvent interactions and an implicit solvation model to account for bulk solvent effects. This approach yields accurate predictions for Fe 3+ /Fe 2+ redox potentials in water, achieving errors of 0.02 V with ωB97X-V, 0.01 V with ωB97X-D3, 0.04 V with ωB97M-V, and 0.02 V with B3LYP-D3 functionals. We further demonstrate the generality of our model by applying it to additional metal complexes, including the challenging Fe(CN) 6 3−/4− system, where our model successfully achieves close agreement with experimental values, with an error of 0.07 V and an average error of 0.21 V for all five systems. In summary, the presented simple solvation model has broad applicability and potential for enhancing computational efficiency in redox potential predictions across various chemical and industrial processes of metal ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Charge transfer as a mechanism for chlorophyll fluorescence concentration quenching

Highly concentrated solutions of chlorophyll display rapid fluorescence quenching. The same devastating energy loss is not seen in photosynthetic light-harvesting antenna complexes, despite the need for chromophores to be in close proximity to facilitate energy transfer. A promising, though unconfirmed mechanism for the observed quenching is energy transfer from an excited chlorophyll monomer to a closely associated chlorophyll pair that subsequently undergoes rapid nonradiative decay to the ground state via a short-lived intermediate charge-transfer state. In this work, we make use of newly emerging fast methods in quantum chemistry to assess the feasibility of this proposed mechanism. We calculate rate constants for the initial charge separation, based on Marcus free-energy surfaces extracted from molecular dynamics simulations of solvated chlorophyll pairs, demonstrating that this pathway will compete with fluorescence (i.e., drive quenching) at experimentally measured quenching concentrations. We show that the rate of charge separation is highly sensitive to interchlorophyll distance and the relative orientations of chromophores within a quenching pair. We discuss possible solvent effects on the rate of charge separation (and consequently the degree of quenching), using the light-harvesting complex II (LH2) protein from rps. acidophila as a specific example of how this process might be controlled in a protein environment. Crucially, we reveal that the LH2 antenna protein prevents quenching, even at the high chlorophyll concentrations required for efficient energy transfer, by restricting the range of orientations that neighboring chlorophyll pairs can adopt.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Coarse-grained explicit-solvent molecular dynamics simulations of semidilute unentangled polyelectrolyte solutions

In this study, we present results from explicit-solvent coarse-grained molecular dynamics (MD) simulations of fully charged, salt-free, and unentangled polyelectrolytes in semidilute solutions. The inclusion of a polar solvent in the model allows for a more physical representation of these solutions at concentrations, where the assumptions of a continuum dielectric medium and screened hydrodynamics break down. The collective dynamic structure factor of polyelectrolytes, S(q, t), showed that at q > q*, where q* = 2π/ξ is the polyelectrolyte peak in the structure factor S(q) and ξ is the correlation length, the relaxation time obtained from fits to stretched exponential was $\tau$ KWW ~ q -3 , which describes unscreened Zimm-like dynamics. This is in contrast to implicit-solvent simulations using a Langevin thermostat where $\tau$ KWW ~ q -2 . At q < q*, a crossover region was observed that eventually transitions to another inflection point $\tau$ KWW ~ q -2 at length scales larger than ξ for both implicit- and explicit-solvent simulations. The simulation results were also compared to scaling predictions for correlation length, ξ ~ c$-½\atop{p}$, specific viscosity, η sp ~ c$½\atop{p}$, and diffusion coefficient, D ~ c$0\atop{p}$, where c p is the polyelectrolyte concentration. The scaling prediction for ξ holds; however, deviations from the predictions for η sp and D were observed for systems at higher c p , which are in qualitative agreements with recent experimental results. This study highlights the importance of explicit-solvent effects in molecular dynamics simulations, particularly in semidilute solutions, for a better understanding of polyelectrolyte solution behavior.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Computational Methods for Modeling Electrospray Microdroplet Chemistry for Improved Quantitative Mass Spectrometry

This project aimed at enhancing the quantitative analysis capabilities of electrospray ionization mass spectrometry (ESI-MS) by developing advanced computational methods. The primary focus was to integrate continuum and molecular dynamics simulations to study the behavior of microdroplets in the ESI process, from formation to evaporation. Through this research, we sought to bridge significant length and time scales to provide a comprehensive understanding of how analyte concentrations evolve from bulk solutions into gas-phase ions. This understanding is crucial for addressing challenges such as ionization efficiency, solvent effects, and ion suppression, which currently limit the accuracy of quantitative ESI-MS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Stability of Polyethylene Glycol-Coated Copper Nanoparticles and Their Optical Properties

Oxidation is a corrosion reaction where the corroded metal forms an oxide. Prevention of oxidation at the nanoscale is critically important to retain the physicochemical properties of metal nanoparticles. In this work, we studied the stability of polyethylene glycol (PEG) coated copper nanoparticles (PEGylated CuNPs) against oxidation. The freshly-prepared PEGylated CuNPs mainly consist of metallic Cu which are quite stable in air although their surfaces are typically covered with a few monolayers of cuprous oxide. However, they are quickly oxidized in water due to the presence of protons that facilitate oxidation of the cuprous oxide to cupric oxide. PEG with carboxylic acid terminus could slightly delay the oxidation process compared to that with thiol terminus. It was found that a solvent with reducing power such as ethanol could greatly enhance the stability of PEGylated CuNPs by preventing further oxidation of the cuprous oxide to cupric oxide and thus retain the optical properties of CuNPs. The reducing environment also assists the galvanic replacement of these PEGylated CuNPs to form hollow nanoshells; however, they consist of ultra-small particle assemblies due to the co-reduction of gold precursor during the replacement reaction. As a result, these nanoshells do not exhibit strong optical properties in the near-infrared region. This study highlights the importance of solvent effects on PEGylated nonprecious metal nanoparticles against oxidation corrosion and its applications in preserving physicochemical properties of metallic nanostructures.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
NASA NTRS1972

Activation energies for addition of O/3P/ to simple olefins.

Description of relative rate measurements for the addition of O(3P) to C2H4, C2F4, C3H6, and C4H8-1 in liquid argon at 87.5 K. The data strongly indicate that the activation energies for the addition of O(3P) to the double bonds of propylene and butene-1 are identical, probably to within 0.1 kcal/mole. It is very doubtful that differences in pre-exponential factors or other factors such as solvent effects, could invalidate this conclusion. A similar argument holds for the C2H4 and C2F4 reactions. Furthermore, the experiments suggest that the activation energy for addition of O(3P) to the double bond of butene-1 is about 0.1 kcal/mole.

Demore, W. B.↗
NASA NTRS1998

Syntheses of Octasubstituted Metal Phthalocyanines for Nonlinear Optics

Many organic materials can be used as nonlinear optical media. Phthalocyanines are of special interest because they show an unusually large third order nonlinear response, they are thermally and photochemically stable and they can be formed into oriented thin films (Langmuir-Blodgett films). They also can be easily complexed by a large variety of metals, which place them at the interface between organics and organometallics, and allows for fine tuning of the macro cycle electronic properties by the coordinated metal and substituent groups. A series of 1,4,8,11,15,18,22,25-octaalkoxy metal-free and metal phthalocyanines and 2,3,9,10,16,17,23,24-octaalkoxy metal phthalocyanines has been synthesized. Their nonlinear optical properties have been measured. The physical properties of all the phthalocyanines synthesized in this work are subject to both acid and solvent effects.

Guo, Huaisong↗
NASA NTRS2011

A Theoretical Investigation of the Plausibility of Reactions Between Ammonia and Carbonyl Species (Formaldehyde, Acetaldehyde, and Acetone) in Interstellar Ice Analogs at Ultracold Temperatures

We have reexamined the reaction between formaldehyde and ammonia, which was previously studied by us and other workers in modestly sized cluster calculations. Larger model systems with up to 12H2O were employed, and reactions of two more carbonyl species, acetaldehyde and acetone, were also carried out. Calculations were performed at the B3LYP/6-31+G** level with bulk solvent effects treated with a polarizable continuum model; limited MP2/6-31+G** calculations were also performed. We found that while the barrier for the concerted proton relay mechanism described in previous work remains modest, it is still prohibitively high for the reaction to occur under the ultracold conditions that prevail in dense interstellar clouds. However, a new pathway emerged in more realistic clusters that involves at least one barrierless step for two of the carbonyl species considered here: ammonia reacts with formaldehyde and acetaldehyde to form a partial charge transfer species in small clusters (4H2O) and a protonated hydroxyamino intermediate species in large clusters (9H2O, 12H2O); modest barriers that decrease sharply with cluster size are found for the analogous processes for the acetone-NH3 reaction. Furthermore, if a second ammonia replaces one of the water molecules in calculations in the 9H2O clusters, deprotonation can occur to yield the same neutral hydroxyamino species that is formed via the original concerted proton relay mechanism. In at least one position, deprotonation is barrierless when zero-point energy is included. In addition to describing the structures and energetics of the reactions between formaldehyde, acetaldehyde, and acetone with ammonia, we report spectroscopic predictions of the observable vibrational features that are expected to be present in ice mixtures of different composition.

Chen, Lina↗