Toward Atomistic Understanding of Materials with the Conversion–Alloying Mechanism in Li-Ion Batteries

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Preparation, characterization, molecular and electronic structures, TDDFT, and TDDFT/PCM study of the solvatochromism in cyanovinylferrocenes

Cis and trans isomers of ferrocene-based donor-acceptor assemblies, Fc-C(I)=CH(I), Fc-C(I)=CH(CN), and Fc-C(CN)=CH(CN) (Fc is ferrocene), along with the Fc-C(CN)=C(CN)_2 complex have been prepared and characterized by ^1H, ^(13)C, gHMQC, and gHMBC NMR spectra, IR, UV-vis, and MCD spectroscopy methods, as well as elemental analyses. The oxidation potentials, investigated by cyclic voltammetry, of all donor-acceptor assemblies are in agreement with the electron-acceptor strength of the substituents attached to the ferrocene core. X-ray crystallography studies of cis and trans isomers of Fc-C(I)=CH(CN) and Fc-C(CN)=CH(CN) reveal a significant rotational flexibility of the cyanovinyl group, which was explained on the basis of semiempirical PM3 calculations. Electronic structures and solvatochromic properties of all complexes were investigated by UV-vis spectroscopy, density functional theory (DFT), time-dependent DFT (TDDFT), and polarized continuum model (PCM) TDDFT approaches. The calculated vertical excitation energies and magnitudes of solvatochromic effect are consistent with the experimental data and clearly suggest the dominance of metal-to-ligand charge-transfer bands in the visible region of the UV-vis spectra for all complexes

Enabling Increased Delithiation Rates in Silicon-Based Anodes through Alloying with Phosphorus

The capability of battery materials to deliver not only high lithium storage capacity, but also the ability to operate at high charge/discharge rates is an essential property for development of new batteries. In the present work, the influence on the charge/discharge rate behaviour of substoichiometric concentrations of phosphorus (P) in silicon (Si) nanoparticles was studied. The results revealed an increase in rate capability as a function of the P concentration between 0 and 5.2 at %, particularly during delithiation. The stoichiometry of the nanoparticles was found to strongly affect the formation of the Li3.5Si phase during lithiation. Cyclic stability experiments demonstrated an initial increase in capacity for the SiPx materials. Galvanostatic intermittent titration technique and electrochemical impedance spectroscopy demonstrated the increased lithium diffusivity with inclusion of P. Density functional theory and ab initio molecular dynamics were deployed to provide a rationale for the electrochemical behaviour of SiPx.publishedVersio

Enabling Increased Delithiation Rates in Silicon-Based Anodes through Alloying with Phosphorus

The capability of battery materials to deliver not only high lithium storage capacity, but also the ability to operate at high charge/discharge rates is an essential property for development of new batteries. In the present work, the influence on the charge/discharge rate behaviour of substoichiometric concentrations of phosphorus (P) in silicon (Si) nanoparticles was studied. The results revealed an increase in rate capability as a function of the P concentration between 0 and 5.2 at %, particularly during delithiation. The stoichiometry of the nanoparticles was found to strongly affect the formation of the Li3.5Si phase during lithiation. Cyclic stability experiments demonstrated an initial increase in capacity for the SiPx materials. Galvanostatic intermittent titration technique and electrochemical impedance spectroscopy demonstrated the increased lithium diffusivity with inclusion of P. Density functional theory and ab initio molecular dynamics were deployed to provide a rationale for the electrochemical behaviour of SiPx.publishedVersio

Mixed-valence states formation in conformationally flexible metal-free 5,10,15,20-tetraferrocenylporphyrin and 5,10-bisferrocenyl-15,20-bisphenylporphyrin

Metal-free 5,10,15,20-tetraferrocenylporphyrin and 5,10-bisferrocenyl-15,20-bisphenylporphyrin have been prepared and characterized by UV-Vis, MCD, ^1H, ^(13)C, and variable-temperature NMR, APCI- and ESI-MS, and Mössbauer spectroscopy, while their redox properties were investigated using electrochemical (cyclic voltammetry and differential pulse voltammetry), spectroelectrochemical, and chemical oxidation approaches. The electronic structure calculations at Density Functional Theory level reveal that both compounds adopt saddle conformations and the HOMOs in both complexes are predominantly metal-centered, while the LUMOs predominantly consist of porphyrin π* orbitals. In spite of the rotational freedom of ferrocenyl substituents at room temperature, both metal-free 5,10,15,20-tetraferrocenylporphyrin and 5,10-bisferrocenyl-15,20-bisphenylporphyrin are able to form mixed-valence states upon the successive ferrocene-based two- and one-electron oxidations, respectively, as confirmed by UV-Vis, MCD, Mössbauer, electro-, and spectroelectrochemical methods, and thus, the earlier suggested (Boyd et al. Chem. Commun., 1999, 637) requirements for the formation of mixed-valence states in ferrocene-containing porphyrins should be revised

Mixed-valence states formation in conformationally flexible metal-free 5,10,15,20-tetraferrocenylporphyrin and 5,10-bisferrocenyl-15,20-bisphenylporphyrin

Metal-free 5,10,15,20-tetraferrocenylporphyrin and 5,10-bisferrocenyl-15,20-bisphenylporphyrin have been prepared and characterized by UV-Vis, MCD, ^1H, ^(13)C, and variable-temperature NMR, APCI- and ESI-MS, and Mössbauer spectroscopy, while their redox properties were investigated using electrochemical (cyclic voltammetry and differential pulse voltammetry), spectroelectrochemical, and chemical oxidation approaches. The electronic structure calculations at Density Functional Theory level reveal that both compounds adopt saddle conformations and the HOMOs in both complexes are predominantly metal-centered, while the LUMOs predominantly consist of porphyrin π* orbitals. In spite of the rotational freedom of ferrocenyl substituents at room temperature, both metal-free 5,10,15,20-tetraferrocenylporphyrin and 5,10-bisferrocenyl-15,20-bisphenylporphyrin are able to form mixed-valence states upon the successive ferrocene-based two- and one-electron oxidations, respectively, as confirmed by UV-Vis, MCD, Mössbauer, electro-, and spectroelectrochemical methods, and thus, the earlier suggested (Boyd et al. Chem. Commun., 1999, 637) requirements for the formation of mixed-valence states in ferrocene-containing porphyrins should be revised

Constraints on decaying Dark Matter from XMM-Newton observations of M31

We derive constraints on parameters of the radiatively decaying Dark Matter (DM) particles, using XMM-Newton EPIC spectra of the Andromeda galaxy (M31). Using the observations of the outer (5'-13') parts of M31 we improve the existing constraints. For the case of sterile neutrino DM, combining our constraints with the latest computation of abundances of sterile neutrino in the Dodelson-Widrow (DW) scenario, we obtain the lower mass limit m_s < 4 keV, which is stronger than the previous one m_s < 6 kev, obtained recently by Asaka et al. (2007) [hep-ph/0612182]. Comparing this limit with the most recent results on Lyman-alpha forest analysis of Viel et al. (2007) [arXiv:0709.0131] (m_s > 5.6 kev), we argue that the scenario in which all the DM is produced via DW mechanism is ruled out. We discuss however other production mechanisms and note that the sterile neutrino remains a viable candidate of Dark Matter, either warm or cold.Comment: 13 pages, 12 figure

Constraining DM properties with SPI

Using the high-resolution spectrometer SPI on board the International Gamma-Ray Astrophysics Laboratory (INTEGRAL), we search for a spectral line produced by a dark matter(DM) particle with a mass in the range 40keV < M_DM < 14MeV, decaying in the DM halo of the Milky Way. To distinguish the DM decay line from numerous instrumental lines found in the SPI background spectrum, we study the dependence of the intensity of the line signal on the offset of the SPI pointing from the direction toward the Galactic Centre. After a critical analysis of the uncertainties of the DM density profile in the inner Galaxy, we find that the intensity of the DM decay line should decrease by at least a factor of 3 when the offset from the Galactic Centre increases from 0 to 180 degrees. We find that such a pronounced variation of the line flux across the sky is not observed for any line, detected with a significance higher than 3 sigma in the SPI background spectrum. Possible DM decay origin is not ruled out only for the unidentified spectral lines, having low (~3 sigma) significance or coinciding in position with the instrumental ones. In the energy interval from 20 keV to 7 MeV, we derive restrictions on the DM decay line flux, implied by the (non-)detection of the DM decay line. For a particular DM candidate, the sterile neutrino of mass MDM, we derive a bound on the mixing angle.Comment: Minor changes; v.2 - Final version appeared in MNRA

A lower bound on the mass of Dark Matter particles

We discuss the bounds on the mass of Dark Matter (DM) particles, coming from the analysis of DM phase-space distribution in dwarf spheroidal galaxies (dSphs). After reviewing the existing approaches, we choose two methods to derive such a bound. The first one depends on the information about the current phase space distribution of DM particles only, while the second one uses both the initial and final distributions. We discuss the recent data on dSphs as well as astronomical uncertainties in relevant parameters. As an application, we present lower bounds on the mass of DM particles, coming from various dSphs, using both methods. The model-independent bound holds for any type of fermionic DM. Stronger, model-dependent bounds are quoted for several DM models (thermal relics, non-resonantly and resonantly produced sterile neutrinos, etc.). The latter bounds rely on the assumption that baryonic feedback cannot significantly increase the maximum of a distribution function of DM particles. For the scenario in which all the DM is made of sterile neutrinos produced via non-resonant mixing with the active neutrinos (NRP) this gives m_nrp > 1.7 keV. Combining these results in their most conservative form with the X-ray bounds of DM decay lines, we conclude that the NRP scenario remains allowed in a very narrow parameter window only. This conclusion is independent of the results of the Lyman-alpha analysis. The DM model in which sterile neutrinos are resonantly produced in the presence of lepton asymmetry remains viable. Within the minimal neutrino extension of the Standard Model (the nuMSM), both mass and the mixing angle of the DM sterile neutrino are bounded from above and below, which suggests the possibility for its experimental search.Comment: 20 pages, published in JCA