• Energy Research

The work presented in this chapter has been published as a journal article entitled ‘A Halomethane Thermochemical Network from iPEPICO Experiments and Quantum Chemical Calculations’ in 2012 by J. Harvey, R. P. Tuckett and A. Bodi, in the Journal of Physical Chemistry A, volume 116, issue 39, pages 9696-9705. The majority of the data collection and analysis was performed by the author, however, the assistance lent by Ms Nicola Rogers, Drs Mathew Simpson Andras Bodi, Melanie Johnson and Professor Richard Tuckett during beamtime with the collection of the data is gratefully acknowledged. The modelling program was developed by Sztaray [1]. The threshold photoelectron spectra can be found in Appendix C.

Abstract The elimination of HBr from CH 3 Br by ground state of Cu + and Au + has been investigated by using DFT methods. A mechanism of one-step HBr elimination leading to CuCH 2 + was identified. For the formation of AuCH 2 + , besides the one-step mechanism, another two-step HBr elimination pathway through a C–Br bond insertion intermediate was also found, and this pathway is energetically more favorable than the one-step mechanism. The calculated reaction energy barriers show that the formation of AuCH 2 + is energetically much more favorable than the formation of CuCH 2 + . The experimental observations are well explained.

Publisher Summary This chapter describes several computational studies of the thermodynamics of the Catalytica Pt(II) catalysts for selective oxidation of CH 4 to CH 3 OH. All calculations were carried out at the B3LYP/LACVP(+) level, including the Poisson–Boltzmann continuum approximation to describe salvation effects. The chapter examines the thermodynamics of four possible reaction pathways, involving dissociative versus associative pathways; and oxidation-after (before)-activation pathways. The reaction energy profiles for the C–H activation via electrophilic substitution are presented. The results are summarized—(1) the dissocative pathway outweighs the associative pathway in the ammine system; while the associative pathway is competitive with the dissociative pathway in the bpym system, (2) the ammine system should be more active than the bpym systems, as both activation and oxidation steps are easier in the ammine system, in agreement with the experimental observation, and (3) the oxidation-after-activation pathways are preferable to the oxidation-before-activation pathways for the bpym systems; whereas the ammine ligands are in favor of the oxidation-before-activation pathways.

Using the idea of Materials Genome Initiative (MGI) for reference, by means of the First-principle calculation method, according to the known MNCl (M = Zr, Hf) structure to build model, we systematically calculated and analysised the binding energy and reaction energy of two phases of lanthanon replaced ReNCl compounds. Finally, we established the mathematical model, predicted the synthesis of ReNCl theoretically. Keywords-simulation; first-principles calculations; nitride chlorides

More than 60% of the Q-value measurements of charged primary particle reactions used in nuclidic mass adjustments have been calibrated with natural α-particle energy standards, predominantly 210Po; in some other cases, 212Po and 212Bi have been used. 214Po has been used in a few relative measurements of reaction energy standards. Additional application of absolute α-energies is found in α-spectroscopy, where even less abundant α-groups are useful, in order to cover the full range between 4 and 10 MeV.