A computational investigation of adsorption of organics on mineral surfaces: Implications for organics delivery in the early solar system

Asaduzzaman, Abu; Zega, T. J.; Laref, S.; Runge, Keith; Deymier, Pierre A.; Muralidharan, Krishna

doi:10.1016/j.epsl.2014.10.029

Cited by 15 publications

(20 citation statements)

References 55 publications

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“…PBE-D4 is consistent with the PW method using PBE-D2. 54 The interatomic distances, calculated with PBE-D4, between the center of the ring and the Mg atom are in good agreement with the B3LYP-D2 calculation. 53 However, the binding energy calculated at the PBE-D4/CP-DZP level differs from B3LYP-D2/TZP//B3LYP-D2/DZP 53 by 0.45 eV.…”

Section: Results and Discussionsupporting

confidence: 67%

“… 46 Here, we focus on the level of theory for the adsorption of a small aromatic molecule, benzene, on {010}-fo. 53 , 54 …”

Section: Results and Discussionmentioning

confidence: 99%

“… 5 , 6 , 86 , 87 However, due to the large computational cost, little has been done to study the chemical and physical properties of PAHs on minerals. 53 , 54 In this work, we identified a DFT method that can accurately compute the binding energy of aromatic molecules on a mineral surface. The PBE-D4/DZP binding energies are accurate enough to be used in astronomical gas-grain models to predict the abundance of aromatic species in some regions of interstellar medium.…”

Section: Discussionmentioning

confidence: 99%

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Interaction of Aromatic Molecules with Forsterite: Accuracy of the Periodic DFT-D4 Method

et al. 2021

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Density functional theory (DFT) has provided deep atomic-level insights into the adsorption behavior of aromatic molecules on solid surfaces. However, modeling the surface phenomena of large molecules on mineral surfaces with accurate plane wave methods (PW) can be orders of magnitude more computationally expensive than localized atomic orbitals (LCAO) methods. In the present work, we propose a less costly approach based on the DFT-D4 method (PBE-D4), using LCAO, to study the interactions of aromatic molecules with the {010} forsterite (Mg 2 SiO 4 ) surface for their relevance in astrochemistry. We studied the interaction of benzene with the pristine {010} forsterite surface and with transition-metal cations (Fe 2+ and Ni 2+ ) using PBE-D4 and a vdW-inclusive density functional (Dion, Rydberg, Schröder, Langreth, and Lundqvist (DRSLL)) with LCAO methods. PBE-D4 shows good agreement with coupled-cluster methods (CCSD(T)) for the binding energy trend of cation complexes and with PW methods for the binding energy of benzene on the forsterite surface with a difference of about 0.03 eV. The basis set superposition error (BSSE) correction is shown to be essential to ensure a correct estimation of the binding energies even when large basis sets are employed for single-point calculations of the optimized structures with smaller basis sets. We also studied the interaction of naphthalene and benzocoronene on pristine and transition-metal-doped {010} forsterite surfaces as a test case for PBE-D4. Yielding results that are in good agreement with the plane wave methods with a difference of about 0.02–0.17 eV, the PBE-D4 method is demonstrated to be effective in unraveling the binding structures and the energetic trends of aromatic molecules on pristine and transition-metal-doped forsterite mineral surfaces. Furthermore, PBE-D4 results are in good agreement with its predecessor PBE-D3(BJM) and with the vdW-inclusive density functionals, as long as transition metals are not involved. Hence, PBE-D4/CP-DZP has been proven to be a robust theory level to study the interaction of aromatic molecules on mineral surfaces.

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Section: Results and Discussionsupporting

confidence: 67%

“… 46 Here, we focus on the level of theory for the adsorption of a small aromatic molecule, benzene, on {010}-fo. 53 , 54 …”

Section: Results and Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

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Interaction of Aromatic Molecules with Forsterite: Accuracy of the Periodic DFT-D4 Method

et al. 2021

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“…Such a process may be compatible with the organosynthesis route we suggest here. Interestingly, direct adsorption of organic material onto mineral surfaces as been advocated as an efficient way of producing more complex organic molecules of astrobiological interest, such as amino acids ( 61 ), and consequently may have strong implications on organic delivery to early Earth.…”

Section: Discussionmentioning

confidence: 99%

Synthesis of refractory organic matter in the ionized gas phase of the solar nebula

Kuga

Marty

Marrocchi

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

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SignificanceRefractory organics are the main hosts of carbon, nitrogen, and other biogenic elements in primitive solar system material. We have synthesized refractory organics by ionizing a gas mixture reminiscent of the composition of the protosolar nebula, at temperatures up to 1,000 K in a plasma. Synthesized compounds share chemical and structural features with chondritic organics, and trapped noble gases reproduce well the elemental and isotopic characteristics of meteoritic noble gases. Our study suggests that organosynthesis took place in the solar system, including in its warm regions, and was ubiquitous anywhere the nebular gas was subject to ionization.

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“…The interaction of forsterite surfaces (Mg-rich olivine) with several molecules, such as water, glycine, ammonia, CO, CO 2 , CH 4 etc. has been studied using several theoretical methodologies finding chemisorption processes in the solid-gas interphase (Asaduzzaman et al, 2014;Moreno, 2012, 2013;Escamilla-Roa et al, 2017).…”

Section: Introductionmentioning

confidence: 99%

DFT study of electronic and redox properties of TiO2 supported on olivine for modelling regolith on Moon and Mars conditions

Escamilla‐Roa

Zorzano

Martín‐Torres

et al. 2020

Planetary and Space Science

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Titanium dioxide (TiO 2) is one of the most studied oxides in photocatalysis, due to its electronic structure and its wide variety of applications, such as gas sensors and biomaterials, and especially in methane-reforming catalysis. Titanium dioxide and olivine have been detected both on Mars and our Moon. It has been postulated that on Mars photocatalytic processes may be relevant for atmospheric methane fluctuation, radicals and perchlorate productions etc. However, to date no investigation has been devoted to modelling the properties of TiO 2 adsorbed on olivine surface. The goal of this study is to investigate at atomic level with electronic structure calculations based on the Density Functional Theory (DFT), the atomic interactions that take place during the adsorption processes for formation of a TiO regolith. These models are formed with different titanium oxide films adsorbed on olivine (forsterite) surface, one of the most common minerals in Universe, Earth, Mars, cometary and interstellar dust. We propose three regolith models to simulate the principal phases of titanium oxide (TiO, Ti 2 O 3 and TiO 2). The models show different adsorption processes i.e. physisorption and chemisorption. Our results suggest that the TiO is the most reactive phase and produces a strong exothermic effect. Besides, we have detailed, from a theoretical point of view, the effect that has the adsorption process in the electronic properties such as electronic density of states (DOS) and oxide reduction process (redox). This theoretical study can be important to understand the formation of new materials that can be used as support in the catalytic processes that occur in the Earth, Mars and Moon. Also, it may be important to interpret the present day photochemistry and interaction of regolith and airborne aerosols in the atmosphere on Mars or to define possible catalytic reactions of the volatiles captured on the Moon regolith.

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A computational investigation of adsorption of organics on mineral surfaces: Implications for organics delivery in the early solar system

Cited by 15 publications

References 55 publications

Interaction of Aromatic Molecules with Forsterite: Accuracy of the Periodic DFT-D4 Method

Interaction of Aromatic Molecules with Forsterite: Accuracy of the Periodic DFT-D4 Method

Synthesis of refractory organic matter in the ionized gas phase of the solar nebula

DFT study of electronic and redox properties of TiO2 supported on olivine for modelling regolith on Moon and Mars conditions

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