https://ogma.newcastle.edu.au/vital/access/ /manager/Index ${session.getAttribute("locale")} 5 Role of Graphitic Bowls in Temperature Dependent Fullerene Formation https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:52124 I_h-C₆₀ to investigate the formation mechanisms of fullerenes at high temperature conditions. From the results of these DFTB-MD calculations we were able to develop a thermokinetic model to describe the free energies and kinetics of fullerene formation at a range of temperatures. Direct observation of the mechanism revealed fullerenes readily forming in nanosecond times between 2000 and 3000 K but were hindered above this temperature window. Analysis revealed temperature dependent formation mechanisms where at low temperatures (<2750K) flat graphitic bowls play an important part as metastable intermediates while highly curved bowls follow a direct fast transformation. Meanwhile at higher temperatures (>2750 K), flat bowls become the transitory structure between chains and fullerene. Free energy analysis from our thermokinetic model shows this change in graphitic bowls to being transitory hinders fullerene formation at high temperatures compared to lower temperatures, essentially kinetically trapping C₆₀ as chain networks. This investigation gives new key insights into the formation mechanisms of C₆₀ fullerenes and highlights important intermediates while also illuminating the temperature window for fullerene formation, facilitating better optimization of experimental methods.]]> Thu 28 Sep 2023 15:04:39 AEST ]]> Mechanism and rate of thermal decomposition of hexachlorocyclopentadiene and its importance in PCDD/F formation from the combustion of cyclodiene pesticides https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:31498 2. This process has been studied by quantum chemical calculation, and a reaction potential energy surface has been developed. The rate constant of initial Cl atom fission has been calculated by canonical variational transition state theory as k = 1.45 × 10¹⁵ exp(−222 ± 9 kJ mol^–1/RT) s^–1 between 500 and 2000 K. A minimal kinetic model was developed to model the decomposition and major products. Oxidative decomposition was studied in nitrogen with O₂ contents of 1, 6, 12, and 20 mol %. Increasing O₂ to 6–8% increased the rate of decomposition of HCCP and decreased the yield of 8ClNP. Above 823 K, hexachlorobenzene (HCB) and CO became major products. The oxidative reaction has also been studied quantum chemically. At high O₂ content (>∼10%), the rate of decomposition of HCCP declined as did yields of 8ClNP and HCB, but CO yields increased]]> Sat 24 Mar 2018 08:44:07 AEDT ]]> Molecular dynamics simulation of the low-temperature partial oxidation of CH4 https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:8284 Sat 24 Mar 2018 08:40:28 AEDT ]]> Kinetics and mechanism of carbamate formation from CO₂(aq), carbonate species, and monoethanolamine in aqueous solution https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:8321 Sat 24 Mar 2018 08:36:59 AEDT ]]> Quantum chemical study of low temperature oxidation mechanism of dibenzofuran https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:996 Sat 24 Mar 2018 08:29:49 AEDT ]]> Theoretical study of the ammonia-hypochlorous acid reaction mechanism https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:10414 Sat 24 Mar 2018 08:12:38 AEDT ]]> Comprehensive study of the hydration and dehydration reactions of carbon dioxide in aqueous solution https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:10423 Sat 24 Mar 2018 08:12:37 AEDT ]]> Theoretical study of unimolecular decomposition of catechol https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:9906 Sat 24 Mar 2018 08:07:40 AEDT ]]> Theoretical study on the thermodynamic properties and self-decomposition of methylbenzenediol isomers https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:9905 Sat 24 Mar 2018 08:07:40 AEDT ]]> Thermochemical properties and decomposition pathways of three isomeric semiquinone radicals https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:9907 Sat 24 Mar 2018 08:07:40 AEDT ]]> Comprehensive kinetic and thermodynamic study of the reactions of CO2(aq) and HCO3− with monoethanolamine (MEA) in aqueous solution https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:17531 2(aq) and monoethanolamine (MEA) has been investigated using stopped-flow spectrophotometry by following the pH changes during the reactions with colored acid–base indicators. Multivariate global analysis of both the forward and backward kinetic measurements for the reaction of CO₂(aq) with MEA yielded the rate and equilibrium constants, including the protonation constant of MEA carbamate, for the temperature range of 15–45 °C. Analysis of the rate and equilibrium constants in terms of the Arrhenius, Eyring, and van’t Hoff relationships gave the relevant thermodynamic parameters. In addition, the rate and equilibrium constants for the slow, reversible reaction of bicarbonate with MEA are reported at 25.0 °C. At high pH, reactions of the amine with CO₂ and with bicarbonate are significant.]]> Sat 24 Mar 2018 08:03:56 AEDT ]]> Reactions of CO₂ with aqueous piperazine solutions: formation and decomposition of mono- and dicarbamic acids/carbamates of piperazine at 25.0 degrees °C https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:19664 Sat 24 Mar 2018 08:01:10 AEDT ]]> Kinetics of the reversible reaction of CO2(aq) with ammonia in aqueous solution https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:17954 Sat 24 Mar 2018 07:56:27 AEDT ]]> Kinetics of the reversible reaction of CO2(aq) and HCO 3- with sarcosine salt in aqueous solution https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:27723 Sat 24 Mar 2018 07:36:44 AEDT ]]> SERS and NMR studies of typical aggregation-induced emission molecules https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:27580 Sat 24 Mar 2018 07:23:43 AEDT ]]> Computational study of the oxidation and decomposition of dibenzofuran under atmospheric conditions https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:4437 Sat 24 Mar 2018 07:22:47 AEDT ]]> Quantum chemical and kinetic study of formation of 2-chlorophenoxy radical from 2-chlorophenol: unimolecular decomposition and bimolecular reactions with H, OH, Cl, and O₂ https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:4438 Sat 24 Mar 2018 07:22:47 AEDT ]]> Interaction between tetramethylcucurbit[6]uril and some pyridine derivates https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:3187 Sat 24 Mar 2018 07:21:56 AEDT ]]> Understanding and improving solid-state polymer/C₇₀-fullerene bulk-heterojunction solar cells using ternary porphyrin blends https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:3196 Sat 24 Mar 2018 07:21:55 AEDT ]]> Ab initio study of bonding between nucleophilic species and the nitroso group https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:3422 Sat 24 Mar 2018 07:21:37 AEDT ]]> Theoretical study of reaction pathways of dibenzofuran and dibenzo-p-dioxin under reducing conditions https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:3410 Sat 24 Mar 2018 07:21:36 AEDT ]]> Quantum chemical investigation of formation of polychlorodibenzo-p-dioxins and dibenzofurans from oxidation and pyrolysis of 2-chlorophenol https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:3500 Sat 24 Mar 2018 07:20:36 AEDT ]]> Ab initio procedure for aqueous-phase pKa calculation: the acidity of nitrous acid https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:3394 Sat 24 Mar 2018 07:18:57 AEDT ]]> Rovibrational spectra of LiH₂⁺, LiHD⁺ and LiD₂⁺ determined from FCI property surfaces https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:3180 band was found to have the greatest spectral intensity with respect to the ground electronic states of ⁶,⁷LiH₂⁺, ⁶,⁷LiHD⁺, and ⁶,⁷LiD₂⁺. In each case, the most intense rovibrational transitions have been assigned unequivocally using the J, Ka, Kc assignment scheme.]]> Sat 24 Mar 2018 07:18:09 AEDT ]]> Ab initio structures and stabilities of doubly charged diatomic metal helides for the first row transition metals https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:3181 Sat 24 Mar 2018 07:18:08 AEDT ]]> A mechanistic and kinetic study on the decomposition of morpholine https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:22300 Sat 24 Mar 2018 07:11:06 AEDT ]]> Performance of DFT for C-₆₀ isomerization energies: a noticeable exception to Jacob's ladder https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:41901 Mon 15 Aug 2022 14:08:26 AEST ]]> On The Existence of Nonunique Equilibrium States https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:54739 Mon 11 Mar 2024 14:20:03 AEDT ]]> Lewis strength determines specific-ion effects in aqueous and nonaqueous solvents https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:36712 Fri 26 Jun 2020 09:26:42 AEST ]]> Accurate Thermochemical and Kinetic Stabilities of C84 Isomers https://ogma.newcastle.edu.au/vital/access/ /manager/Repository/uon:42970 Fri 09 Sep 2022 12:32:51 AEST ]]>