Jonas Elm

Assessment of Density Functional Theory in Predicting Structures and Free Energies of Reaction of Atmospheric Prenucleation Clusters

This work assesses different computational strategies for predicting structures and Gibbs free energies of reaction of atmospheric prenucleation clusters. The performance of 22 Density Functional Theory functionals in predicting equilibrium structures of molecules and water prenucleation clusters of atmospheric relevance is evaluated against experimental data using a test set of eight molecules and prenucleation clusters: SO2, H2SO4, CO2·H2O, CS2·H2O, OCS·H2O, SO2·H2O, SO3·H2O, and H2SO4·H2O. Furthermore, the functionals are tested and compared for their ability to predict the free energy of reaction for the formation of five benchmark atmospheric prenucleation clusters: H2SO4·H2O, H2SO4·(H2O)2, H2SO4·NH3, HSO4(-)·H2O, and HSO4(-)·(H2O)2. The performance is evaluated against experimental data, coupled cluster, and complete basis set extrapolation procedure methods. Our investigation shows that the utilization of the M06-2X functional with the 6-311++G(3df,3pd) basis set represents an improved approach compared to the conventionally used PW91 functional, yielding mean absolute errors of 0.48 kcal/mol and maximum errors of 0.67 kcal/mol compared to experimental results.

Molecular Interaction of Pinic Acid with Sulfuric Acid: Exploring the Thermodynamic Landscape of Cluster Growth

We investigate the molecular interactions between the semivolatile α-pinene oxidation product pinic acid and sulfuric acid using computational methods. The stepwise Gibbs free energies of formation have been calculated utilizing the M06-2X functional, and the stability of the clusters is evaluated from the corresponding ΔG values. The first two additions of sulfuric acid to pinic acid are found to be favorable with ΔG values of -9.06 and -10.41 kcal/mol. Addition of a third sulfuric acid molecule is less favorable and leads to a structural rearrangement forming a bridged sulfuric acid-pinic acid cluster. The involvement of more than one pinic acid molecule in a single cluster is observed to lead to the formation of favorable (pinic acid)2(H2SO4) and (pinic acid)2(H2SO4)2 clusters. The identified most favorable growth paths starting from a single pinic acid molecule lead to closed structures without the further possibility for attachment of either sulfuric acid or pinic acid. This suggests that pinic acid cannot be a key species in the first steps in nucleation, but the favorable interactions between sulfuric acid and pinic acid imply that pinic acid can contribute to the subsequent growth of an existing nucleus by condensation.

Towards Solar Energy Storage in the Photochromic Dihydroazulene–Vinylheptafulvene System

One key challenge in the field of exploitation of solar energy is to store the energy and make it available on demand. One possibility is to use photochromic molecules that undergo light-induced isomerization to metastable isomers. Here we present efforts to develop solar thermal energy storage systems based on the dihydroazulene (DHA)/vinylheptafulvene (VHF) photo/thermoswitch. New DHA derivatives with one electron-withdrawing cyano group at position 1 and one or two phenyl substituents in the five-membered ring were prepared by using different synthetic routes. In particular, a diastereoselective reductive removal of one cyano group from DHAs incorporating two cyano groups at position 1 turned out to be most effective. Quantum chemical calculations reveal that the structural modifications provide two benefits relative to DHAs with two cyano groups at position 1: 1) The DHA-VHF energy difference is increased (i.e., higher energy capacity of metastable VHF isomer); 2) the Gibbs free energy of activation is increased for the energy-releasing VHF to DHA back-reaction. In fact, experimentally, these new derivatives were so reluctant to undergo the back-reaction at room temperature that they practically behaved as DHA to VHF one-way switches. Although lifetimes of years are at first attractive, which offers the ultimate control of energy release, for a real device it must of course be possible to trigger the back-reaction, which calls for further iterations in the future.

Computational methodology study of the optical and thermochemical properties of a molecular photoswitch.

We assess how the utilization of different DFT functionals for obtaining the equilibrium geometries and vibrational frequencies affect the description of the thermochemistry and subsequent calculation of the optical properties of a dihydroazulene-vinylheptafulvene photoswitch. The assessment covers nine popular DFT functionals (BLYP, B3LYP, CAM-B3LYP, M06-L, M06, M06-2X, PBE, PBE0, and ωB97X-D) in conjugation with five different Pople style basis sets (6-31+G(d), 6-31++G(d,p), 6-311+G(d), 6-311++G(d,p), and 6-311++G(3df,3pd)). It is identified that only CAM-B3LYP, M06-2X, and PBE0 are able to quantitatively describe the correct trends in the thermochemical properties. The subsequent calculation of the optical properties using the CAM-B3LYP functional shows that there is little difference in whether the CAM-B3LYP, M06-2X, or PBE0 functionals have been used to calculate the equilibrium geometries. Utilizing the identified functionals, we investigate how the number of electron withdrawing cyano substituents influence the thermochemistry and optical properties of the molecular photoswitch.

Influence of nucleation precursors on the reaction kinetics of methanol with the OH radical.

The mechanism and kinetics of the reaction of methanol with the OH radical in the absence and presence of common atmospheric nucleation precursors (H2O, NH3, and H2SO4) have been investigated using different computational methods. The statistical Gibbs free energy of formation has been calculated using M06-2X/6-311++G(3df,3pd) in order to assess cluster stability. Methanol is found to have an unfavorable interaction with water and ammonia but form stable complexes with sulfuric acid. The reaction kinetics with the OH radical and methanol with or without the presence of nucleation precursors has been studied using a CCSD(T)-F12a/VDZ-F12//BH&HLYP/aug-cc-pVTZ∥Eckart methodology, and it is found that the presence of water is unlikely to change the overall reaction rate and mechanism of hydrogen abstraction from methanol. Ammonia is able to both enhance the reaction rate and change the reaction mechanism, but due to a very weak interaction with methanol, this process is unlikely to occur under atmospheric conditions. Sulfuric acid is, in contrast, found to be able to act as a stabilizing factor for methanol and is able to change the reaction mechanism. These findings show the first indications that nucleation precursors such as ammonia and sulfuric acid are able to alter the reaction mechanism of an atmospherically relevant organic compound.

Interaction of Glycine with Common Atmospheric Nucleation Precursors

The interaction between the simplest amino acid glycine in three different protonation states and common atmospheric nucleation precursors (H2O, NH3, and H2SO4) has been investigated using computational methods. Each nucleation step has been thoroughly sampled, and statistical Gibbs free energies of formation have been calculated using M06-2X/6-311++G(3df,3pd). From the stepwise ΔG values, the stabilities of the molecular clusters have been evaluated. Glycine in all three protonation states is found to have a favorable interaction with sulfuric acid with a higher cluster stabilizing effect than ammonia. The deprotonated glycine molecule is found to yield the highest stabilizing effect on the sulfuric acid clusters through the interaction of both the amino and carboxylic moieties, while the protonated glycine molecule is found to have a high stabilizing effect on the addition of water and ammonia. Furthermore, we find that a single sulfuric acid molecule is capable of stabilizing the glycine zwitterion. Sulfuric acid is found to be able to catalyze the spontaneous formation of the zwitterion and subsequently stabilize the formed ion. The formation of the glycine zwitterion occurs with a low Gibbs free energy barrier of 2.10 kcal/mol, indicating that this formation could occur rapidly in the atmosphere.

Direct probing of ion pair formation using a symmetric triangulenium dye

The 2,6,10-tris(dialkylamino)trioxatriangulenium dyes (ATOTA(+)) are highly stabilised cationic chromophores with D(3h) symmetry. The symmetry gives rise to a degeneracy of the main electronic transition. In low polarity solvents significant splitting of this degenerate transition is observed and assigned to ion pair formation. Ion pairing of the 2,6,10-tris(dioctylamino)trioxatriangulenium ion with Cl(-), BF(4)(-), PF(6)(-) and TRISPHAT anions was studied using absorption spectroscopy. A clear correlation is found between the size of the anion and the splitting of the ATOTA(+) transitions. In benzene the Cl(-) salt displays a splitting of 1955 cm(-1), while the salt of the much larger TRISPHAT ion has a splitting of 1543 cm(-1). TD-DFT calculations confirm the splitting of the states and provide a detailed insight into the electronic structure of the ion pairs. The different degree of splitting in different ion pairs is found to correlate with the magnitude of the electric field generated in each ion pair, thus leading to the conclusion that the effect seen is an internal Stark effect. By insertion of an amphiphilic derivative of the ATOTA(+) chromophore in an oriented lamellar liquid crystal, it was possible to resolve the two bands of the double peak spectrum and show their perpendicular orientation in the molecular framework, as predicted by the calculations.

Computational Study of the Clustering of a Cyclohexene Autoxidation Product C6H8O7 with Itself and Sulfuric Acid

We investigate the molecular interactions between sulfuric acid and a recently reported C6H8O7 ketodiperoxy acid formed through autoxidation from cyclohexene and ozone. Structurally similar but larger ELVOC (extremely low volatility organic compound) products formed from autoxidation of monoterpenes are believed to play a major role in the formation and early growth of atmospheric aerosol particles. Utilizing density functional theory geometries, with a DLPNO-CCSD(T)/def2-QZVPP single point energy correction, the stepwise Gibbs free energies of formation have been calculated, and the stabilities of the molecular clusters have been evaluated. C6H8O7 interacts weakly with both itself and sulfuric acid, with standard free energies of formation (ΔG at 298 K and 1 atm) around or above 0 kcal/mol. This is due to the presence of strong intramolecular hydrogen bonds in the peroxyacid groups of C6H8O7. These stabilize the isolated molecule with respect to its clusters, and lead to unfavorable interaction energies. The addition of sulfuric acid to clusters containing C6H8O7 is somewhat more favorable, but the formed clusters are still far more likely to evaporate than to grow further in atmospheric conditions. These findings indicate that the O/C ratio cannot exclusively be used as a proxy for volatility in atmospheric new particle formation involving organic compounds. The specific molecular structure, and especially the number of strong hydrogen binding moieties, are equally important. The interaction between the C6H8O7 compound and aqueous phase sulfate ions indicates that ELVOC-type compounds can contribute to aerosol mass by effectively partitioning into the condensed phase.

Aromaticity-Controlled Energy Storage Capacity of the Dihydroazulene-Vinylheptafulvene Photochromic System.

Photochemical conversion of molecules into high-energy isomers that, after a stimulus, return to the original isomer presents a closed-cycle of light-harvesting, energy storage, and release. One challenge is to achieve a sufficiently high energy storage capacity. Here, we present efforts to tune the dihydroazulene/vinylheptafulvene (DHA/VHF) couple through loss/gain of aromaticity. Two derivatives were prepared, one with aromatic stabilization of DHA and the second of VHF. The consequences for the switching properties were elucidated. For the first type, sigmatropic rearrangements of DHA occurred upon irradiation. Formation of a VHF complex could be induced by a Lewis acid, but addition of H2 O resulted in immediate regeneration of DHA. For the second type, the VHF was too stable to convert into DHA. Calculations support the results and provide new targets. We predict that by removing one of the two CN groups at C-1 of the aromatic DHA, the heat storage capacity will be further increased, as will the life-time of the VHF. Calculations also reveal that a CN group at the fulvene ring retards the back-reaction, and we show synthetically that it can be introduced regioselectively.

Computational study of the effect of glyoxal-sulfate clustering on the Henry's law coefficient of glyoxal.

We have used quantum chemical methods to investigate the molecular mechanism behind the recently reported ( Kampf , C. J. ; Environ. Sci. Technol . 2013 , 47 , 4236 - 4244 ) strong dependence of the Henrys law coefficient of glyoxal (C2O2H2) on the sulfate concentration of the aqueous phase. Although the glyoxal molecule interacts only weakly with sulfate, its hydrated forms (C2O3H4 and C2O4H6) form strong complexes with sulfate, displacing water molecules from the solvation shell and increasing the uptake of glyoxal into sulfate-containing aqueous solutions, including sulfate-containing aerosol particles. This promotes the participation of glyoxal in reactions leading to secondary organic aerosol formation, especially in regions with high sulfate concentrations. We used our computed equilibrium constants for the complexation reactions to assess the magnitude of the Henrys law coefficient enhancement and found it to be in reasonable agreement with experimental results. This indicates that the complexation of glyoxal hydrates with sulfate can explain the observed uptake enhancement.