Search results for "Electronic"
showing 10 items of 17076 documents
Calculation of electronic g-tensors using coupled cluster theory.
2009
A scheme for the calculation of the electronic g-tensor at the coupled cluster (CC) level is presented. The reported implementation employs an effective one-electron spin-orbit operator, allows the inclusion of arbitrary excitations in the cluster operator, and offers various options concerning the treatment of orbital relaxation and choice of reference determinants. In addition, the use of gauge-including atomic orbitals (GIAOs) is possible to overcome the gauge origin problem. Benchmark calculations for the NH ((3)Sigma(-)) radical reveal the importance of electron correlation effects for the accurate prediction of the g-shift as well as the slow basis set convergence of such calculations…
Bond Dissociation Energies for Diatomic Molecules Containing 3d Transition Metals: Benchmark Scalar-Relativistic Coupled-Cluster Calculations for 20 …
2017
Benchmark scalar-relativistic coupled-cluster calculations for dissociation energies of the 20 diatomic molecules containing 3d transition metals in the 3dMLBE20 database ( J. Chem. Theory Comput. 2015 , 11 , 2036 ) are reported. Electron correlation and basis set effects are systematically studied. The agreement between theory and experiment is in general satisfactory. For a subset of 16 molecules, the standard deviation between computational and experimental values is 9 kJ/mol with the maximum deviation being 15 kJ/mol. The discrepancies between theory and experiment remain substantial (more than 20 kJ/mol) for VH, CrH, CoH, and FeH. To explore the source of the latter discrepancies, the …
Gas-Phase Synthesis of the Elusive Trisilicontetrahydride Species (Si3H4)
2016
The bimolecular gas-phase reaction of ground-state atomic silicon (Si; 3P) with disilane (Si2H6; 1A1g) was explored under single-collision conditions in a crossed molecular beam machine at a collision energy of 21 kJ mol–1. Combined with electronic structure calculations, the results suggest the formation of Si3H4 isomer(s) along with molecular hydrogen via indirect scattering dynamics through Si3H6 collision complex(es) and intersystem crossing from the triplet to the singlet surface. The nonadiabatic reaction dynamics can synthesize the energetically accessible singlet Si3H4 isomers in overall exoergic reaction(s) (−93 ± 21 kJ mol–1). All reasonable reaction products are either cyclic or …
Carbonyl compounds of Tc, Re, and Bh: Electronic structure, bonding, and volatility.
2018
Calculations of molecular properties of M(CO)5 and MH(CO)5, where M = Tc, Re, and Bh, and of the products of their decomposition, M(CO)4 and MH(CO)4, were performed using density functional theory and coupled-cluster methods implemented in the relativistic program suits such as ADF, DIRAC, and ReSpect. The calculated first M—CO bond dissociation energies (FBDEs) of Bh(CO)5 and BhH(CO)5 turned out to be significantly weaker than those of the corresponding Re homologs. The reason for that is the relativistic destabilization and expansion of the 6d AOs, responsible for weaker σ-forth and π-back donations in the Bh compounds. The relativistic FBDEs of M(CO)5 have, therefore, a Λ-shape behavior …
Antineutrino monitoring of spent nuclear fuel
2016
Military and civilian applications of nuclear energy have left a significant amount of spent nuclear fuel over the past 70 years. Currently, in many countries world wide, the use of nuclear energy is on the rise. Therefore, the management of highly radioactive nuclear waste is a pressing issue. In this letter, we explore antineutrino detectors as a tool for monitoring and safeguarding nuclear waste material. We compute the flux and spectrum of antineutrinos emitted by spent nuclear fuel elements as a function of time, and we illustrate the usefulness of antineutrino detectors in several benchmark scenarios. In particular, we demonstrate how a measurement of the antineutrino flux can help to…
Comparaison expérimentale de techniques de caractérisation en intensité et phase d'impulsions optiques ultracourtes
2006
Nous comparons experimentalement les resultats de la caracterisation en intensite et en phase d'impulsions optiques ultracourtes obtenus par differentes techniques employant un montage auto/inter-correlateur en intensite et un analyseur de spectre. Nous employons pour ces tests une impulsion en limite de Fourier, une impulsion affectee par l'auto-modulation de phase et une impulsion similariton.
Effective characterization of the phase and intensity profiles of asymmetrically distorted light pulses in optical fiber systems
2009
International audience; We address the problem of characterization of light pulses that propagate in long-haul high-bit-rate optical communication systems under strongly perturbed conditions. We show that the conventional technique for characterization of the phase and intensity profile of such pulses becomes qualitatively inconsistent when the pulse's profile is asymmetrically distorted with respect to its center of mass. We resolve these inconsistencies by partially reformulating the conventional technique by means of appropriate pulse parameters, which we call upgraded parameters, that allow a fair characterization of the intensity and phase of all types of light pulses, including those …
Active components for integrated plasmonic circuits
2009
International audience; We present a comprehensive study of highly efficient and compact passive and active components for integrated plasmonic circuit based on dielectric-loaded surface plasmon polariton waveguides.
Les enjeux de la sécurité des objets connectés et applications de santé
2016
International audience; The challenges of security of connected objects and health applicationsThe market for connected objects and health applications is booming and is expected to be several billion euros in revenue in the coming years. Their development will have a similar impact to what we experienced with the development of internet earlier this century but even more it should disrupt the organization of our health system, profoundly change the management of care and revolutionize prevention, but it could also call into question medical confidentiality and protection of personal data. This article analyses the societal implications of OCS, the need for a dual medical and ethical evalua…
A solvent-directed stereoselective and electrocatalytic synthesis of diisoeugenol.
2018
A stereoselective and electrocatalytic coupling reaction of isoeugenol has been reported for the first time in a 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP)/boron-doped diamond (BDD) electrode system. This particular C-C bond formation and diastereoselectivity is driven by a solvate interaction between the radical species and another isoeugenol molecule. Due to an electrocatalytic cycle, only understoichiometric amounts of charge are necessary. Since electric current is directly employed as the oxidant, the reaction is metal and reagent-free. In addition, the electrolysis can be conducted in a very simple undivided beaker-type cell under constant current conditions. Therefore, the protocol is …