text:
\section{Introduction}\label{sec;intro}

Li-rich layered-oxide \ce{Li2MnO3} and related materials have been of great interest for high-capacity lithium-ion battery electrodes.\cite{Thackeray2005JMC,Croguennec2015JACS} The materials are also found to be intriguing for having an unconventional delithiation mechanism involving anionic redox processes, in contrast or in addition to the conventional mechanism involving redox reactions of transition-metal cations. The title compound, also known as Li[Li$_{1/3}$Mn$_{2/3}$]O$_2$, has a layered structure\cite{Massarotti1997} with Li$^+$ and Mn$^{4+}$ ions occupying the octahedral lattice sites formed by alternating layers of oxygen as shown in Fig.~\ref{fig;struct}. Though initially believed to be electrochemically inactive, it was later discovered that \ce{Li2MnO3} can be made active by, for instance, charging to a high voltage.\cite{Kalyani1999} The undoped compound, however, exhibits only a very limited electrochemical capacity.\cite{Sathiya2013}

Recently,\cite{Hoang2015PRA} we showed that the intrinsic delithiation mechanism in \ce{Li2MnO3} involves oxidation at the oxygen lattice site where O$^{2-}$ is oxidized to O$^-$ upon lithium extraction. The localized electron hole states on oxygen\cite{Sathiya2013,Luo2016NC} and the associated local lattice distortion constitute an oxygen hole polaron $\eta_{\rm O}^+$ bound to other defects such as the negatively charged lithium vacancy $V_{\rm Li}^-$ (i.e., the void in the lattice left by the removal of a Li$^{+}$ ion); the species was, therefore, referred to as ``bound oxygen hole polaron'' or ``O$^-$ bound polaron.'' The difficulty in activating \ce{Li2MnO3} and the poor electrochemical performance could be attributed in part to the lack of percolation pathways for efficient $\eta_{\rm O}^+$ transport in the bulk at the onset of delithiation where the lithium vacancy concentration is low. We also argued that the electrochemical performance could be improved via ion substitution according to which partial replacement of, e.g., Mn by electrochemically active ions would introduce additional charge-compensation and electronic conduction mechanisms highly needed at the beginning of delithiation.\cite{Hoang2015PRA}

\begin{figure}
\centering
\includegraphics[width=8.4cm]{fig1}
\vspace{-0.2cm}
\caption{Monoclinic ($C2/m$) structure of Li-rich layered-oxide \ce{Li2MnO3}. Large gray spheres at the $2b$, $2c$, and $4h$ Wyckoff positions are Li, medium blue spheres at the $4g$ Wyckoff position are Mn, and small red spheres are O.}
\label{fig;struct}
\end{figure}

Experimental studies of doping/co-doping in \ce{Li2MnO3} have been carried out by various research groups.\cite{Yu2016JMCA,Xiang2017Ionics,Yuge2017JPS,Luo2016JACS,Tang2017JPCL,Lu2001,Matsunaga2016JPCL,Ma2014CEJ,Mori2011JPS,Sathiya2013} Back in the early 2000s, for example, Lu and Dahn\cite{Lu2001} already considered Li[Li$_{1/3-2x/3}$Mn$_{2/3-x/3}$Ni$_x$]O$_2$, which is a Ni-doped \ce{Li2MnO3} system. Recent investigations of doped \ce{Li2MnO3} materials focused more on understanding the electrochemical activity associated with oxygen redox processes.\cite{Luo2016JACS,Sathiya2013} On the theory side, a number of computational studies have been carried out for \ce{Li2MnO3} doped with various impurities,\cite{Kong2015JMCA,Kong2015JPCC,Lee2015JPS,Gao2014JMCA,Gao2015CM,Yang2017AFM} using density-functional theory (DFT) with the on-site Hubbard correction (DFT$+U$).\cite{Anisimov1997JPCM} Yet, a detailed understanding of the lattice site preference of the dopants in the material under different preparation conditions as well as effects of doping on the electronic structure and hence the delithiation mechanism is still lacking. Besides, DFT$+U$ with $U$ applied only on the transition-metal $d$ states, used in the previous studies,\cite{Gao2014JMCA,Kong2015JMCA,Kong2015JPCC,Gao2015CM,Lee2015JPS,Yang2017AFM,Koyama2009,Xiao2012,Xiao2012JPCC,Marusczyk2017JMCA} cannot capture the intriguing physics of \ce{Li2MnO3} as discussed in Ref.~\citenum{Hoang2015PRA}, suggesting that a more rigorous approach is required.

We herein present a detailed study of \ce{Li2MnO3} doped with representative non-transition-metal (Mg and Al) and transition-metal (Fe, Ni, Mo, and Ru) impurities, using first-principles calculations based on a hybrid DFT/Hartree-Fock approach in which all electronic states in the materials are treated on equal footing. We start with defect calculations which mainly consider the impurities in the dilute doping limit where the lattice site preference and charge and spin states of the dopants as well as charge-compensation mechanisms in the materials are determined. We then develop structural models to investigate heavily doped \ce{Li2MnO3} systems where the focus is on the electronic structure and the interplay with the delithiation mechanism. Finally, we present voltage profiles calculated for the doped compounds and discuss the role of doping in \ce{Li2MnO3}-based cathode materials.

\section{Methodology}\label{sec;method}

The calculations are based on DFT, using the Heyd-Scuseria-Ernzerhof (HSE06) functional,\cite{heyd:8207} the projector augmented wave method,\cite{PAW1} and a plane-wave basis set, as implemented in the Vienna {\it Ab Initio} Simulation Package (\textsc{vasp}).\cite{VASP2} The Hartree-Fock mixing parameter ($\alpha$) and the screening length are set to the standard values of 25\% and 10 {\AA}, respectively. It was previously shown that, with these parameters, HSE06 gives the \ce{O2} molecule a binding energy of 5.16 eV, in excellent agreement with experiments (5.12 eV).\cite{Hoang2014JMCA} The ferromagnetic spin configuration is assumed for the transition-metal sublattice in \ce{Li2MnO3} as it was found that the ferromagnetic and antiferromagnetic configurations are almost degenerate in energy.\cite{Hoang2015PRA} The plane-wave basis-set cutoff is set to 500 eV and spin polarization is included. Convergence with respect to self-consistent iterations is assumed when the total energy difference between cycles is less than $10^{-4}$ eV and the residual forces are less than $0.01$ eV/{\AA}.

\begin{figure}
\centering
\includegraphics[width=8.4cm]{fig2}
\vspace{-0.2cm}
\caption{Chemical-potential diagram for \ce{Li2MnO3}, constructed using data from Ref.~\citenum{Hoang2015PRA}. Only Li$-$Mn$-$O phases that define the stability region, shown as a shaded polygon, are indicated. The dotted blue lines correspond to the $\mu_{\rm O}$ levels associated oxygen in air at 500 $^\circ$C and 950 $^\circ$C. Actual synthesis conditions are expected to be in the shaded region enclosed approximately by points $L$, $H$, $H'$, and $D$.}
\label{fig;chempot}
\end{figure}

The impurities in \ce{Li2MnO3} in the dilute doping limit are modeled using 108-atom hexagonal supercells;\cite{Hoang2015PRA} integrations over the supercell Brillouin zone are carried out using the $\Gamma$ point. In these defect calculations, the lattice parameters are fixed to the calculated bulk values but all the internal coordinates are fully relaxed. The formation energy of an intrinsic defect, impurity (dopant), or defect complex X (hereafter often referred commonly to as ``defect'') in charge state $q$ is defined as
\begin{equation}\label{eq;eform}
E^f({\mathrm{X}}^q)=E_{\mathrm{tot}}({\mathrm{X}}^q)-E_{\mathrm{tot}}({\mathrm{bulk}})-\sum_{i}{n_i\mu_i}+q(E_{\mathrm{v}}+\mu_{e})+ \Delta^q ,
\end{equation}
where $E_{\mathrm{tot}}(\mathrm{X}^{q})$ and $E_{\mathrm{tot}}(\mathrm{bulk})$ are, respectively, the total energies of a supercell containing the defect and that of the perfect bulk material. $\mu_{i}$ is the atomic chemical potential of species $i$ (and is referenced to bulk metals or O$_{2}$ molecules at 0 K). $n_{i}$ is the number of atoms of species $i$ that have been added ($n_{i}>$0) or removed ($n_{i}<$0) to form the defect. $\mu_{e}$ is the electronic chemical potential, i.e., the Fermi level, that is, as a convention, referenced to the valence-band maximum (VBM) in the bulk ($E_{\mathrm{v}}$). $\Delta^q$ is the correction term to align the electrostatic potentials of the bulk and defect supercells and to account for finite-size effects on the total energies of charged defects.\cite{Freysoldt2009} In the calculation of $\Delta^q$, a total static dielectric constant of 17.69, previously calculated for \ce{Li2MnO3},\cite{Hoang2015PRA} is used.

Under thermal equilibrium, the concentration of a defect is related to its formation energy:\cite{walle:3851}
\begin{equation}\label{eq;con}
c=N_{\mathrm{sites}}N_{\mathrm{config}}\mathrm{exp}\left(\frac{-E^{f}}{k_{B}T}\right),
\end{equation}
where $N_{\mathrm{sites}}$ is the number of high-symmetry sites in the lattice per unit volume on which the defect can be incorporated, $N_{\mathrm{config}}$ is the number of equivalent configurations (per site), and $k_{B}$ is Boltzmann's constant. Equation (\ref{eq;con}) indicates that $c$ is higher at higher temperatures and/or when the defect has a lower formation energy.

The atomic chemical potentials of Li, Mn, and O in \ce{Li2MnO3} are not arbitrary but subject to thermodynamic constraints which can be used to represent actual experimental conditions, e.g., during materials preparation. Figure~\ref{fig;chempot} shows the chemical-potential diagram for \ce{Li2MnO3}, produced with data from Ref.~\citenum{Hoang2015PRA}. The region in which the compound is thermodynamically stable is determined by considering equilibria with other Li$-$Mn$-$O phases.\cite{Hoang2015PRA} In principle, $\mu_{\rm Li}$, $\mu_{\rm Mn}$, and $\mu_{\rm O}$ can take any values within the stability region in which
\begin{equation}\label{eq;li2mno3}
2\mu_{\rm Li}+\mu_{\rm Mn}+3\mu_{\rm O}=\Delta H^{f}({\rm Li}_{2}{\rm Mn}{\rm O}_{3}),
\end{equation}
where $\Delta H^{f}$ is the formation enthalpy (previously calculated to be $-12.30$ eV per formula unit,\cite{Hoang2015PRA} in good agreement with the experimental value $12.78\pm 0.05$ eV\cite{Cupid2016JCSJ} reported more recently). More realistic $\mu_i$ values, however, can be identified by taking into account actual experimental conditions. For example, \ce{Li2MnO3} is often prepared by solid-state reaction in the temperature range from 500$^\circ$C to 950$^\circ$C.\cite{Massarotti1997,Kalyani1999,Robertson2002,Kubota2012} The synthesis conditions can thus be identified with the shaded region between the two dotted lines in Fig.~\ref{fig;chempot} which corresponds to the range of the oxygen chemical potential $\mu_{\rm O} = -0.87$ eV (e.g., at point $L$) to $-1.47$ eV (points $H$ and $H'$).\cite{Hoang2015PRA} This region is enclosed approximately by points $L$, $H$, $H'$, and $D$. Note that $\mu_{\rm O}$ is related to temperature and the oxygen partial pressure; it is lower at higher temperatures and/or lower oxygen partial pressures and/or in the presence of oxygen-reducing agents.\cite{Hoang2015PRA} In Fig.~\ref{fig;chempot}, $\mu_{\rm O}=0$ eV along the \ce{O2} line (which also corresponds to $T=0$ K).

For the impurities in \ce{Li2MnO3}, their chemical potential values are between minus infinity and zero (with respect to the total energy per atom of the bulk metals). More realistic values can be estimated based on solubility-limiting phases that may be formed between the impurities and the constituting elements of the host compound.\cite{walle:3851} In the following, the chemical potentials of Mg, Al, Fe, Ni, Mo, and Ru impurities are set as $\mu_{\rm Mg} = -7.0$ eV, $\mu_{\rm Al} = -9.0$ eV, $\mu_{\rm Fe} = -5.0$ eV, $\mu_{\rm Ni} = -4.0$ eV, $\mu_{\rm Mo} = -7.0$ eV, and $\mu_{\rm Ru} = -5.0$ eV. These chemical potential values are chosen somewhat arbitrarily; however, the choice does not affect the physics of what we are presenting as we are interested only in the relative formation energies of the impurities.

Heavy doping of \ce{Li2MnO3} with Ni, Mo, or Ru is simulated using smaller, monoclinic cells containing 24 atoms. Starting with the conventional unit cell of undoped \ce{Li2MnO3} as shown in Fig.~\ref{fig;struct}, Mn-site doping corresponds to replacing one of the Mn atoms at the $4g$ lattice site with the dopant. As for Li-site doping, the dopant replaces one of the Li atoms either at the $2b$, $2c$, or $4h$ lattice site. Simultaneous doping at the Li site and the Mn site is also considered. Voltage profiles are calculated using the 24-atom cell size and the expression for the deintercalation voltage derived previously,\cite{Aydinol1997,Hoang2015PRA} assuming topotactic transitions between compositions with different lithium concentrations. In these calculations, integrations over the Brillouin zone are carried out using a $\Gamma$-centered $3\times 2 \times 3$ $k$-point mesh; $6\times 3 \times 6$ or denser $k$-point meshes are used in calculations to obtain high-quality electronic densities of states. Additional calculations make use of monoclinic supercells containing 48 atoms. Note that, unlike in the dilute doping case, the cell volume and shape and internal coordinates are all relaxed in the calculations for heavily doped \ce{Li2MnO3}.

Finally, we note that calculations of bulk \ce{Li2MnO3} using the HSE06 functional but with a smaller Hartree-Fock mixing parameter, e.g., $\alpha=17\%$, have also been reported in the literature.\cite{Seo2016NC} In our calculations, we find both the standard $\alpha$ value and $\alpha =17\%$ give Li$_{2-x}$MnO$_3$ ($0\leq x\leq2$) similar electronic structures, especially the nature of the electronic states near the band edges; the difference is mainly in the calculated band gaps, see Ref.~\citenum{SM}. The results also indicate that \ce{Li2MnO3} remains non-mettalic upon lithium extraction.\cite{SM} Also note that previous calculations using DFT$+U$ with the $U$ term applied only on the Mn $3d$ orbitals show that \ce{Li2MnO3} becomes a metal upon lithium extraction,\cite{Koyama2009,Xiao2012,Xiao2012JPCC,Yang2017AFM,Marusczyk2017JMCA} which is in contrast to the results obtained using the HSE06 functional\cite{Hoang2015PRA,Chen2016CM,SM} or DFT$+U$ with the on-site Hubbard corrections applied on both the Mn $3d$ and O $2p$ states\cite{Hoang2015PRA} according to which the material remains non-metallic. Experiments should, therefore, be carried out to determine the nature of bulk electronic conduction in partially delithiated Li$_{2-x}$MnO$_3$ (especially in the nearly fully lithiated regime, i.e., $x\ll 1$); the results may also be able to validate one computational method over another.

\section{Results and Discussion}\label{results}

\subsection{Lattice site preference and charge and spin states in the dilute doping limit}\label{sec;dilute}

\begin{figure}
\centering
\includegraphics[width=8.6cm]{fig3}
\vspace{-0.2cm}
\caption{Formation energies of substitutional impurities at the Li site or the Mn site in \ce{Li2MnO3} obtained at point $H$ in the chemical-potential diagram (Fig.~\ref{fig;chempot}) and plotted as a function of Fermi level from the VBM to the conduction-band minimum (CBM): (a) Mg, (b) Al, (c) Fe, (d) Ni, (e) Mo, and (f) Ru. The slope in the energy plots indicates charge state $q$: Positively (negatively) charged defects have positive (negative) slopes. For each defect, only true charge states are indicated. The vertical dotted line marks the Fermi level of undoped \ce{Li2MnO3}, $\mu_{e}^{\rm{int}}$, determined by the intrinsic defects.\cite{Hoang2015PRA}}
\label{fig;fe}
\end{figure}

Figure~\ref{fig;fe} shows the formation energies of Mg, Al, Fe, Ni, Mo, and Ru incorporated into \ce{Li2MnO3} at the Li site or the Mn site, obtained under the conditions at point $H$ in the chemical-potential diagram. Calculations are carried out for the impurities at all three inequivalent Li lattice sites, however, only the lowest-energy configuration is reported. Among possible values of $q$, true charge states are indicated in the figure and their corresponding defect configurations are called elementary defects; the other (nominal) charge states correspond to complexes consisting of the elementary defects and electron polaron(s) $\eta^-$ or electron-hole-related species. As reported in Ref.~\citenum{Hoang2015PRA}, Mn in undoped \ce{Li2MnO3} is stable as Mn$^{4+}$ and $\eta^-$ is the localized electron and local lattice distortion associated with the high-spin Mn$^{3+}$ ion at the Mn site; the hole-related species can be oxygen hole polaron $\eta_{\rm O}^+$ (i.e., a hole localized on an O ion or, equivalently, O$^-$) or, occasionally, $\eta_{\rm O\ast}^+$ (a hole delocalized over two O ions), depending on specific defect complexes and their effective charge states. $\eta_{\rm O}^+$ is a bound polaron; i.e., it is stable only in the presence of a negatively charged defect such as lithium vacancy $V_{\rm Li}^-$.\cite{Hoang2015PRA} Mg$_{\rm Li}^0$, for example, is a complex of Mg$_{\rm Li}^+$ (i.e., Mg$^{2+}$ at the Li site) and $\eta^-$; Mg$_{\rm Mn}^-$ is a complex of Mg$_{\rm Mn}^{2-}$ (i.e., Mg$^{2+}$ at the Mn site) and $\eta_{\rm O}^+$; see Fig.~\ref{fig;fe}(a). $\eta_{\rm O\ast}^+$ is found to be present only in Al$_{\rm Mn}^0$, a complex of Al$_{\rm Mn}^-$ (i.e., Al$^{3+}$ at the Mn site) and $\eta_{\rm O\ast}^+$, and in Al$_{\rm Mn}^+$, a complex of Al$_{\rm Mn}^-$, $\eta_{\rm O}^+$, and $\eta_{\rm O\ast}^+$.

\begin{figure}
\centering
\includegraphics[width=8.6cm]{fig4}
\vspace{-0.2cm}
\caption{Difference between the formation energy at the Li site and that at the Mn site, obtained under the conditions at different points in the chemical-potential diagram (Fig.~\ref{fig;chempot}). $\Delta E > 0$ means the impurity is energetically more favorable at the Mn lattice site. Points $L$, $H$, $H'$, and $D$ can be regarded as being close to actual conditions during materials preparation.}
\label{fig;fe;diff}
\end{figure}

The lattice site preference is determined by examining the formation energy of the energetically most stable configuration of the impurities at the Li site and that at the Mn site.\cite{Hoang2012JPS,Hoang2017PRMoxides} For a given set of the atomic chemical potentials, which corresponds to a point in the chemical-potential diagram, the energies are obtained at the Fermi level of undoped \ce{Li2MnO3} ($\mu_{e}^{\rm{int}}$, indicated by the vertical dotted line in Fig.~\ref{fig;fe}), determined by intrinsic defects.\cite{Hoang2015PRA} Figure~\ref{fig;fe} indicates that, under the conditions at point $H$, e.g., Mg is energetically most stable as Mg$_{\rm Li}^+$; Al as Al$_{\rm Mn}^-$; Fe as Fe$_{\rm Mn}^-$ (high-spin Fe$^{3+}$ at the Mn site); Ni as Ni$_{\rm Li}^+$ (Ni$^{2+}$ at the Li site); Mo as Mo$_{\rm Mn}^+$ (Mo$^{5+}$ at the Mn site); and Ru as Ru$_{\rm Mn}^0$ (low-spin Ru$^{4+}$ at the Mn site).

We note that the energies of Mg$_{\rm Li}^+$, as an isolated defect, at the $2c$ site and the $4h$ site are degenerate and lower than the energy at the $2b$ site by 0.04 eV. Isolated Ni$_{\rm Li}^+$, on the other hand, has the lowest energy at the $2b$ lattice site; the energy at the $2c$ site or the $4h$ site is higher by 0.08 eV. These energy differences are independent of the choice of atomic chemical potentials.

Figure~\ref{fig;fe;diff} shows the formation-energy difference, $\Delta E$, between the Li site and the Mn site under the conditions at different points in the chemical-potential diagram. $\Delta E$ is defined as the difference between the formation energy (at $\mu_{e}^{\rm{int}}$) of the lowest-energy defect configuration at the Li site and that at the Mn site.\cite{Hoang2017PRMoxides} $\Delta E > 0$ means the impurity is energetically more favorable at the Mn site than at the Li site; for $\Delta E \sim 0$, one should expect that the impurity can be incorporated simultaneously at both the lattice sites with almost equal concentrations. The results show that the lattice site preference of the impurities can be dependent on the relative abundance of the host constituents during synthesis, expressed in terms of the atomic chemical potentials in our computational approach. Focusing on the conditions at points $L$, $H$, $H'$, and $D$, we find that Al, Fe, Mo, and Ru would be incorporated into \ce{Li2MnO3} at the Mn site, whereas Mg would be at the Li site. These results are thus in agreement with the corresponding doped \ce{Li2MnO3} compositions observed in experiments.\cite{Yu2016JMCA,Xiang2017Ionics,Yuge2017JPS,Ma2014CEJ,Mori2011JPS} Yu et al.,\cite{Yu2016JMCA} for example, reported that Mg occupies the Li ($4h$) site in \ce{Li2MnO3}, which is consistent with the results for Mg. We note that, though Mg$_{\rm Li}^+$ has the same energy at the $4h$ site and the $2c$ site as mentioned above, its concentration at $4h$ is higher than that at $2c$ because the number of the $4h$ sites in the supercell is twice that of the $2c$ sites.

Interestingly, under the conditions at points $H$, $H'$, and $D$, Ni is energetically most favorable when incorporated at the Li ($2b$) site, whereas, at point $L$, the impurity is more favorable at the Mn ($4g$) site and stable as Ni$_{\rm Mn}^-$ (low-spin Ni$^{3+}$ at the Mn site), when considered as an isolated defect. Our results thus indicate that the lattice site preference and hence the ratio between the concentration of Ni$_{\rm Li}$ and that of Ni$_{\rm Mn}$ are dependent on the preparation conditions: a higher Ni$_{\rm Li}$/Ni$_{\rm Mn}$ ratio, for example, can be obtained at higher synthesis temperatures (i.e., lower $\mu_{\rm O}$ values). It is important to keep in mind that, in addition to affecting the formation energy through the chemical potential terms in Eq.~(\ref{eq;eform}), the synthesis temperature also strongly affects the defect concentration via $k_{B}T$ in the exponential in Eq.~(\ref{eq;con}).

The results for Ni are consistent with experiments reported by Matsunaga et al.\cite{Matsunaga2016JPCL} in which Ni was found to be incorporated mainly at the $2b$ site in Li$_2$(Ni$_z$Mn$_{1-z}$)O$_3$ samples annealed at 900 $^\circ$C in air (see Table 1 of Ref.~\citenum{Matsunaga2016JPCL}), though it is quite surprising that no Li was found in the Li layers,\cite{Matsunaga2016JPCL} given that Ni$_{\rm Li}^+$ has a relatively small energy difference between the $2b$ site and the $4h$ ($2c$) site. The reason could be kinetically related and/or due to defect-defect interaction. We note that the experimental conditions used in Ref.~\citenum{Matsunaga2016JPCL} can be regarded as being close to those associated with the $H-H'$ segment in Fig.~\ref{fig;chempot}.

Let us now briefly compare some of the above results for \ce{Li2MnO3} with those for the same impurities but in layered \ce{LiMO2} (M = Co, Ni, Mn) reported recently.\cite{Hoang2017PRMoxides} It was found that Al and Fe impurities in \ce{LiMO2} are most favorable at the M site, under realistic conditions, similar to the results for Al and Fe in \ce{Li2MnO3}. Regarding Mg, it can be incorporated into \ce{LiMO2} (M = Co, Ni) at the M site or both the M and Li sites; in \ce{LiMnO2}, Mg can be incorporated at the Mn or Li site or both the lattice sites.\cite{Hoang2017PRMoxides} The results are thus different from those for \ce{Li2MnO3} which show that Mg is always more favorable energetically at the Li site; see Fig.~\ref{fig;fe;diff}. As for Ni, the impurity can be incorporated into \ce{LiCoO2} at the Co site and \ce{LiMnO2} at the Mn site or both the Mn and Li sites.\cite{Hoang2017PRMoxides} In \ce{Li2MnO3}, on the other hand, Ni can be incorporated at the Mn site or the Li site or both the lattice sites, as reported earlier. All these results suggest that, in materials such as $z$\ce{Li2MnO3}$\cdot$($1-z$)\ce{LiMO2} composites, the lattice site preference of a dopant may not be the same in \ce{LiMO2}-rich vs. \ce{Li2MnO3}-rich regions.

\begin{table}
\caption{\ Defect models for the impurities in the dilute doping limit, obtained under the conditions at points $L$, $H$, $H'$, and $D$ in the chemical-potential diagram. Only the most stable configurations are reported; other configurations that are close in energy are listed in the footnotes. It is noted that defect-defect interaction may change the relative stability of the complexes and the charge and spin states of the transition-metal impurities; see the text for further discussions.}\label{tab;models}
\begin{center}
\begin{ruledtabular}
\begin{tabular}{lcccc}
&$L$&$H$&$H'$&$D$ \\
\hline
Mg&Mg$_{\rm Li}^+$$-$$\eta^-$&Mg$_{\rm Li}^+$$-$$\eta^-$&Mg$_{\rm Li}^+$$-$$\eta^-$&Mg$_{\rm Li}^+$$-$$V_{\rm Li}^-$$^a$ \\
Al&Al$_{\rm Mn}^-$$-$Li$_i^+$&Al$_{\rm Mn}^-$$-$Li$_i^+$&Al$_{\rm Mn}^-$$-$Mn$_{\rm Li}^+$&Al$_{\rm Mn}^-$$-$Mn$_{\rm Li}^+$ \\
Fe&Fe$_{\rm Mn}^0$&Fe$_{\rm Mn}^0$$^b$&Fe$_{\rm Mn}^-$$-$Mn$_{\rm Li}^+$&Fe$_{\rm Mn}^-$$-$Mn$_{\rm Li}^+$ \\
Ni&Ni$_{\rm Mn}^0$&Ni$_{\rm Li}^+$$-$$\eta^-$&Ni$_{\rm Li}^+$$-$$\eta^-$&Ni$_{\rm Li}^+$$-$$\eta^-$$^c$ \\
Mo&Mo$_{\rm Mn}^0$&Mo$_{\rm Mn}^0$&Mo$_{\rm Mn}^0$&Mo$_{\rm Mn}^+$$-$$V_{\rm Li}^-$$^d$ \\
Ru&Ru$_{\rm Mn}^0$&Ru$_{\rm Mn}^0$&Ru$_{\rm Mn}^0$&Ru$_{\rm Mn}^0$ \\
\end{tabular}
\end{ruledtabular}
\end{center}
\begin{flushleft}
$^a$Mg$_{\rm Li}^+$$-$$\eta^-$ ($+0.00$ eV). $^b$Fe$_{\rm Mn}^-$$-$Li$_i^+$ ($+0.10$ eV). $^c$Ni$_{\rm Li}^+$$-$$V_{\rm Li}^-$ ($+0.16$ eV). $^d$Mo$_{\rm Mn}^0$ ($+0.02$ eV).
\end{flushleft}
\end{table}

Since many of the stable configurations for the impurities in \ce{Li2MnO3} are positively or negatively charged, charge compensation is needed when they occur in the material, which can be provided by intrinsic point defects or by having the transition-metal impurity ion change its charge state. Explicit calculations for possible low-energy defect complexes between the charged impurities and intrinsic defects based on the results for the latter reported in Ref.~\citenum{Hoang2015PRA} are carried out. Table \ref{tab;models} summarizes the results obtained under the conditions at points $L$, $H$, $H'$, and $D$ in the chemical-potential diagram. We find that Mg$_{\rm Li}^+$ can occur in the form of Mg$_{\rm Li}^+$$-$$\eta^-$; i.e., the incorporation of Mg at the Li site is charge-compensated by the formation of $\eta^-$ (i.e., Mn$^{3+}$) in the host. The complex has a binding energy $E_b = 0.44$ eV with respect to its isolated constituents. At point $D$, this complex becomes degenerate in energy with Mg$_{\rm Li}^+$$-$$V_{\rm Li}^-$ ($E_b = 0.37$ eV). Al$_{\rm Mn}^-$ is most stable in the form of Al$_{\rm Mn}^-$$-$Li$_i^+$ ($E_b = 0.31$ eV) at points $L$ and $H$, where Li$_i^+$ corresponds to an interstitial Li$^+$ ion in the Li layer,\cite{Hoang2015PRA} or Al$_{\rm Mn}^-$$-$Mn$_{\rm Li}^+$ ($E_b = 0.39$ eV) at points $H'$ and $D$, where Mn$_{\rm Li}^+$ corresponds to Mn$^{2+}$ in the Li layer. Fe$_{\rm Mn}^-$, as isolated defect, can occur in the form of Fe$_{\rm Mn}^0$ (i.e., Fe$^{4+}$ at the Mn site); in this case, Fe changes its charge state from $+3$ to $+4$ to maintain charge neutrality. In the presence of other positively charged impurities, however, such as in Li$_{1.23}$Fe$_{0.15}$Ni$_{0.15}$Mn$_{0.46}$O$_2$,\cite{Yuge2017JPS} where Ni is likely stable as Ni$_{\rm Li}^+$, Fe remains as Fe$_{\rm Mn}^-$.

As for the other impurities, Ni$_{\rm Mn}^+$, as an isolated defect, can occur in the form of Ni$_{\rm Mn}^0$ (i.e., Ni$^{4+}$ at the Mn site) at point $L$; Ni$_{\rm Li}^+$ as Ni$_{\rm Li}^+$$-$$\eta^-$ ($E_b = 0.55$ eV) at points $H$, $H'$, and $D$. We note that, if both Ni$_{\rm Li}$ and Ni$_{\rm Mn}$ occur in the material, the charge-compensation mechanism will be different (see more details below). Mo$_{\rm Mn}^+$ is found to occur in the form of Mo$_{\rm Mn}^0$ (i.e., Mo$^{4+}$ at the Mn site); however, Mo$_{\rm Mn}^0$ is stable only in isolation as this defect configuration becomes unstable toward forming a complex of Mo$_{\rm Mn}^+$ and $\eta^-$ when there is more than one Mo impurity in the supercell (As will be discussed in Sec.~\ref{sec;heavy}, in heavily doped \ce{Li2MnO3}, Mo is also stable as Mo$^{5+}$ and the corresponding defect Mo$_{\rm Mn}^+$ is charge-compensated by $\eta^-$). Under the conditions at point $D$, Mo$_{\rm Mn}^0$ and Mo$_{\rm Mn}^+$$-$$V_{\rm Li}^-$ ($E_b = 0.48$ eV) are degenerate in energy; see Table \ref{tab;models}. Experimentally, Mo was reported to be stable as Mo$^{5+}$.\cite{Ma2014CEJ} Finally, Ru is stable as Ru$_{\rm Mn}^0$ as mentioned earlier, consistent with experiments.\cite{Mori2011JPS,Sathiya2013}

We also carry out explicit calculations for Ni-doped \ce{Li2MnO3} with Ni at both the Li site and the Mn site, using two different models. The first model for the doped system involves one Ni atom at the Li ($2b$) site and one at the Mn ($4g$) site. In this case, the impurities can be described as consisting of Ni$_{\rm Li}^+$ and Ni$_{\rm Mn}^-$. The Ni ion at the Mn site thus adopts the charge state $+3$ and becomes the charge-compensating defect for the Ni$^{2+}$ ion at the Li site. In the second model, two Ni atoms are incorporated at the $2b$ site and one at the $4g$ site. In this case, the impurities are found to occur as a complex of two Ni$_{\rm Li}^+$ and one Ni$_{\rm Mn}^{2-}$; i.e., all the Ni ions are in the $+2$ charge state. The Ni ion at the Mn site thus lowers its charge state further in the presence of the additional Ni$_{\rm Li}^+$ defect. The observations here indicate that charge (and spin) states of a transition-metal impurity can be affected by defect-defect interaction, as also seen in the case of Fe$_{\rm Mn}$ and Mo$_{\rm Mn}$. These results are consistent with those reported in Fig.~\ref{fig;fe}(d), in which all three charge states (+2, +3, and +4) of Ni are found to be stable. We note that the second model can be employed to describe the series of Ni-doped \ce{Li2MnO3} cathode materials Li[Ni$_z$Li$_{1/3-2z/3}$Mn$_{2/3-z/3}$]O$_2$ ($0 \leq z \leq 1/2$), synthesized first by Lu and Dahn\cite{Lu2001} and widely studied and reported in the literature. In our calculations, $z=1/9$, $1/4$, and $1/2$, corresponding to three Ni atoms in the 108-, 48-, and 24-atom cell models, respectively.

\subsection{Electronic structure vis-\`{a}-vis delithiation mechanism in heavy doping}\label{sec;heavy}

Given the lattice site preference and the stable charge and spin states of the impurities reported in the previous section, we can now develop suitable models to describe heavily doped \ce{Li2MnO3} systems and investigate their electronic structure as well as delithiation mechanism. Here, we focus on the Ni, Mo, and Ru impurities, as they are often selected for ion substitution, and make use of the smaller, 24-atom cell size. Since Ni can be incorporated into \ce{Li2MnO3} at the Li site and/or the Mn site, we consider cell models with the following compositions: (i) Li$_{1.75}$Ni$_{0.25}$MnO$_3$ with Ni at the $2b$, $2c$, or $4h$ site, (ii) Li$_2$Mn$_{0.75}$Ni$_{0.25}$O$_3$ with Ni at the $4g$ site, and (iii) Li$_{1.5}$Ni$_{0.75}$Mn$_{0.75}$O$_3$ with two Ni at the $2b$ site and one at the $4g$ site per cell. Model (iii) can also be expressed as Li[Ni$_z$Li$_{1/3-2z/3}$Mn$_{2/3-z/3}$]O$_2$ with $z=1/2$ or LiNi$_{0.5}$Mn$_{0.5}$O$_2$ as often mentioned in the literature. For Ru and Mo, which are found to be incorporated at the $4g$ site, we consider the following compositions: (iv) Li$_2$Mn$_{0.75}$Mo$_{0.25}$O$_3$ and (v) Li$_2$Mn$_{0.75}$Ru$_{0.25}$O$_3$.

\begin{figure}
\centering
\includegraphics[width=8.6cm]{fig5}
\vspace{-0.2cm}
\caption{Total and atomic-projected electronic densities of states of (a) undoped \ce{Li2MnO3} and \ce{Li2MnO3} doped with Ni at the (b) $2b$, (c) $2c$, (d) $4g$, or (e) both $2b$ and $4g$ lattice sites. The zero of energy is set to the highest occupied state.}
\label{fig;dos1}
\end{figure}

\begin{figure}
\centering
\includegraphics[width=8.6cm]{fig6}
\vspace{-0.2cm}
\caption{Total and atomic-projected electronic densities of states of Li$_{1.75-x}$Ni$_{0.25}$MnO$_3$ (Ni at the $2b$ site): (a) $x=0.00$, (b) $x=0.25$, (c) $x=0.50$, (d) $x=0.75$, and (e) $x=1.00$. The zero of energy is set to the highest occupied state.}
\label{fig;dos2}
\end{figure}

Figure \ref{fig;dos1} shows the total and atomic-projected electronic density of states (DOS) of undoped and Ni-doped \ce{Li2MnO3}. The electronic structure of the Ni-doped system with Ni at the $4h$ site is very similar to that at the $2c$ site and thus not included in the figure. We find that Ni is stable as Ni$^{2+}$ at the Li site (either $2b$, $2c$, or $4h$) and charge-compensated by Mn$^{3+}$ formed at the Mn site (i.e., $\eta^-$), in agreement with the results obtained in the dilute doping limit. On the other hand, Ni is stable as Ni$^{4+}$ at the $4g$ site and all Ni in Li$_{1.5}$Ni$_{0.75}$Mn$_{0.75}$O$_3$ are stable as Ni$^{2+}$ at the $2b$ and $4g$ sites as reported earlier; $\eta^-$ is not found in these two cases. The electronic structure, particularly near the band edges, is strongly dependent on the lattice site of the dopant. We are mostly interested in the nature of the electronic structure near the VBM as it provides information on the mechanism for lithium extraction.\cite{Hoang2011CM,Hoang2015PRA} The results show that the VBM of Li$_{1.75}$Ni$_{0.25}$MnO$_3$ is composed predominantly of the $3d$ states from the Mn$^{3+}$ ion; see Fig.~\ref{fig;dos1}(b) and \ref{fig;dos1}(c). In Li$_2$Mn$_{0.75}$Ni$_{0.25}$O$_3$, the VBM is predominantly the O $2p$ states, see Fig.~\ref{fig;dos1}(d), similar to that in undoped \ce{Li2MnO3} [Fig.~\ref{fig;dos1}(a)]. This is because when doped at the $4g$ site only, Ni is stable as Ni$^{4+}$ and the Ni $3d$ states are in the conduction band. Finally, in Li$_{1.5}$Ni$_{0.75}$Mn$_{0.75}$O$_3$, the VBM is predominantly the $3d$ states from the Ni$^{2+}$ ions; see Fig.~\ref{fig;dos1}(e). Note that, though the atomic-decomposed DOS in the figures shows the total contribution from the materials' constituting elements, our analysis is based on contributions from individual atoms which contain more details on the nature of the electronic structure.

The features observed in the electronic structure of the Ni-doped \ce{Li2MnO3} systems will result in different delithiation mechanisms. As Li in the material already donates its electron to the lattice and becomes Li$^+$, lithium extraction involves removing the Li$^{+}$ ion and one electron from the lattice (specifically, from the highest occupied state).\cite{Hoang2011CM,Hoang2015PRA} The electronic structures in Fig.~\ref{fig;dos1} indicate that, upon delithiation, Mn$^{3+}$ in Li$_{1.75}$Ni$_{0.25}$MnO$_3$ will be the first to be oxidized; Li$_2$Mn$_{0.75}$Ni$_{0.25}$O$_3$ will have the same delithiation mechanism as undoped \ce{Li2MnO3} which was found to involve the oxidation of O$^{2-}$ to O$^-$;\cite{Hoang2015PRA} and the oxidation will occur first with Ni$^{2+}$ in Li$_{1.5}$Ni$_{0.75}$Mn$_{0.75}$O$_3$. The mechanism for subsequent stages of delithiation will be determined by the electronic structure of the partially delithiated compounds.

\begin{figure}
\centering
\includegraphics[width=8.6cm]{fig7}
\vspace{-0.2cm}
\caption{Total and atomic-projected electronic densities of states of Li$_{2-x}$Mn$_{0.75}$Mo$_{0.25}$O$_3$ (Mo at the $4g$ site): (a) $x=0.00$, (b) $x=0.25$, (c) $x=0.50$, (d) $x=0.75$, and (e) $x=1.00$. The zero of energy is set to the highest occupied state.}
\label{fig;dos3}
\end{figure}

\begin{figure}
\centering
\includegraphics[width=8.6cm]{fig8}
\vspace{-0.2cm}
\caption{Total and atomic-projected electronic densities of states of Li$_{2-x}$Mn$_{0.75}$Ru$_{0.25}$O$_3$ (Ru at the $4g$ site): (a) $x=0.00$, (b) $x=0.25$, (c) $x=0.50$, (d) $x=0.75$, and (e) $x=1.00$. The zero of energy is set to the highest occupied state.}
\label{fig;dos4}
\end{figure}

In order to demonstrate how the electronic structure of a Ni-doped \ce{Li2MnO3} material changes upon delithiation, we show in Fig.~\ref{fig;dos2} the DOS of Li$_{1.75-x}$Ni$_{0.25}$MnO$_3$ (with the dopant at the $2b$ site only) for different degrees of delithiation. At $x=0$, the valence-band top is predominantly the $3d$ states from the Mn$^{3+}$ ion; see Fig.~\ref{fig;dos2}(a). Once an electron is removed from Mn$^{3+}$ and the ion is oxidized to Mn$^{4+}$, at $x=0.25$, the Mn $3d$ states are empty and pushed to the conduction band; the valence-band top is now predominantly the $3d$ states from the Ni$^{2+}$ ion; see Fig.~\ref{fig;dos2}(b). Next, an electron is removed from the Ni$^{2+}$ $3d$ states and the ion is oxidized to Ni$^{3+}$; see Fig.~\ref{fig;dos2}(c). The Ni$^{3+}$ is then oxidized to Ni$^{4+}$ at $x=0.75$; see Fig.~\ref{fig;dos2}(d). Now, Ni and Mn are all in the charge state $+4$ and the valence-band top is predominantly the O $2p$ states which is similar to that of undoped \ce{Li2MnO3}. Lithium extraction beyond this point involves the oxidation of O$^{2-}$ to O$^{-}$. For example, at $x=1.00$, Li$_{1.75-x}$Ni$_{0.25}$MnO$_3$ has electronic states at $\sim$2 eV that are associated with the oxygen hole polaron $\eta_{\rm O}^+$ (i.e., O$^-$); see Fig.~\ref{fig;dos2}(e).

We note that, since the nature of the electronic structure near the band edges is the same for \ce{Li2MnO3} doped with Ni at the $2b$ site, the $2c$ site, or the $4h$ site, the delithiation mechanisms are the same in these systems.

Figure \ref{fig;dos3} shows the DOS of Li$_{2-x}$Mn$_{0.75}$Mo$_{0.25}$O$_3$ (with the dopant incorporated at the $4g$ site) for different degrees of delithiation. Mo is stable as Mo$^{5+}$ and charge-compensated by Mn$^{3+}$ as mentioned in Sec.~\ref{sec;dilute}. At $x=0$, the valence-band top is predominantly the Mn$^{3+}$ $3d$ and Mo$^{5+}$ $4d$ states. We find that an electron is removed first from Mn$^{3+}$ and the ion is oxidized to Mn$^{4+}$; the valence-band top becomes predominantly the Mo$^{5+}$ $4d$ states after the removal; see Fig.~\ref{fig;dos3}(b). Subsequent removal of lithium turns Mo$^{5+}$ into Mo$^{6+}$ and the Mo $4d$ states become empty and are pushed up in energy; see Fig.~\ref{fig;dos3}(c). From this point onward, lithium extraction involves the oxidation of O$^{2-}$ to O$^-$. For example, the DOS peak at about 2.5 eV in Fig.~\ref{fig;dos3}(d) is associated with an oxygen hole polaron $\eta_{\rm O}^+$ resulted from the O$^{2-/-}$ redox reaction. At $x=1.00$, the DOS shows two peaks at $\sim$2.0$-$2.5 eV, corresponding to $\eta_{\rm O}^+$ defects present in the partially delithiated compound; see Fig.~\ref{fig;dos3}(e).

\begin{figure}
\centering
\includegraphics[width=8.6cm]{fig9}
\vspace{-0.2cm}
\caption{Charge densities associated with the oxygen hole polaron $\eta_{\rm O}^+$ (i.e., O$^-$) in Li$_{2-x}$Mn$_{0.75}$M$_{0.25}$O$_3$ ($x=0.75$): (a) M = Mo and (b) M = Ru. The iso-value for the isosurface (yellow) is set to 0.05 e/{\AA}$^3$. Large gray spheres are Li, medium blue spheres are Mn, and small red spheres are O.}
\label{fig;eta}
\end{figure}

Figure \ref{fig;dos4} shows the DOS of Li$_{2-x}$Mn$_{0.75}$Ru$_{0.25}$O$_3$ (with the dopant at the $4g$ site) for different degrees of delithiation. Similar to the other doped \ce{Li2MnO3} systems discussed earlier, the electronic structure of the Ru-doped one, particularly the nature of the electronic states near the band edges, changes as the delithiation process progresses. At $x=0$, the top of the valence band is predominantly the Ru $4d$ states; see Fig.~\ref{fig;dos4}(a). The first two stages of delithition involve oxidation of Ru$^{4+}$ to Ru$^{5+}$, see Fig.~\ref{fig;dos4}(b), and then from Ru$^{5+}$ to Ru$^{6+}$, see Fig.~\ref{fig;dos4}(c). For $x\geq 0.75$, oxygen in the material becomes oxidized, leading to the formation of oxygen hole polarons $\eta_{\rm O}^+$. The DOS peaks (at the bottom of the conduction band) associated with $\eta_{\rm O}^+$ can be observed in Figs.~\ref{fig;dos4}(d) and \ref{fig;dos4}(e). There is a strong mixing of the $\eta_{\rm O}^+$ states and Ru $4d$ states, a feature that is not seen in the Ni- or Mo-doped system, indicating strong Ru$-$O interactions. Figure \ref{fig;eta} shows charge densities associated with the oxygen hole polaron $\eta_{\rm O}^+$ in Li$_{2-x}$Mn$_{0.75}$M$_{0.25}$O$_3$ ($x=0.75$, M = Mo, Ru); $\eta_{\rm O}^+$ is found to be located between two Mn in one compound and between Mn and Ru in the other.

We note that the doped \ce{Li2MnO3} materials all exhibit non-metallic behavior and they remain non-metallic upon delithiation. This observation is consistent with our analysis of defect physics in \ce{Li2MnO3} reported previously\cite{Hoang2015PRA} according to which the material cannot be doped $n$- or $p$-type like a conventional semiconductor; any attempt to deliberately shift the Fermi level to the VBM or CBM will result in having intrinsic point defects formed spontaneously to counteract the effect of shifting. Our results are thus in contrast to those reported by other research groups, often obtained in DFT$+U$ calculations, according to which partially delithiated (and even some fully lithiated) \ce{Li2MnO3}-based materials show metallic behavior.\cite{Yang2017AFM,Gao2014JMCA,Gao2015CM} Like in the case of undoped \ce{Li2MnO3} discussed earlier (Sec.~\ref{sec;method}), experiments should be performed to confirm the nature of bulk electronic conduction.

\subsection{Doping as enabler of the anionic oxidation reaction during delithiation}

Figure \ref{fig;voltage} shows the voltage profiles of the undoped and doped \ce{Li2MnO3} materials. The redox couples associated with different voltage points are indicated in the figure; unmarked points in the shaded region are associated with the redox activity on oxygen, which can be assigned to the O$^{2-/-}$ couple, at least nominally. All these redox couples are determined by observing changes on the magnetic moment and charge density induced by lithium removal. We find that the voltage of undoped \ce{Li2MnO3} is high at the beginning but lower after the first stage of delithiation. The voltage profile of Li$_{2-x}$Ni$_{0.75}$Mn$_{0.75}$O$_3$ (with Ni at the $4g$ site only) follow closely that of undoped \ce{Li2MnO3}, which is expected, given that the nature of the valence band of the two systems is very similar. In Li$_{1.5-x}$Ni$_{0.75}$Mn$_{0.75}$O$_3$, only the Ni ions are oxidized because they provide already enough electrons for delithiation. We note that, if the Ni concentration is lower, i.e., Li[Ni$_z$Li$_{1/3-2z/3}$Mn$_{2/3-z/3}$]O$_2$ with $z<1/2$, oxygen would be oxidized at high degrees of delithiation, as also observed in experiments.\cite{Luo2016JACS} This is, indeed, the case, as seen in our calculations using the 48-atom supercells which correspond the composition with $z=1/4$. For the other doped \ce{Li2MnO3} systems, oxidation occurs first with the transition-metal ions whereas contributions from the oxygen usually occurs at higher voltages. These results are thus consistent with our analysis of the calculated electronic structure reported earlier.

\begin{figure}
\centering
\includegraphics[width=8.6cm]{fig10}
\vspace{-0.2cm}
\caption{Voltage profiles of undoped \ce{Li2MnO3} (black circles) and \ce{Li2MnO3} doped with Ni at the $4g$ site (orange half-filled squares), the $2b$ site (green half-filled circles), or both the $2b$ and $4g$ sites (gray squares); Mo (red half-filled triangles) or Ru (blue diamonds) at the $4g$ site. Each voltage point is the average voltage between the two Li concentrations used to calculate it. Unmarked voltage points in the shaded area are those associated with the redox activity on oxygen.}
\label{fig;voltage}
\end{figure}

As discussed in Ref.~\citenum{Hoang2015PRA}, the difficulty in activating the undoped \ce{Li2MnO3} material electrochemically is likely due to the high extraction voltage and a lack of percolation pathways for efficient electronic conduction in the bulk at the onset of delithiation. Other delithiation mechanisms, including non-intrinsic ones, may thus become essential in the early stages of the delithiation process; these include simultaneous removal of lithium and oxygen at the surfaces and/or interfaces (which leads to oxygen release as often discussed in the literature), oxidation of preexisting Mn$^{3+}$ defects in the material, and/or oxidation of the electrolyte and exchange of H$^+$ for Li$^+$.\cite{Hoang2015PRA} For example, when a Li is replaced by H, the resulted impurity (nominally denoted as H$_{\rm Li}^0$) can be regarded as a defect complex of a positively charged hydrogen interstitial H$_i^+$ and a negatively charged lithium vacancy $V_{\rm Li}^-$. The exchange of H$^+$ for Li$^+$ thus also results in the formation of $V_{\rm Li}^-$ that is needed to stabilize $\eta_{\rm O}^+$ and to establish the percolation pathways. Indeed, we find that $\eta_{\rm O}^+$ forms upon electron removal from H-doped (partially protonated) \ce{Li2MnO3}. The average voltage between Li$_{1.75}$H$_{0.25}$MnO$_3$ and Li$_{1.50}$H$_{0.25}$MnO$_3$ is calculated to be 5.06 V, which is lower than that obtained for undoped \ce{Li2MnO3} during the first stage of delithiation.

In Ni-, Mo-, or Ru-doped \ce{Li2MnO3}, charge compensation and bulk electronic conduction in the initial stages of delithiation are provided by the electrochemically active transition-metal ions. The lower voltages associated with these non-oxygen redox couples also make it easier for lithium removal. The mechanism involving the O$^{2-/-}$ redox couple is expected to be more efficient in the later stages where the $V_{\rm Li}^-$ concentration is high and hence bulk electronic transport via $\eta_{\rm O}^+$ becomes possible.\cite{Hoang2015PRA}

Finally, we note that the average voltage associated with the oxide redox reaction in the intermediate stages of delithiation is $\sim$4.9 V; see Fig.~\ref{fig;voltage}. This value is thus only about 0.4 V higher than the $\sim$4.5 V plateau\cite{Lu2002JES,Koga2014JPCC,Luo2016JACS} often observed in \ce{Li2MnO3}-based materials during first charge and attributed to the oxidation of oxygen in the bulk lattice. The voltage difference is well within that often seen in voltage calculations; see, e.g., Ref.~\citenum{Chevrier2010}.

\section{Conclusions}

A detailed study of doping in Li-rich cathode material \ce{Li2MnO3} has been carried out using hybrid density-functional calculations. We consider the impurities in both the dilute doping limit and heavy doping with attention to charge-compensation mechanisms and the effects of defect-defect interaction on the stable charge and spin states of the transition-metal ions. Al, Fe, Mo, and Ru impurities are found to be energetically most favorable when incorporated at the Mn lattice site, whereas Mg is most favorable when doped at the Li sites; Ni can be incorporated at the Li site and/or the Mn site. There is a strong interplay between the lattice site preference and charge and spin states of the dopant, the electronic structure of the doped material, and the mechanism for lithium extraction. The calculated electronic structures and voltage profiles provide specific information on the delithiation mechanisms, including the order in which the redox couples are activated. In these mechanisms, electrochemically active transition-metal ions provide charge-compensation and bulk electronic conduction mechanisms in the initial stages of the delithiation process and hence enable the mechanism involving the oxidation of the lattice oxygen in the later stages.

\begin{acknowledgments}

The calculations were carried out using computing resources at the Center for Computationally Assisted Science and Technology at North Dakota State University.

\end{acknowledgments}

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text:
JCEP: a growing union of hearts and minds
By Herminio Rico SJ, Jesuit Conference of European Provincials (JCEP) Socius
Europe, a small continent in the middle of a vast world map, and, in it, so many nations and countries, a babel of languages, an enormous variety of cultures. Difference and richness. The Jesuit Europe reveals no lesser diversity. It guards the original places of Ignatian history: Loyola and Manresa, Paris and Rome, even Jerusalem is within the territory of the Conference. And it is blessed with a treasure of tradition, which all want to honour and sustain. Provinces both larger and smaller, with stronger or weaker institutional structures, look for new ways to sustain their main works and continue to serve their mission in the long term. All feel the challenge of fast diminishing numbers of Jesuits. Reality has been leading the Conference to a greater openness to closer collaboration and more extended sharing of responsibilities. A sense of common mission, though lived in very different religious and ecclesial contexts, and the experience of belonging to a larger apostolic body have been growing fruits of the regular Conference meetings.
The last General Assembly, that took place, online, from 9 to 13 October, in eight two-hour sessions, was a good step forward. In a final serene time of prayerful evaluation, the experience of consolation was unanimous: encouragement, enthusiasm, optimism, greater openness to the universal body, energy and commitment, inspiration, belonging… were the sentiments shared after the time together, listening and discussing, making decisions, sharing prayer and life. A somewhat surprising result, against the odds. The Conference had not been all together for a year, since the Assembly in Zagreb in October 2019. Out of the 19 Major Superiors, seven were new; the agenda was heavy and demanding; hour after hour with the eyes focused on a computer screen, trying to identify the speaker in the mosaic of faces, or following yet another PowerPoint in the shared screen. And everything in English, a language that for only two of the twenty three participants is the mother tongue. Yet the Spirit brought consolation and enthusiasm for the future. Although some blunt facts may be worrisome and many numbers depressing, the way forward is to let ourselves be led by the Spirit, through, but also over, the most pragmatic facing of reality.
Father General participated in one of the sessions and urged all to take seriously the work of vocation promotion. The Assembly approved the priority calls for the JCEP Apostolic Plan and the first one is precisely: "to support and resource the vigorous promotion of the Jesuit vocation in Europe". A vote confirmed the new Statutes for the Conference that are now with Fr. General for his final approval. There was time for reports by the directors of the Conference main works and networks: Jesuit European Social Centre; JRS-E with JRS International and JRS-Middle East and Northern Africa; primary and secondary education (JECSE), higher education (Kircher Network). Other topics to mention: accounts and budget, personnel needs for the Conference, formation centres, European tertianship and safeguarding.
Through hard work, but mostly by the action of the Spirit, the Assembly was a successful step forward in building unity of hearts and minds among the Major Superiors of the European Conference.
JCEP
The Good Samaritan: Life is full of journeys
African Jesuits condemn the killing of school children in Cameroon
IntelSoc: Jesuits in Leuven want to unite intellectual and social apostolates
The Jesuits on the quays of Marseilles: reaching out to people wherever they are
JRS Belgium: Letting the light shine through
Promoting Ignatian Spirituality in a school… without Jesuits
Not forgetting Syria… and its Christians
Daring to live out the values of the Society of Jesus

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And an in-text citation book citation in Sexuality & Culture looks like this: (Angelou 1969)
How to reference a journal article in the Sexuality & Culture citation style?
How do you cite scientific papers in Sexuality & Culture format?
To cite a research paper or journal article following the Sexuality & Culture formatting guide, follow these easy steps
Here's a Sexuality & Culture journal citation example using placeholders:
Author1 LastnameA. F., & Author3 LastnameA. F. (2000). Title. Container, Volume(Issue), pages Used. https://doi.org/DOI
So if we want to reference this scientific article: "Testing consumer preferences for iced-coffee: Does the drinking environment have any influence?" by C. Petit and J.M. Sieffermann in Sexuality & Culture:
Petit, C., & Sieffermann, J. (2007). Testing consumer preferences for iced-coffee: Does the drinking environment have any influence?, 18(1), 161-172. https://doi.org/10.1016/j.foodqual.2006.05.008
And an in-text citation would look like this: (Petit and Sieffermann 2007)
How to cite a website in a paper in Sexuality & Culture style?
If you're writing a research paper, you'll likely do a fair amount of research online. If you have websites that you want to use as sources for your paper in Sexuality & Culture, follow this simple guide
Here's an Sexuality & Culture example website reference:
Author1 LastnameA. F., & Author2 LastnameA. F. (2000, January 1). Title. Publisher. https://www.example.com. Accessed 29 January 2022
To reference the article located at this link:
https://www.theguardian.com/world/2008/nov/05/uselections20083
on The Guardian website:
Tran, M. (2008, November 5). Barack Obama To Be America's First Black President. The Guardian. https://www.theguardian.com/world/2008/nov/05/uselections20083. Accessed 29 January 2022
And an in-text citation would look like this: (Tran 2008)
Citing websites and links in Sexuality & Culture is much easier with the Citationsy Chrome Extension →
How to cite a YouTube video Sexuality & Culture
Are you wondering if it's ok to reference a YouTube video in a research paper? Here's how to cite it in Sexuality & Culture
Here's a Sexuality & Culture citation YouTube video example:
ChannelName. (2000, January 1). Title. YouTube. https://www.youtube.com/watch?v=XXXXXX. Accessed 29 January 2022
So how to cite a video Sexuality & Culture?
Pixar. (2015, June 3). Pizza Clip — Inside Out. YouTube. https://www.youtube.com/watch?v=8W6rntBADUQ. Accessed 29 January 2022
And an in-text video citation would look like this: (Pixar 2015)
How to cite a podcast using Sexuality & Culture referencing style
Citing a podcast in Sexuality & Culture is pretty straight forward. Here's how you can do it
It is becoming more and more common to reference podcasts in essays or other school work.
Here's how to reference a podcast it in Sexuality & Culture.
Lastname, F. (2000, January 1). Title. Publisher. http://www.example.com. Accessed 29 January 2022
Podcast referencing example in Sexuality & Culture using "This American Life" episode 640:
This American Life. (2018, March 2). 640: Five Women. WBEZ Radio. https://thisamericanlife.org/640/five-women. Accessed 29 January 2022
And an in-text citation would look like this: (This American Life 2018)
How to cite a piece of music or a song using Sexuality & Culture referencing style?
Did you know there are well over 100 million different songs you can cite and reference? Here's a simple guide to reference any song in Sexuality & Culture
An example song citation in Sexuality & Culture.
Lastname, F. (2000). Song Title. Album. http://www.example.com. Accessed 29 January 2022
Let's say we want to reference "Here Comes the Sun" off The Beatles "Abbey Road" album in Sexuality & Culture:
The Beatles. (1969). Here Comes the Sun. Abbey Road. https://itunes.apple.com/us/album/here-comes-the-sun/401186200?i=401187150. Accessed 29 January 2022
And an in-text citation would look like this: (The Beatles 1969)
You can automate citing and referencing any source in Sexuality & Culture using Citationsy.
Cite sources using the Sexuality & Culture Citation Machine
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It has a free trial and has iPhone and Android apps available. Sign up now →
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2008-05-01 14:10 Keep a long-term perspective; know your "sales cycle"
2007-03-07 20:14 Layered Architecture in Java off the server -- not?
2007-03-06 20:56 So what is a server-side guy doing at the Java Posse Roundup 2007?
2005-09-21 00:56 Why make a free runtime for Java?
2005-04-16 00:56 If Open Source were a girl, would she dump you?
2004-02-16 23:44 Kathy Sierra read my weblog!
2004-01-19 23:59 Head First Java - yep, reading it and proud of it.
2003-09-13 01:45 Testing, testing...is this thing on?


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UL announces 'major goal' of all students returning to campus for 21-22 academic year
The Deputy President of the University of Limerick, Professor Nigel Healey, has said "it is our very strong hope and a major goal that the next Academic Year 2021/22 will see all of us back on campus."
In an email sent to UL students this morning, Dr. Healey paid tribute to "an extraordinary academic year, dominated by genuinely inspiring examples of resilience, tenacity and innovation from you, our student body, and from our hugely committed staff community."
The email added "we will have a chance to welcome, in particular, our current first year students in person when they return to campus as second years."
"The precise nature of that return will, of course, be dependent on the public health guidance at the time, and discussions will take place with Minister Simon Harris and his department over the coming weeks to plot the best way forward for a more normal campus life."
"The light is at the end of the tunnel, but we need to get there safely, so please continue to follow public health advice," the email read.
The University recently rolled out a trial of a Covid-19 day pass and encouraged the student body to avail of the trial, with the email stating "the trial may also help us to return to a more conventional student experience next September."
Breaking: Zebo set for Munster return
Limerick cancer survivor urges people to check for lumps


text:
AML updates
AML Basics
AML Case studies / Reports
AML Softwares
Webinar and Presentations
Sanctions and Fines
AML Essentials
AML / Compliance certifications
AML software vendors
AML fines on historical timeline scale
Screening software vendors
Worldwide (FIU's) website
AML communities
Abhishek Dwivedi
AMLabc
Latvia fines Sweden's SEB over anti-money laundering controls, sanction violation
South Africa: Reserve Bank fines Standard Bank R30m, imposes penalties on…
Finland: S-Bank fined nearly €1m over lax monitoring of money laundering
Tanzania fines five banks for lax anti-money laundering controls
Latvia: FCMC applies a fine of 1 million euro to JSC…
Home AML Sanctions and Fines Settlement Agreement between the Central Bank of Ireland and Drimnagh Credit Union...
Settlement Agreement between the Central Bank of Ireland and Drimnagh Credit Union Limited
The Central Bank of Ireland imposes a fine of €125,000 on Drimnagh Credit Union Limited for breaches of the Credit Union Act 1997 and the Criminal Justice (Money Laundering and Terrorist Financing) Act 2010. The Central Bank of Ireland (the "Central Bank") has fined Drimnagh Credit Union Limited ("Drimnagh Credit Union") €125,000 and reprimanded it for two breaches of the Credit Union Act 1997 (the "CUA 1997") and five breaches of the Criminal Justice (Money Laundering and Terrorist Financing) Act 2010 (the "CJA 2010"). All seven breaches have been admitted by Drimnagh Credit Union.
The breaches of the CUA 1997 occurred from 1 August 2013 to 30 November 2014 and relate to the following:
The prohibited payments to certain directors and a Board Oversight Committee member of Drimnagh Credit Union in breach of section 68 of the CUA 1997; and
Failings in Drimnagh Credit Union's systems of control in relation to the claiming, recording and approving of officers' expenses.
SOURCEwww.centralbank.ie
South Africa: Reserve Bank fines Standard Bank R30m, imposes penalties on 4 other banks
Latvia: FCMC applies a fine of 1 million euro to JSC "PrivatBank" and imposes a number of legal obligations
Hungary: Equilor was fined $ 30 million
Turkey: MASAK, Transaction Currency money-laundering center
The Financial Crime Investigation Office of the Ministry of Treasury and Finance has reported to the court that the Transaction Exchange Office that defrauded...
Russia: Moscow "PFS-Bank" could be deprived of a license for money laundering
The Central Bank of Russia has revealed the reasons for the deprivation of PFS-Bank's license, saying that the bank is suspected of money laundering...
Chain Analysis published report – Cybercrime and Money Laundering
The Chain Analysis company is involved in investigating cybercrimes, analysing blockchain system, and reporting to an investigative authority. In its last analysis and report,...
Estonia: Danske Banks Money Laundering Probe Expands
The Estonia branch of Danske Bank's money laundering probe has been expanded from 2 cases to more than 10 cases, concerned with suspicious transactions...
Bermuda Confirmed as a Global Leader in the Fight Against Money Laundering and Financing...
Following the recent assessment carried out on Bermuda's regulatory system, which lasted for 14 months, by the Caribbean Financial Action Task Force (CFATF), and...
Get the latest updates from all over the world in the field of financial economic crimes, primarily focussed on money laundering, terrorist financing etc.
© Copyright 2020 - AMLabc
FinCEN Penalizes Texas Bank for Violations of Anti-Money Laundering Laws
FinCEN Fines Michigan MSB and Its Owner/Compliance Officer for Ignoring AML...
17-Dec-2002: FSA fines Royal Bank of Scotland Plc 750,000 for money...


We are always looking for bright, driven and ambitious people to join our team. Whether you are an accomplished professional or a promising new talent, you'll be challenged by the work, the people on your team, and the clients we serve. You'll be constantly learning, and your ideas will be welcomed in an atmosphere of collaboration and teamwork.
We are also united by our shared values, which inspire our people and guide them to do the right thing, and our commitment to quality, which is embedded in who we are and everything we do.


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New automated packaging for Country Chef
Tuesday, 14 April, 2015 | Supplied by: Rockwell Automation Australia
European packaging machinery supplier Cama Group recently opened an Australian office to service the local market. Cama designs and develops packaging machines and robotic systems for use in food and non-food industries, and covers the primary and secondary packaging processes. The Cama Group is headquartered in Italy, with subsidiaries in France, the United Kingdom, Germany, Thailand, the United States, China and now Australia.
At a time when the local manufacturing industry is facing unprecedented challenges, the foresight of Cama to invest in Australia and to lead the way for European packaging suppliers demonstrates its innovation and commitment to the market here.
According to Cameron Traum, general manager, Cama Australia, "Cama understands the importance of direct contact with our clients, and we want to make sure our service standards are the best in market. The only way to make sure we can do that is by investing in the market and being here in Australia."
One of Cama's Australian customers, Country Chef, recently upgraded its slicing and flow wrap machines but needed an advanced end-of-line packaging solution to exploit and leverage the new efficiency and speed gains. Replacing a labour-intensive manual operation with a machine like the IF316 provides small businesses with greater efficiencies and, in this case, allows Country Chef to compete more readily on a national level, supplying the biggest retailers.
Cama's IF316 is a compact machine which includes a compact former, a loading system with delta robot and a closing system with a two interpolated axis robot incorporating a specific lidding tool. The machine is set up for the secondary packaging of flow-packed snack bars but can be adapted to pack other kinds of products, and can be easily integrated in a packaging line just before the palletising station.
The IF316 has been built by Cama according to its cabinet-free design concept, offering a reduced footprint by integrating the electrical and pneumatic component control cabinets into the machine pedestals' angles. Such compactness helps to minimise cabling and makes it easier to place the utility devices right where they are needed, with further benefits in terms of accessibility for maintenance tasks.
The automation system on the IF316 has been designed and built using Rockwell Automation components. An Allen Bradley 1756-L72S GuardLogix controller manages the machine's functions by synchronising the three phases of the packaging process.
Using RSLogix programming software Cama configured a 10-axis motion system, managed by Allen-Bradley Kinetix drives. Synchronisation among the drives has been programmed using a virtual axis master. An Allen-Bradley PanelView Plus operator panel has been selected for visualisation tasks and is configured through FactoryTalk View software. Flexible I/O and EtherNet/IP connectivity complete the automation architecture on the machine.
"Rockwell Automation is recognised all over the world as a leading automation, motion and safety supplier to the packaging industry, so it makes sense that Cama uses a company that can offer us the same levels of supplies and services that we offer to our customers," said Traum.
"While the local market is very mature and robust, companies are still actively seeking ways to improve efficiency and reliability in manufacturing and they understand the need to invest in technology to remain competitive."
Cama's value proposition is its well-known brand and reputation, together with its experience and range of secondary packaging solutions. This is further enhanced by Cama's new Australian presence, allowing customers to deal with a local office in a local time zone.
According to Traum, "The key is being here and offering the service from the first contact. We make sure that everything we do is best in the market, including our speed of response and service with attention to detail.
"The reaction to our local presence - having our own spare parts and service established within Australia - has been overwhelming. We are involved in significant projects in the market, so it looks as though we will exceed all our expectations in terms of involvement in the market and returns in the first 12 months."
Online: www.rockwellautomation.com/en_au
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text:
The Ben Simmons Trade Sweepstakes Has Reportedly Narrowed Down to 3 Teams
by Jack Dougherty twitter | More Articles: NBA
We're less than two months away from the NBA trade deadline, and Ben Simmons remains a member of the Philadelphia 76ers. You can bet the Sixers will be feverishly working the phones over the next few weeks in an effort to move their disgruntled All-Star. If they do, ESPN's Brian Windhorst believes three teams have emerged as the most likely players in a potential deal.
The 76ers are still looking to trade Ben Simmons
Ben Simmons of the Philadelphia 76ers shoots the ball against the Boston Celtics | Mitchell Leff/Getty Images
The 76ers have now played 30 games this season, and Simmons hasn't been present for any of them. At this point, it would be a shock if he suited up for the team ever again.
Simmons has made it clear he wants no part of the Sixers organization for the rest of his career. Philadelphia has tried to convince him to stay for the last few months, but that doesn't seem to be a realistic solution to his bizarre problem.
So, the 76ers have until February 10 to find a trade for their 25-year-old All-Star. President of basketball operations Daryl Morey is still holding out hope that he can land a superstar in exchange for Simmons, but he might have to settle for less to get the team's biggest distraction out of the building for good.
Simmons trade sweepstakes reportedly down to three teams
NBA fans and experts alike have been trying to predict Simmons' landing spot for months. Could he team up with Kevin Durant and James Harden on the Brooklyn Nets? Would the Golden State Warriors be interested in making a deal? What about the Portland Trail Blazers in light of all their issues?
But according to Brian Windhorst of ESPN, the Minnesota Timberwolves, Houston Rockets, and Sacramento Kings have emerged as the most likely players in a Simmons deal. He explained on a recent episode of The Hoop Collective podcast.
"There've been a number of rumors that've gone around the league in the last few weeks about Ben Simmons trades involving the Morey quadrangular. The Morey quadrangular would be the Philadelphia 76ers, Daryl Morey, general manager, president, whatever his title is; Minnesota Timberwolves, who are run now by Sachin Gupta, who worked for Daryl Morey; the Kings, who are run by Monte McNair, who worked for Daryl Morey; and the Rockets, who are run by Rafael Stone, while there's some scar tissue there, who worked for Daryl Morey.
"I am not going to tell you some of these preposterous scenarios that have been floated to me, but let's just say there's been a lot of discussion."
Keep your eyes on the Morey quadrangular
It's Time to Finally Detonate the Sacramento Kings, and a 3-Way Trade Involving Ben Simmons Should Light the Fuse
Windhorst's prediction makes perfect sense. Morey has probably been communicating with his old friends regularly over the past few months, and they might be the most likely to say yes to a deal.
"As you look at it, the Timberwolves really would like to get Ben Simmons. That is not a secret, that is not new.
"The Kings are really struggling and really want to be competitive, they've already fired Luke Walton, and they have surplus perimeter players. It's not news that Buddy Hield is available.
"And then of course you've got the Rockets."
The Morey quadrangular could be the key to Simmons' eventual departure.
"I've had executives tell me that when Ben Simmons is traded, it will include one or more of the quadrangular. Not necessarily that that's where Ben Simmons would go, but that they would be involved in the trade. Because a Ben Simmons trade is likely to wind up being a multi-team deal."
Time is ticking, Daryl.
Like Sportscasting on Facebook. Follow us on Twitter @sportscasting19.
Tags:Ben Simmons Houston Rockets Minnesota Timberwolves Philadelphia 76ers Sacramento Kings


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text: redis-cli flushall && watch -n 0.2 python tools/redis_watch.py

redpajama_set_name: RedPajamaGithub


Any energy healing practiced by Hiroko Takano, in person or by proxy, is not a substitute for medical care. This information is not intended as medical advice and is not medical diagnosis or treatment. Information given to you by Hiroko Takano is not intended to create physician-patient relationship, nor should be considered a replacement a healthcare professional. Any questions or concerns should be directed to a healthcare provider. Hiroko Takano makes no claims to healing or recovering any illness. Healing sessions are confidential and personal information will never be shared. After completing your first session if you believe that you have not benefited or received any value whatsoever, your fee will be promptly refunded. By viewing or using this web site, you consent to the exclusive jurisdiction and venue of a court of competent jurisdiction in Oakland, California, and to the exclusive use of the laws of California.
copyright©2012 LunaChic. All Rights Reserved.


Michael has a natural insight and empathy for challenges facing commercial clients, derived from a commercial career spanning two decades. He was responsible for contract drafting and settlement negotiations in a broad range of commercial situations, and worked with Counsel in litigation on a number of occasions.
During pupillage, Michael undertook work with Andrew Peebles on an application for a Freezing Injunction in the High Court, and accompanied his supervisor Changez Khan on commercial cases in the High Court and Court of Appeal.
Michael is keen to develop this area of his practice. Outside of his court practice, Michael utilises his blend of commercial acumen and legal experience to advise Companies and Directors on contractual matters, strategy and tactics.
Prior to being called to the Bar, Michael enjoyed a successful commercial career. With particular skill and experience in the fields of sales and marketing, he progressed from junior sales roles to senior management and Board positions, with responsibilities including negotiating and managing contractual relationships on many high-profile consumer promotions involving mobile networks including o2, EE and 3.
Michael's operational experience included an elected role on the Executive Committee of a UK Trade Body where he supported the response of the retail industry to a Law Commission consultation on prepayments made by consumers. He also gained inspiration for his future career by working alongside Counsel in pursuit of remedy to contractual breaches by clients, including a successful application for a Freezing Injunction and consequent award of damages.
For the final 7 years of Michael's commercial career he read law and undertook the BPTC while simultaneously fulfilling a senior board role in a stock market listed technology company, and managing his own consultancy business.
Michael is married with three sons, and lives in Sevenoaks, Kent.
In his spare time he enjoys drinking good wine with his wife and eldest son, and trying – largely unsuccessfully – to maintain parity with his 10 year old's science knowledge, and his 9 year old's football skills.


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First-Crop Yearlings: Superstars Impress as Sires
By Pati on July 12, 2018 • ( 2 Comments )
HIP 171- yearling filly by Mucho Macho Man // Pati Szpyra Photo
There is always a buzz around the first yearling auction of the season, especially when so many good horses entered their breeding careers at the same time. This is considered to be the glimpse into the rest of the season as the larger, more well-known auctions like the Saratoga Select and Keeneland September start to loom on the horizon and the farms around Kentucky start intense preparations.
While there was a lot of activity and interest surrounding the yearlings of American Pharoah, the sale only had two representatives to look at this year; other first-crop sires faired better as Palace, Palace Malice, Tapiture, and Constitution all had significantly larger offerings on display that generated lively bidding in the ring.
The old guard of established sires also struck hard and fast at this sale as Flatter went home with top prize as the sire of the sale's topper when a colt of his sold for $520,000 to Al Rashid Stable. Street Sense, Into Mischief, and Violence locked up the top spots as the first-crop sire with the largest price at the sale wound up being Palace Malice, who "finished" seventh in that tally.
Among the more interesting offerings was HIP 171, a chestnut filly by Mucho Macho Man that came as the offering of Maine Chance Farm, which is part of the University of Kentucky. She was long and her hindquarters needed some filling, but she walked like a horse with a purpose. The filly sold for $15,000 to Grassroots TRN & Sales LLC, suggesting that she might go back up for offer at the 2YO sales later next year as a horse in training.
HIP 40- Malibu Moon filly out of Samsational // Pati Szpyra Photo
HIP 40- One that I lovingly called "Rachel Face", she was a nice, full filly that brought plenty of attention to Barn 3. She was bright and attentive with a big, swinging walk that impressed the large majority of the potential buyers that saw her.
Her family was equally as impressive, with her second dam's offspring drawing the most attention, as the one-time Kentucky Derby favorite of his year I Want Revenge makes an appearance under Meguial (Arg). She is only the second foal of her dam, Samsational, who could potentially be continuing the trend of successful, young Unbridled's Song mares to produce talented racers.
In the ring, she spurred a bidding war that lasted until she hit $180,000, though this would ultimately result in an RNA. She was later sold privately for $147,000 to JSM Equine LLC.
HIP 46 became a high priced sale for her young sire, Palace. Already named (quite a few in this sale were), Palace Two Step went to Hartley/Derenzo Thoroughbreds for $160,000; she is a registered Florida bred with a nomination to the Breeders' Cup.
Eclipse Thoroughbreds came to the Fasig-Tipton auction prepared to play as the group went for another filly by a first time Palace, but this time in the sire Palace Malice. HIP 60, the daughter of the Belmont Stakes winner drew eager early bids, but eventually was hammered down at $275,000 to the fan-favorite black and baby blue silks.
As for the two yearlings by American Pharoah, HIP 205 was declared an out and HIP 131 initially RNA'd in the ring before being sold for $200,000 privately.
In terms of high-end price tags, Will Take Charge and Into Mischief led the charge with both sires having three yearlings sell for $200,000 or more. The former's first foals are 2YOs of 2018 while Into Mischief has eight crops on the ground.
Overall, the sale experienced gains in every category: horses sold rose from 172 (2017) to 196; total amount sold was $19,762,500 from $16,107,000 last year; average increased to $100,829 from $93,645 and the median rose to $75,000 from $70,000. The RNA count rose to 86 horses.
Categories: Bloodstock, Sales
Tagged as: American Pharoah, Eclipse Thoroughbreds, Hartley/Derenzo Thoroughbreds, Maine Chance Farm, Mucho Macho Man, Palace, Palice Malice
Fasig-Tipton July Horses of Racing Age Recap
Photographing the Races: Newcomer's Guide
Published by Pati
A "long time" young fan of racing and traveling, I have set my sights on blogging about what I love most! Opinions are my own and there are plenty of them; engage at your own risk!	View all posts by Pati
edgerules says:
Reblogged this on edgerocks and commented:
Great job, Pati!!!
Great recap, Pati. Love it.


Kaemark's salon chair selection stands above the rest. Presenting our Kaemark Klassics, our selection includes styles for every salon type, personality, and budget. Shop for your dream chairs today!
During the design process of Design 1 Salon Spa in Portage, Kaemark was wonderful to work with. From the customized hair stations, sleek shampoo units, and men's barbering area, there was nothing that Kaemark could not provide us with. We look forward to continuing our business relationship with them in the future when we start designing our next location.
Skills Development Fund grant will provide safety and skills training for approximately 100 local workers.
"We were pleased with our experience with Kaemark. They are very detailed oriented which worked great for our specific needs. The quality of the materials and craftsmanship is what will make us a returning client doing another salon!"


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In addition to the branded tanks we stock, we also manufacture glass aquarium tanks here onsite in our workshop facility; we have many years of experience in aquarium manufacture.
The cost of glass is very variable and affects our tank prices, so please call or email if you would like a quote for a specific tank size.
When purchasing any aquarium tank, be sure to check the glass thickness used, this is critical to the strength of the tank.
The standard glass thickness we use for smaller tanks is 6mm. As a general rule, tanks taller than 18" (46cm) are manufactured in 10mm glass. In addition, tanks with a base width (front-to-back) of 15" (38cm) or more will have a 10mm glass base.
Please note that the highest we can manufacture tanks in 10mm glass is 24-26" (60-65cm).
Our glass tanks cannot be supplied by courier delivery, and are only available by collection, or delivery with our own truck within the mainland UK - please contact us with your postcode for a quote.
We also supply custom made aquarium cabinets and vivariums, see Gallery for some examples.
The table below details some of the common standard sizes of aquarium tanks - the sizes given in the table are just examples - we can manufacture the exact size you require.
* The tank volumes (shown in imperial gallons and litres) allow for the actual fill volume, and so give a more realistic actual volume.


Manage daily and long-term operation of an inbound customer contact call center responsible for a wide variety of center-level results.Achieve results by managing daily activities of center employees and continuously adapting processes, systems, and programs to meet the needs of the business.Responsibilities consist of but are not limited to:Problem solving and decision making based on a large amount of consistently changing data to strategize and plan for future center needs.Implement any change initiative that takes place in the office.Uses current business data to organize and delegate the activities of management and represented employees appropriately throughout the center as daily circumstances (promotions, losses, varied skill levels and experiences) and demands (changes in marketplace/customer) change.Motivates and develops management and represented employees to improve business and interpersonal skills as well as work behaviors.Provide necessary and timely interventions, counseling, feedback and training opportunities to center employees to build employee skills in critical areas.Counsel management on leadership issues as well as short and long term career goals.Conduct performance appraisals and recommends salary adjustments based performance observed and documented.Responsible for discipline and discharge of management employees when necessary.Educate self and center employees on multiple, important business issues which may include but are not limited to corporate, organization or office policies and procedures.Handle all presidential level complaints in South Carolina as it relates to Customer Information Services.Partners with the CWA local President to ensure an excellent working relationship as well as work through issues that may surface.Perform necessary special projects and organizational supported duties.Share office and departmental information on a monthly basis at our monthly COT meeting.Currently manage approximately 125 employees including a center assistant and 8 Managers.
Primary duty was to manage a group of call center employees.Supervised a team of 15 or more service/sales representatives located in a Consumer Services Call Center.Directed, coached, motivated and developed telephone sales, service and negotiation skills of subordinates to ensure that sales and service goals are met, orders are properly negotiated, billing inquires are properly addressed, complaints are resolved, and revenue in protected through correct negotiation of deposits and adjustments.Worked closely with other groups in the company to ensure service requests are met.Resolved complex and sensitive customer complaints and appeals, informed upper management of escalated complaints.Ensured accuracy and efficiency of service, maximization of sales revenue, and adhered to established policies and procedures.Ensured compliance with FCC and PSC regulations.Recommended and initiated associated personnel actions.
Responsible for the installation and repair of small business and residential phone lines.Reviewed and interpreted service orders, trouble reports, circuit diagrams and followed standard practices.Installed, rearranged, and removed telephone equipment and associated plant including wiring and cabling associated with services such as non-design watts, ISDN, etc.Operated computer access terminal equipment in some assignments to communicate with on-line data bases for testing, receiving and closing work assignments. Operated test equipment to send and receive signals on gain devices.Repaired, adjusted, cleaned, or replaced faulty telephone equipment.Contacted the appropriate centers and other designated organizations during tour for other assignments.Tested facilities and equipment on which trouble was reported.Changed out Subscriber Line Carrier channel units as required.Operated electrical instruments to locate and mark below ground facilities.Operated cable plats and test equipment to isolate conductor faults.Analyzed trouble conditions and determined the work that needed to be done.