Electron impact ionisation energies of some halo-cyclotriphosphazenes

Clare, Philip; Sowerby, D. Bryan

doi:10.1016/0022-1902(81)80486-1

Cited by 7 publications

(2 citation statements)

References 16 publications

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“…This is also obtained in terms of total energy differences between the neutral and the positively and negatively charged molecule, namely with the SCF method. This returns a quasiparticle energy gap I MOL − A MOL of 11.02 eV, in good agreement (within 4.5%) with the experimental value [25,26]. Likewise we also determine the Fermi level (W F ) of graphene, which is found to be 4.45 eV.…”

Section: A Single Benzene On Pristine Graphenesupporting

confidence: 83%

Charge transfer energies of benzene physisorbed on a graphene sheet from constrained density functional theory

2016

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Constrained density functional theory (CDFT) is used to evaluate the energy level alignment of a benzene molecule as it approaches a graphene sheet. Within CDFT the problem is conveniently mapped onto evaluating total energy differences between different charge-separated states, and it does not consist in determining a quasiparticle spectrum. We demonstrate that the simple local density approximation provides a good description of the level alignment along the entire binding curve, with excellent agreement to experiments at an infinite separation and to GW calculations close to the bonding distance. The method also allows us to explore the effects due to the presence of graphene structural defects and of multiple molecules. In general, all our results can be reproduced by a classical image charge model taking into account the finite dielectric constant of graphene.

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Section: A Single Benzene On Pristine Graphenesupporting

confidence: 83%

Charge transfer energies of benzene physisorbed on a graphene sheet from constrained density functional theory

2016

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“…A likely candidate would be AsBr 4 + [Al(OR) 4 ] À , which we have shown to react with CS 2 to give CS 2 Br 3 + . [61] Since the ionization energies-as a measure of the HOMO energies-of CS 2 (10.08 eV) [62] and (PNCl 2 ) 3 (10.05 eV) [63] are very similar, the use of AsBr 4 + as an ionizing agent is promising (e.g., AsBr 4 + + P 3 N 3 X 3 !P 3 N 3 X 5 + + BrX + AsBr 3 ).…”

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confidence: 99%

Silver Complexes of Cyclic Hexachlorotriphosphazene

Gonsior

Antonijevic

Krossing

2006

Chemistry A European J

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The first solid-state structures of complexed P3N3X6 (X = halogen) are reported for X = Cl. The compounds were obtained from P3N3Cl6 and Ag[Al(OR)4] salts in CH2Cl2/CS2 solution. The very weakly coordinating anion with R = C(CF3)3 led to the salt Ag(P3N3Cl6)2+[Al(OR)4]- (1), but the more strongly coordinating anion with R' = C(CH3)(CF3)2 gave the molecular adduct (P3N3Cl6)AgAl(OR')4 (3). Crystals of [Ag(CH2Cl2)(P3N3Cl6)2]+[Al(OR)4]- (2), in which Ag+ is coordinated by two phosphazene and one CH2Cl2 ligands, were isolated from CH2Cl2 solution. The three compounds were characterized by their X-ray structures, and 1 and 3 also by NMR and vibrational spectroscopy. Solution and solid-state 31P NMR investigations in combination with quantum chemically calculated chemical shifts show that the 31P NMR shifts of free and silver-coordinated P3N3Cl6 differ by less than 3 ppm and indicate a very weakly bound P3N3Cl6 ligand in 1. The experimental silver ion affinity (SIA) of the phosphazene ligand was derived from the solid-state structure of 3. The SIA shows that (PNCl2)3 is only a slightly stronger Lewis base than P4 and CH2Cl2, while other ligands such as S8, P4S3, toluene, and 1,2-Cl2C2H4 are far stronger ligands towards the silver cation. The energetics of the complexes were assessed with inclusion of entropic, thermal, and solvation contributions (MP2/TZVPP, COSMO). The formation of the cations in 1, 2, and 3 was calculated to be exergonic by delta(r)G(degrees)(CH2Cl2) = -97, -107, and -27 kJ mol(-1), respectively. All prepared complexes are thermally stable; formation of P3N3Cl5+ and AgCl was not observed, even at 60 degrees C in an ultrasonic bath. Therefore, the formation of P3N3Cl5+ was investigated by quantum chemical calculations. Other possible reaction pathways that could lead to the successful preparation of P3N3X5+ salts were defined.

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Competitive Transient Electrostatic Adsorption for In Situ Regeneration of Poisoned Catalyst

et al. 2019

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Catalyst deactivation by poisoning species is one important concern in catalysis processes and causes significant catalyst material and operation costs due to process shutdown and catalyst replacement. We report one new in situ catalyst regeneration method, which utilizes competitive electrostatic adsorption of charged ions which are generated with moderate DC voltage supply following the Townsend discharge mechanism to desorb poisoning species and the transient characteristic of electrostatically adsorbed ions to recover the active sites for catalysis. We demonstrate effectiveness of this new concept using HCOOH decomposition on Pt catalyst as model reaction and find the deactivated Pt regains the activity in presence of Ar+ generation. DFT simulations and classical electrical discharge calculations show Ar+ ions have significantly higher electrostatic adsorption energy than desorption energy of CO poisoning species that helps to desorb CO from Pt and generate more available active sites. This new in situ catalyst regeneration method, with convenient, noninvasive and low operation cost features, provides a promising strategy to overcome the challenges associated with current technologies that handle catalyst deactivation.

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Electron impact ionisation energies of some halo-cyclotriphosphazenes

Cited by 7 publications

References 16 publications

Charge transfer energies of benzene physisorbed on a graphene sheet from constrained density functional theory

Charge transfer energies of benzene physisorbed on a graphene sheet from constrained density functional theory

Silver Complexes of Cyclic Hexachlorotriphosphazene

Competitive Transient Electrostatic Adsorption for In Situ Regeneration of Poisoned Catalyst

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