Determination of adiabatic ionization potentials and electron affinities of energetic molecules with the Gaussian-4 method

Manaa, M. Riad

doi:10.1016/j.cplett.2017.04.038

Cited by 7 publications

(6 citation statements)

References 44 publications

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“…These objectives are accomplished by photolytically triggering the decomposition of FOX-7 by pumping energy into these molecules via single wavelength ultraviolet photodissociation (UVPD) in experiments at 532 nm (2.33 eV; 225 kJ mol −1 ) and 355 nm (3.49 eV; 337 kJ mol −1 ) probing the n → π* and π→ π* transitions while tracing the reactive intermediates and products formed in these processes in an ultrahigh-vacuum chamber. These excitation energies are well below the ionization energy of FOX-7 of 9.13 eV, 36 thus excluding any ion chemistry in the condensed phase. However, the selected energies are below (532 nm; 225 kJ mol −1 ) and above (355 nm; 337 kJ mol −1 ) the energy of the transition state involved in the nitro-to-nitrite isomerization of 244−247 kJ mol −1 .…”

Section: Introductionmentioning

confidence: 89%

Exploring the Photochemistry of Solid 1,1-Diamino-2,2-dinitroethylene (FOX-7) Spanning Simple Bond Ruptures, Nitro-to-Nitrite Isomerization, and Nonadiabatic Dynamics

et al. 2022

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The UV photolysis of solid FOX-7 at 5 K with 355 and 532 nm photons was investigated to unravel initial isomerization and decomposition pathways. Isomer-selective single photon ionization coupled with reflectron time-of-flight mass spectrometry (ReTOF-MS) documented the nitric oxide (NO) loss channel at 355 nm along with a nitro-to-nitrite isomerization, which was observed by using infrared spectroscopy, representing the initial reaction pathway followed by O�NO bond rupture of the nitrite moiety. A residual gas analyzer detected molecular oxygen for the 355 and 532 nm photolysis at a ratio of 4.3 ± 0.3:1, which signifies FOX-7 as an energetic material that provides its own oxidant once the decomposition starts. Overall branching ratios for molecular oxygen versus nitric oxide were derived to be 700 ± 100:1 at 355 nm. It is notable that this is the first time that molecular oxygen was detected as a decomposition product of FOX-7. Computations show that atomic oxygen, which later combines to form molecular oxygen, is likely released from a nitro group involving conical intersections. The condensed phase potential energy profile computed at the CCSD(T) and CASPT2 level correlates well with the experiments and highlights the critical roles of conical intersections, nonadiabatic dynamics, and the encapsulated environment that dictate the mechanism of the reaction through intermolecular hydrogen bonds.

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Section: Introductionmentioning

confidence: 89%

Exploring the Photochemistry of Solid 1,1-Diamino-2,2-dinitroethylene (FOX-7) Spanning Simple Bond Ruptures, Nitro-to-Nitrite Isomerization, and Nonadiabatic Dynamics

et al. 2022

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“…The relativistic corrected values are also shown in Tables 1 and 2. About the correlation between the second electron affinity and the polarizability, an important observation must be done: the polarizability reference values [1] for O, S, and Se have an estimated accuracy of 2%, whereas for tellurium (5.5) such estimated accuracy is high as 25%, making a possible correlation unreliable.…”

Section: Resultsmentioning

confidence: 99%

“…In Figure 2, the calculated second electron affinities for phosphorus, arsenic, and antimony are plotted as a function of their polarizabilities: 3.63, 4.32, and 6.6 for P, As and Sb, respectively [1]. The obtained curve (r= 0.9692) provides the equation: 0.987 3.889…”

Section: Resultsmentioning

confidence: 99%

“…As is known, atoms are the simplest chemical systems; electron affinity of an atom A is equal to the difference of ground state total energies (Etot) of A and its negative ion A-, and can be given as: [1]. In the Conceptual Density Functional Theory [2], chemical concepts such as hardness, electronegativity, chemical potential, and softness have been associated with ionization energy and electron affinity values of chemical species via the following equations.…”

Section: Introductionmentioning

confidence: 99%

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Electron affinities for highly charged groups 15 and 16 anions

Kaya

Farias

2021

Cumhuriyet Science Journal

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Electron affinity, electronegativity, and electrophilicity are chemical concepts that have been related to electron accepting power of chemical species. In the literature, although there are many theoretical approaches proposed to calculate the electronegativity and electrophilicity of atoms, ions, and molecules, just a few approaches suggested are related to the prediction of sequential electron affinities of atoms. In the present work, the electron affinities for highly charged groups 15 and 16 anions are calculated by the semi-empirical (PM6) method. The obtained values are compared with those from literature. So far, the authors are concerned, the third and fourth electron affinities for S, P, As and Sb are calculated for the first time. It is well-known that in the calculation of the lattice energy of any inorganic ionic crystal via Born-Haber thermochemical cycle, many parameters regarding any crystal the atoms forming the crystal are considered. One of these parameters is electron affinity. It should be noted that our electron affinity values calculated are in good agreement with both experimental data, other theoretical approaches, and the data obtained in the light of the Born-Haber cycle.

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“… Manaa (2017 ) defines the value of the calculated electron affinity from Gaussian 4 simulations at the CCSD(T) (coupled cluster single-double and perturbative triple) level of the theory as the sum of the values of energy E e for the neutral and the anion with added zero-point corrections of the two values. (2) EA = [E e (optimized neutral) + ZPE (neutral)]–[E e (anion) + ZPE (anion)].…”

Section: Suitability Of Febid Of the Precursormentioning

confidence: 99%

Dissociative electron attachment to gold(I)-based compounds: 4,5-dichloro-1,3-diethyl-imidazolylidene trifluoromethyl gold(I)

et al. 2023

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With the use of proton-NMR and powder XRD (XRPD) studies, the suitability of specific Au-focused electron beam induced deposition (FEBID) precursors has been investigated with low electron energy, structure, excited states and resonances, structural crystal modifications, flexibility, and vaporization level. 4,5-Dichloro-1,3-diethyl-imidazolylidene trifluoromethyl gold(I) is a compound that is a uniquely designed precursor to meet the needs of focused electron beam-induced deposition at the nanostructure level, which proves its capability in creating high purity structures, and its growing importance in other AuImx and AuClnB (where x and n are the number of radicals, B = CH, CH3, or Br) compounds in the radiation cancer therapy increases the efforts to design more suitable bonds in processes of SEM (scanning electron microscopy) deposition and in gas-phase studies. The investigation performed of its powder shape using the XRPD XPERT3 panalytical diffractometer based on CoKα lines shows changes to its structure with change in temperature, level of vacuum, and light; the sensitivity of this compound makes it highly interesting in particular to the radiation research. Used in FEBID, though its smaller number of C, H, and O atoms has lower levels of C contamination in the structures and on the surface, it replaces these bonds with C–Cl and C–N bonds that have lower bond-breaking energy. However, it still needs an extra purification step in the deposition process, either H2O, O2, or H jets.

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Determination of adiabatic ionization potentials and electron affinities of energetic molecules with the Gaussian-4 method

Cited by 7 publications

References 44 publications

Exploring the Photochemistry of Solid 1,1-Diamino-2,2-dinitroethylene (FOX-7) Spanning Simple Bond Ruptures, Nitro-to-Nitrite Isomerization, and Nonadiabatic Dynamics

Exploring the Photochemistry of Solid 1,1-Diamino-2,2-dinitroethylene (FOX-7) Spanning Simple Bond Ruptures, Nitro-to-Nitrite Isomerization, and Nonadiabatic Dynamics

Electron affinities for highly charged groups 15 and 16 anions

Dissociative electron attachment to gold(I)-based compounds: 4,5-dichloro-1,3-diethyl-imidazolylidene trifluoromethyl gold(I)

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