Structure and Redox Properties of 5-Amino-3-nitro-1<i>H</i>-1,2,4-triazole (ANTA) Adsorbed on a Silica Surface: A DFT M05 Computational Study

Sviatenko, Liudmyla K.; Gorb, Leonid; Hill, Frances C.; Leszczyńska, Danuta; Leszczyński, Jerzy

doi:10.1021/acs.jpca.5b03393

Cited by 13 publications

(16 citation statements)

References 36 publications

(59 reference statements)

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“…The effect of implicit solvation on clusters and molecules was studied using the ORCA 4.0.1.2 software , and the SMD polarizable continuum model (PCM) of water, which has previously been used to study surface adsorption. , Structures were based on the deMon2k-optimized geometries, but further optimization of the central 17 Cu atoms and adsorbates were performed with the 49 edge Cu atoms frozen. The RPBE/Def2-TZVP(-f)//Def2-SVP level of theory was employed, see the Supporting Information for an example input file.…”

Section: Methodsmentioning

confidence: 99%

Spin Uncoupling in Chemisorbed OCCO and CO₂: Two High-Energy Intermediates in Catalytic CO₂ Reduction

et al. 2018

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The production of useful compounds via the electrochemical carbon dioxide reduction reaction (CO2RR) is a matter of intense research. Although the thermodynamics and kinetic barriers of CO2RR are reported in previous computational studies, the electronic structure details are often overlooked. We study two important CO2RR intermediates: ethylenedione (OCCO) and CO 2 covalently bound to cluster and slab models of the Cu(100) surface. Both molecules exhibit a near-unity negative charge as chemisorbed, but otherwise they behave quite differently, as explained by a spinuncoupling perspective. OCCO adopts a high-spin, quartetlike geometry, allowing two covalent bonds to the surface with an average gross interaction energy of −1.82 eV/bond. The energy cost for electronically exciting OCCO − to the quartet state is 1.5 eV which is readily repaid via the formation of its two surface bonds. CO 2 , conversely, retains a low-spin, doubletlike structure upon chemisorption, and its single unpaired electron forms a single covalent surface bond of −2.07 eV. The 5.0 eV excitation energy to the CO 2 − quartet state is prohibitively costly and cannot be compensated for by an additional surface bond.

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Section: Methodsmentioning

confidence: 99%

Spin Uncoupling in Chemisorbed OCCO and CO₂: Two High-Energy Intermediates in Catalytic CO₂ Reduction

et al. 2018

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“…Arid regions are known to contain a high concentration of naturally occurring solid Lewis acids (e.g., silicas, aluminas, ferric oxides) which can interact with the electron-rich substituent groups commonly found in munitions. Because of the heterogeneity of soils ( vide supra ), computational studies are often carried out on individual soil components in order to predict the fate of energetic compounds in this environment. − …”

Section: Introductionmentioning

confidence: 99%

Thermodynamic Adsorption States of TNT and DNAN on Corundum and Hematite

2020

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Adsorption isotherms are a critical tool in determining the transport of environmental contaminants through a particular media. Owing to the inherent heterogeneity of soils, the determination of which soil components are responsible for the adsorption and retention of a particular contaminant remains a challenge. In the current study, we consider several thermodynamic adsorption states in order to predict whether or not 2,4,6-trinitrotoluene (TNT) or 2,4-dinitroanisole (DNAN) would be either a ground-water contaminant or a soil contaminant. In order to reduce the complexity, we only consider two metal oxides (hematite and corundum) that are commonly found in arid regions. We have shown that TNT and DNAN bind favorably across all concentrations, temperatures, and surface hydration considered for α-Al 2 O 3 ; however, only TNT was found to be bound for α-Fe 2 O 3 . Our results indicate that for soils rich in iron oxides, DNAN would be a ground-water contaminant.

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“…For the reduction potentials in both the gas phase and water solution, we employed the Nernst equation where E red ° and E ox ° are the reduction and oxidation potentials, respectively, in either the gas phase or water solution; n is the number of electrons ( n = 1); F is the Faraday constant (96,485.3 C mol –1 ); and E H is the potential for the standard hydrogen electrode (−4.28 eV). − Δ G red ° is the Gibbs free energy required to attach adiabatically an electron to the DNAM conformer in either the gas phase or water solution, and likewise Δ G ox ° is the Gibbs free energy necessary to remove an electron adiabatically in the gas phase or water solution. These terms may be interpreted as simple differences in Gibbs free energy between the radical and neutral species, as shown in eqs and where G is the Gibbs free energy of neutral DNAM and G opt •+ and G opt •– are the Gibbs free energies of the radical cation and anion forms of DNAM, respectively.…”

Section: Computational Detailsmentioning

confidence: 99%

Computational Investigation on Electronic Structures and Properties of 4,6-Bis(nitroimino)-1,3,5-triazinan-2-one: An Insensitive Munition Compound

et al. 2019

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In order to minimize unintentional detonation, munitions researchers have focused on the development of chemical compounds that are insensitive to external stimuli while maintaining their effectiveness. Although these compounds, known as high-performance insensitive munition compounds, are promising in terms of potency and stability, their environmental impacts have either not been fully understood or are yet to be investigated. In the present research, we have performed a quantum chemical investigation on electronic structures and properties of an insensitive munition compound 4,6-bis(nitroimino)-1,3,5-triazinan-2-one (DNAM). The density functional theory using the B3LYP and M06-2X functionals and MP2 methodology were used for geometry optimization of various tautomeric forms of DNAM. The effect of bulk water solution was evaluated using the conductor-like polarizable continuum model and the density-based solvation model. Ionization potentials, electron affinities, redox properties, and pK a values were also computed and compared with the available experimental data. These physical and chemical properties of DNAM have been discussed with regard to the varying tautomeric forms in which DNAM can exist.

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Structure and Redox Properties of 5-Amino-3-nitro-1H-1,2,4-triazole (ANTA) Adsorbed on a Silica Surface: A DFT M05 Computational Study

Cited by 13 publications

References 36 publications

Spin Uncoupling in Chemisorbed OCCO and CO₂: Two High-Energy Intermediates in Catalytic CO₂ Reduction

Spin Uncoupling in Chemisorbed OCCO and CO₂: Two High-Energy Intermediates in Catalytic CO₂ Reduction

Thermodynamic Adsorption States of TNT and DNAN on Corundum and Hematite

Computational Investigation on Electronic Structures and Properties of 4,6-Bis(nitroimino)-1,3,5-triazinan-2-one: An Insensitive Munition Compound

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Structure and Redox Properties of 5-Amino-3-nitro-1H-1,2,4-triazole (ANTA) Adsorbed on a Silica Surface: A DFT M05 Computational Study

Cited by 13 publications

References 36 publications

Spin Uncoupling in Chemisorbed OCCO and CO2: Two High-Energy Intermediates in Catalytic CO2 Reduction

Spin Uncoupling in Chemisorbed OCCO and CO2: Two High-Energy Intermediates in Catalytic CO2 Reduction

Thermodynamic Adsorption States of TNT and DNAN on Corundum and Hematite

Computational Investigation on Electronic Structures and Properties of 4,6-Bis(nitroimino)-1,3,5-triazinan-2-one: An Insensitive Munition Compound

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Spin Uncoupling in Chemisorbed OCCO and CO₂: Two High-Energy Intermediates in Catalytic CO₂ Reduction

Spin Uncoupling in Chemisorbed OCCO and CO₂: Two High-Energy Intermediates in Catalytic CO₂ Reduction