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# Coronal X-ray emission from an intermediate-age brown dwarf

## 1 Introduction

With masses below the hydrogen burning mass limit $`M<`$ 0.08 M = 80 Mjup and cool, nearly neutral surfaces, brown dwarfs (hereafter BDs) had been expected to lack high energy activity. However, X-rays from several young BDs with ages $`t`$1 Myr old were discovered with $`ROSAT`$ in nearby star forming regions (Neuhäuser & Comerón 1998; Neuhäuser, Briceno & Comerón. 1999, Mokler & Stelzer 2002). After the launch of the Chandra X-ray Observatory, the number of X-ray-detected young BDs has increased an order of magnitude (Garmire et al. 2000, Imanishi, Koyama & Tsuboi 2001, Imanishi, Tsujimoto & Koyama 2001, Preibisch & Zinnecker 2001, Feigelson et al. 2002a). In young stellar clusters around 1 Myr old, hard and variable X-rays are now detected from about 1/4 of the BD population near the ‘saturation level’ of $`\mathrm{log}L_X/L_{bol}3`$. These properties are indistinguishable from those of higher mass young objects which will evolve into dM stars.

Nearly all field L- and T-type older BDs with ages $`t`$ 500–1000 Myr lack H$`\alpha `$ emission, a classical signature of active regions and plage, but exhibit radio flares (Gizis et al. 2000, Berger 2002). The weak H$`\alpha `$ in field BDs is particularly surprising in light of their rapid rotation (Basri 2001). One field BD at age $`t500`$ Myr, however, is clearly magnetically active. LP944-20 showed a 1–2 hr flare during a $`Chandra`$ observation with a peak luminosity $`L_X=1\times 10^{26}`$ erg s-1 ($`\mathrm{log}L_X/L_{bol}4.1`$) with a surprisingly soft spectrum, while it exhibited no detectable quiescent X-rays before the flaring (Rutledge et al. 2000). This BD also has exceptionally strong radio emission (Berger et al. 2001) and shows H$`\alpha `$ emission of EW $``$ 1 Å (Tinney 1998). At the intermediate age of $`t100`$ Myr, three probable BDs in the Pleiades have been observed with $`XMMNewton`$ of which one, Roque 9, may have been detected at $`\mathrm{log}L_X/L_{bol}2.6`$ (Briggs & Pye 2002, Stelzer & Neuhäuser 2002).

The evolution of magnetic activity in BDs thus appears confusing: H$`\alpha `$ and X-rays appear to decay as they descend the Hayashi tracks and cool, while radio emission does not. The nonthermal radio emission is particularly puzzling with both flare and persistent components far stronger than expected from the well-established Güdel-Benz radio/X-ray relationship that holds for all other late-type stars (Berger 2002). This contrasts with the theoretical expectation that BD surface magnetic activity should decay with age due to increased resistivity of the atmosphere (Mohanty et al. 2002). The evolution of magnetic activity in higher mass late-type stars is also not fully understood. Various multiwavelength manifestations of magnetic activity (X-ray flares, radio flares, H$`\alpha `$ emission, large starspots, strong surface fields, etc.) are consistently seen at high levels in T Tauri stars, but do not appear to depend on rotation as seen in main sequence stars (Feigelson & Montmerle 1999, Feigelson et al. 2003).

We introduce to this issue the $`Chandra`$ detection of TWA 5B, a BD at the intermediate age of $`t12`$ Myr. TWA 5B is a faint red object ($`H=12`$ mag) located 2′′ north of and co-moving with TWA 5A which itself is a spectroscopic binary (Lowrance et al. 1999, Webb et al. 1999, Neuhäuser et al. 2000). This system is part of the dispersed TW Hydra Association (TWA) of T Tauri stars, all of which are likely outliers of the giant Sco-Cen OB association (Kastner et al. 1997, Mamajek et al. 2000). TWA 5 is the first identified PMS star-BD binary system with an estimated age of $`12\pm 6`$ Myr (Weintraub et al. 2000). We assume here the mean Hipparcos distance to the 4 brightest TWA members of 55 pc. Optical and near-infrared photometry of TWA 5B gives a spectral type of M8.5$``$M9 and bolometric luminosity $`\mathrm{log}L_{bol}/L_{}2.6\pm 0.3`$, giving an inferred mass between 15 and 40 Mjup (Neuhäuser et al. 2000). The equivalent width of H$`\alpha `$ $``$20Å lies between those of young BDs (10–100 Å at $``$1 Myr old) and those of field BDs ($``$ 1 Å at $``$500–5000 Myr). TWA 5B is thus clearly an intermediate-age BD and may be near the end of its brief deuterium burning phase (Weintraub et al. 2000). The inferred mass is not far from the boundary between a brown dwarf and a planet of about 12 Mjup.

## 2 Observations and results

TWA 5B was observed on 2001 April 15 with the Chandra X-ray Observatory for 10.3 ks using the ACIS-S detector (see Weisskopf et al. 2002 for a description of the satellite and instrument). The S3 CCD chip was operated in a rapid readout subarray mode to reduce photon pileup of the primary TWA 5A which was known from $`ROSAT`$ studies to be very bright (Webb et al. 1999). The more frequent readouts resulted in a net on-target exposure of 9.3 ks. Image analysis started with Level 1 events from which we removed a $`\pm `$ 0″.25 positional randomization, filtered with Good Time Intervals, and corrected charge transfer inefficiency problem as described by Townsley et al. (2000). To achieve the highest possible spatial resolution, we applied a correction to estimate the arrival location of each photon within each 0″.5 pixel based on the precise distribution of charge received in adjacent pixels (Tsunemi et al. 2001, Mori et al. 2001). Spectral analysis was performed using Level 2 events provided by the standard satellite pipeline processing.

Visual examination of the raw (Level 2) ACIS S3 CCD image shows very strong emission with about 6200 counts from TWA 5A, a CCD readout stripe oriented NE/SW, and a faint excess of events 2″to the north where TWA 5B lies. The TWA 5B emission becomes much clearer after the special processing steps outlined above. Figure 1 (center) shows this X-ray image in a very soft 0.1–1.2 keV band that highlights the emission from the BD companion. Note that a resolution of $``$ 0″.3 FWHM is achieved using the subpixel process, while the original data has $``$ 0″.5 FWHM (these FWHM values are measured from radial profile binned by 0.05 pixel.)

We extracted 35 photons from standard Level 2 event list around TWA 5B in the 0.1–8 keV band using a 0″.7 radius circle after removal of background from an annulus around TWA 5A (see Figure 1, right panel). Since the extracted region is smaller than the standard $`Chandra`$ point spread function at this position, a modified ‘auxiliary reference file’ was created. The background-subtracted spectrum of TWA 5B was fitted with an optically thin MEKAL thermal plasma model with elemental abundances fixed at 0.3 times of the solar value, based on the fitting results of other young stellar objects (YSOs) detected by $`Chandra`$ and $`ASCA`$ (e.g. Imanishi, Koyama, & Tsuboi 2001). The resulting spectrum, shown in Figure 2, is unusually soft with peak emission at 0.7 keV and no photons above 1.5 keV. Best-fit parameters with 90% confidence levels are: temperature $`kT=0.3_{0.1}^{+0.2}`$ keV, line-of-sight column density $`N_H<6\times 10^{20}`$ cm-2, emission measure $`4\pm 1\times 10^{50}`$ cm-3, and luminosity $`L_X=4\times 10^{27}`$ erg s-1 in the 0.1–8 keV band. The spectral fit was essentially perfect with reduced chi-squared of 0.5 for 3 degrees of freedom. The plasma temperature and the luminosity are close to typical plasma conditions in the Sun today: at solar maximum, typical temperatures are $`kT`$ 0.2–0.5 keV with $`L_X1\times 10^{27}`$ erg s-1 (Peres et al. 2000). During a powerful solar flare, the typical temperatures rise to $`T`$ 1–2 keV, much hotter than seen in TWA 5B but typical of other PMS stars and BDs (e.g. Feigelson et al. 2002a).

A light curve of the photon arrival times was examined and no significant variations were found during the 11 ks duration of the observation. We can exclude variations greater than 50% in amplitude over the 10 ks observation.

## 3 Discussion

### 3.1 Evolution of X-ray emission

As outlined in the Introduction, there is considerable confusion in our understanding of the evolution of BD magnetic activity. Figure 3 shows our current knowledge of the relationship between X-ray emission, parameterized as $`L_X`$/$`L_{bol}`$ and the age of BDs. The X-ray properties for BDs in the Orion Nebula, $`\rho `$ Ophiuchi and IC 348 are obtained from $`Chandra`$ ACIS data by Feigelson et al. (2002a), Imanishi, Tsujimoto & Koyama (2001), and Preibisch & Zinnecker (2001), respectively. The field BD LP 944-20 detection is from Rutledge et al. (2000). Individual BD ages are distributed randomly for one order of magnitudes centered on 0.4 Myr ($`\rho `$ Oph, Orion) and 1.5 Myr (IC348) based on Luhman et al. (2000). For Orion, the upper-limits of X-ray undetected brown dwarfs were obtained as described in Feigelson et al. (2002a, equations 7 and 10) assuming negligible absorbing column and bolometric luminosities from Hillenbrand and Carpenter (2000). The data of LP 944-20 are separately shown for the flare, the upper limit at the quiescent (pre-flare) phase and the time-average during full observation, while the others are shown only for the last one (full observations). Except for LP 944-20, only two sources in $`\rho `$ Oph and one in IC348 have clear flares with amplitudes less than a factor of ten, which are within the range of the data scattering of each field. TWA 5B at $`\mathrm{log}L_X/L_{bol}=3.4`$ lies just below the $``$3.0 saturation limit in main sequence clusters and is consistent with the BDs seen in younger clusters.

Although a clear conclusion cannot be made from one object, this result is consistent with a continued high level of BD X-ray surface activity through $`t12`$ Myr. The decay to lower levels would then occur during the $`10^7`$$`10^8`$ yr phase, considering the averaged level of LP 944-20. This is consistent with the nearly constant (or even slightly rising; see Feigelson et al. 2003) $`\mathrm{log}L_X/L_{bol}`$ distribution from $`t<1`$ Myr through $`t20`$ Myr seen in higher mass late-type stars. The high level in $`\mathrm{log}L_X/L_{bol}`$ in younger phase might be related to the deuterium burning, with the fact that TWA 5B lies just at the end of the burning phase (Weintraub et al. 2000).

A somewhat different result emerges from consideration of the relationship between X-ray plasma temperature and age in BDs (Figure 4). Here the temperatures are derived from spectral fits to $`Chandra`$ ACIS data by the authors listed above. While very young BDs have hotter temperatures above 1 keV, the intermediate-age BD TWA 5B is significantly cooler at $`kT0.3`$ keV similar to the temperature found in the flare of the older LP 944-20 (Rutledge et al. 2000). However, the low temperature in TWA 5B, combined with the lack of variability, suggests that its X-ray emission arises more from a ‘corona’ than a single ‘flare’.

While a similar trend from hotter plasma to cooler plasma is seen in higher-mass YSOs, the timescale for this transition is much longer than implied for BDs. X-ray temperatures are typically $`kT6`$ keV for protostars (e.g. Imanishi, Koyama, & Tsuboi 2001) and $`kT14`$ keV for typical T Tauri stars (e.g. Feigelson et al. 2002a), with highly variable flare-dominated lightcurves. This hotter plasma is dominated by cooler coronal plasma only after $`500`$ Myrs (Güdel, Guinan & Skinner 1997).

It is interesting that the plasma temperature in LP 944-20 flaring is similar to that in TWA 5B quiescent. Considering that the X-ray luminosity of the LP 944-20 flaring is at least an order of magnitudes less than that of TWA 5B quiescent, the X-rays of TWA 5B, which appear like coronal emission, might be explained by a superposition of a number of such small flares. The similar possibility has been suggested and examined for the solar corona (Parker 1988, Shimizu & Tsuneta 1997).

### 3.2 Comments on the relationship between X-ray and H$`\alpha `$ emissions

Figure 5 shows our current knowledge of the relationship between X-ray emission, parameterized as $`L_X`$/$`L_{bol}`$ and the H$`\alpha `$ equivalent widths of BDs. In this plot, the ordinate indicates the X-ray surface brightness at the BD surface, while the abscissa represents the H$`\alpha `$ surface brightness, in the zero’s order. Here the H$`\alpha `$ properties are obtained from Jayawardhana, Mohanty & Basri (2002) for BDs in the $`\rho `$ Ophiuchi, Luhman (1999) and Herbig (1998) for those in IC 348, and Tinney (1998) for the field BD LP 944-20. For the time-averaged X-rays of detected BDs, we obtained a correlation of $`\mathrm{log}(L_X/L_{bol})=1.5\times \mathrm{log}(H\alpha )5.3`$. Such correlation has been already known in higher mass weak-lined T Tauri stars (for a recent example; Preibisch & Zinnecker 2002), which is interpreted by the hypothesis that the chromosphere (traced by the H$`\alpha `$ activity) is heated by a sufficient overlying corona (X-ray activity) (Cram 1982).

Figure 5 also shows that the strongest six ($``$100 Å) in the H$`\alpha `$ equivalent width were not detected in X-rays. As with higher mass classical T Tauri stars, these strong emission lines would be accompanied by IR disks. The relation given in Figure 5 is thus straightforwardly interpreted by the scenario that X-rays are mainly due to the coronal activity while H$`\alpha `$ is dominated by the chromospheric activity ($``$ a few tens Å) and by the disk activity ($``$ a few tens Å). These nondetections also suggest that BD X-ray activity does not likely originate from star-disk interaction but from the solar-like magnetic activity.

## 4 Conclusion

We report the detection of X-rays from an intermediate-age ($`t12`$ Myr) BD at a level of $`L_X4\times 10^{27}`$ erg s-1 (0.1–10 keV band) or $`\mathrm{log}L_X/L_{bol}=3.4`$. The X-ray spectrum is very soft; the dominant plasma temperature is only 0.3 keV. No variability is seen during the 10.3 ks observation. Those characteristics are common to those in the solar corona. Our observation provides a link between the active state seen in younger $`t1`$ Myr stellar clusters, and a relatively inactive state, showing continuity in the evolution of both X-ray luminosity and plasma temperature: $`\mathrm{log}L_X/L_{bol}`$ has not yet decayed by $`t12`$ Myr while $`kT`$ has already substantially cooled. The correlation between X-rays and H$`\alpha `$ implies the idea that the X-rays are mainly due to the coronal activity while H$`\alpha `$ is dominated by the chromospheric activity ($``$ a few tens Å) and by the disk activity ($``$ a few tens Å). Finally, we note that since TWA 5B is not far from the boundary between BDs and the most massive planets found orbiting nearby stars, it raises the possibility that massive planets might emit X-ray during their youth.

We express our thanks to all the $`Chandra`$ team for many efforts of the fabrication of satellite, launching, daily operation, software developments and calibrations. We also thank Leisa Townsley for supplying the CTI corrector of ACIS and Kensuke Imanishi the referee Gibor Basri for useful comments on brown dwarf flares and coronae. This research was supported by NASA contract NAS 8-38252.


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# Structure and electronic properties of new model dinitride systems: A density-functional study of 𝐂𝐍_𝟐, 𝐒𝐢𝐍_𝟐, and 𝐆𝐞𝐍_𝟐

## 1 Introduction

In recent years nitrogen has turned out to play a key role in todays most exciting technological applications of materials science. Important examples are the developement of III-V nitrides (AlN, GaN, InN) for light emitting diodes (LED) and lasers , the investigation of $`\mathrm{Si}_3\mathrm{N}_4`$ and $`\mathrm{SiO}_\mathrm{x}\mathrm{N}_\mathrm{y}`$ as promising candidates for ultrathin high dielectric materials substituting $`\mathrm{SiO}_2`$ in the race for ever shrinking field effect transistor (FET) gate lengths , and, finally, new ultra hard materials with the proposal of a model carbon nitride $`\mathrm{C}_3\mathrm{N}_4`$ as the hardest known material . However, all attempts to grow thin layers of nitrogen rich stoichiometries failed because of the easy release of nitrogen due to the high stability of molecular $`\mathrm{N}_2`$ . This major drawback led to propose nitrogen poor stoichiometries such as $`\mathrm{C}_{11}\mathrm{N}_4`$ . Nevertheless, the process of $`\mathrm{N}_2`$ release from $`\mathrm{CN}_\mathrm{x}`$ has not yet been investigated in detail and only recently a preliminary approach based on a model structure $`\mathrm{CN}_2`$ was presented . However, our knowledge about this class of nitride systems is far from exhaustive. To some extent this is due to the fact that the search for compounds with new materials properties is not straightforward and can be experimentally very demanding. In this situation, state-of-the-art computer simulations built on the principles of quantum mechanics as embodied in density functional theory (DFT) are very helpful. In particular, they even allow to investigate compounds, which are not yet synthesized.
Aiming at a deeper understanding of ultra hard nitrides we report in the present work on investigations of the lightest IV-V compounds $`\mathrm{CN}_2`$, $`\mathrm{SiN}_2`$ and $`\mathrm{GeN}_2`$ as crystallizing in an assumed cubic pyrite structure . This choice of hypothetical structure is guided by the observation that it allows to build up C-N bonds in a three-dimensional network while still satisfying the strong N-N bonding. At the same time, the simplicity of the pyrite structure offers the advantage that the different types of bondings can be easily addressed. Finally, this structure is also adopted by other isoelectronic $`\mathrm{AX}_2`$ compounds, as e.g. $`\mathrm{SiP}_2`$ . Further experimental evidence comes from N- or C-doped $`\mathrm{SiP}_2`$ and related compounds. In the pyrite structure, the N-N entities occupy octahedral holes formed by the C, Si and Ge fcc sublattices. The latter are well known from the cubic structures of diamond, SiC, SiGe, and TiC. As estimates for amorphous $`\mathrm{SiN}_\mathrm{x}`$  and $`\mathrm{SiN}_2`$ clusters  show, $`\mathrm{CN}_2`$ and $`\mathrm{SiN}_2`$ represent the large-$`\mathrm{x}`$ limit of those ultra hard and wide electronic band gap $`\mathrm{CN}_\mathrm{x}`$ and $`\mathrm{SiN}_\mathrm{x}`$ materials, which contain N-N-bonds.
From a chemical point of view, the transition from $`\mathrm{SiP}_2`$ to $`\mathrm{SiN}_2`$, $`\mathrm{CN}_2`$, and $`\mathrm{GeN}_2`$ involves several fundamental issues. These are the behaviour of the light group IV compounds C, Si and Ge in octahedral environments as well as that of nitrogen in the center of tetrahedra formed by one N and three C (Si/Ge) neighbours. The resulting description on the related bonding schemes should be found in between Pauling s covalent bonding  and ionic concepts like $`\mathrm{A}^{4+}[\mathrm{N}_2]^4`$ with the anions isoelectronic to $`[\mathrm{S}_2]^2`$ in pyrite $`\mathrm{FeS}_2`$. While $`[\mathrm{N}_2]^2`$ was proposed to appear in diacenides , covalent N-N-bonds have been proposed for clustered III-V semiconductor nitrides .
In this work we concentrate, using DFT-based methods, on finding the optimal crystal structure parameters of pyrite $`\mathrm{CN}_2`$, $`\mathrm{SiN}_2`$ and $`\mathrm{GeN}_2`$. In addition, we aim at relating the crystal structure stability to the electronic properties as well as to the chemical bonding.

## 2 Computational methods

The electronic structure calculations were performed within the framework of density functional theory and the local density approximation using two complementary approaches. First, full geometry relaxations including optimization of the cell volume and the atomic positions were performed with the help of an ultrasoft pseudopotential scheme as implemented in the VASP code . Calculations were converged at an energy cutoff of 434.82 eV for the plane-wave basis set. The Brillouin zone integration was performed using 11 to 76 irreducible $`𝐤`$ points and the tetrahedron method .
In a second step, the electronic properties of all three compounds were determined using the all-electron augmented spherical wave (ASW) method . In order to represent the correct shape of the crystal potential in the large voids, additional augmentation spheres were inserted into the open pyrite structure. Optimal augmentation sphere positions as well as radii of all spheres were automatically generated by the sphere geometry optimization (SGO) algorithm . The basis sets comprised $`s`$, $`p`$, and $`3d`$ states of the group IV element, N $`2s`$, $`2p`$ states as well as states of the additional augmentation spheres. The Brillouin zone integration was done using an increasing number of $`𝐤`$ points within the irreducible wedge ranging from 11 to 1135 points, again to ensure convergence of the results with respect to the $`𝐤`$-space grid.

## 3 Results and Discussion

### 3.1 Crystal structure optimization

The pyrite structure $`\mathrm{AX}_2`$ is best described in terms of the rocksalt structure with the A atoms and $`\mathrm{X}_2`$ occupying the two sublattices such that cubic symmetry with space group Pa$`\overline{3}`$ is preserved . As a result, the A atoms are found at the center of $`\mathrm{X}_6`$ octahedra, while three A atoms and one X atom form distorted tetrahedra about the X sites, see Fig. 1.

The pyrite structure is fully specified by two parameters, namely, the lattice constant and the positional parameter $`\mathrm{x}`$ of the X atoms.
To start with, we performed a structural optimization for $`\mathrm{SiP}_2`$, where the theoretical results could be checked against experimental data , see Tab. 1.

As expected, the lattice constant is slightly underestimated by the LDA calculations. In contrast, the internal parameter $`\mathrm{x}_\mathrm{P}`$ is almost exactly reproduced and so is the fraction $`\frac{\mathrm{d}_{\mathrm{X}\mathrm{X}}}{\mathrm{d}_{\mathrm{A}\mathrm{X}}}`$, with the P-P distance being shorter than the Si-P bond.
On going to the nitride we observe a drastic volume decrease with a calculated lattice constant of $`4.42`$ Å close to the value of 4.348 Å measured for $`\mathrm{SiC}`$ . In addition, the distance fraction $`\frac{\mathrm{d}_{\mathrm{X}\mathrm{X}}}{\mathrm{d}_{\mathrm{A}\mathrm{X}}}`$ has considerably decreased. While the N-N bond length amounts to 1.454 Å, the Si-N distance of 1.886 Å is very similar to the corresponding value of 1.889 Å observed for $`\mathrm{Si}_3\mathrm{N}_4`$ and is indicative of a single bond. For $`\mathrm{GeN}_2`$, our calculations yield a bigger cell, albeit, with a still shorter N-N distance of 1.428 Å.
Finally, optimizing the pyrite structure for $`\mathrm{CN}_2`$, we obtain an even smaller lattice constant of 3.982 Å. Together with the calculated internal parameter of $`\mathrm{x}_\mathrm{N}=0.403`$ this leads to an N-N distance of 1.34 Å. While still being much larger than in molecular $`\mathrm{N}_2`$ (1.09 Å), this value is considerably smaller than in $`\mathrm{SiN}_2`$ and $`\mathrm{GeN}_2`$ strengthening the double bond. At the same time the C-N distance of 1.695 Å is significantly larger than the 1.47 Å measured for the C-N single bonds of $`\mathrm{C}_3\mathrm{N}_4`$ indicating an even lower order. Applying the usual estimates for the hardness of $`\mathrm{CN}_\mathrm{x}`$ compounds  we calculate a bulk modulus of $`B_0=405`$ GPa from a Birch fit . Since this is harder than cubic BN, $`\mathrm{CN}_2`$ in the pyrite type structure may be regarded as a high-density ultra hard material. Since the energy values given in Tab. 1 are relative to the atomic energies and thus not indicative for the stability of the compounds, we performed additional supercell calculations for atomic C (Si, Ge) as well as molecular $`\mathrm{N}_2`$ and obtained a heat of formation of -4 eV/atom.

### 3.2 Electronic structure

The band structure of $`\mathrm{CN}_2`$ along selected high symmetry lines within the first Brillouin zone of the simple cubic lattice  as well as the partial densities of states (DOS) of all three compounds are shown in Figs. 2

and 3.

In these figures four groups of bands are identified. The two low-energy groups of bands each comprise four single bands. Bands are most easily counted along the line M-R, where they are fourfold degenerate. According to the partial densities of states these bands trace back mainly to the N $`2s`$ states, which form a bonding and antibonding subset of several eV width. Whereas the large splitting between these two groups is due to the short N-N distance the intrinsic band widths of both groups mainly result from the dispersion across the face-centered cubic (fcc) lattice formed by the nitrogen pairs. This is concluded from the level sequence at the $`\mathrm{\Gamma }`$ point into a lower nondegenerate and an upper threefold degenerate state. The latter results from folding the fcc bands into the simple cubic Brillouin zone (for the antibonding group of bands the sequence of levels is reversed). Further support comes from the striking similarity of the density of states especially of the bonding bands to that of a band calculated within the tight-binding approximation for an fcc lattice. Band widths are largest for $`\mathrm{CN}_2`$, which has the smallest lattice constant.
The electronic structure of the valence and conduction band are influenced by different types of bondings. Both groups comprise 20 bands, which derive from hybridization of all orbitals except for the N $`2s`$ states. Note that we have used a rotated coordinate system to separate the N $`2p`$ partial densities of states into contributions from orbitals mediating $`\sigma `$\- and $`\pi `$-type bonding within the $`\mathrm{N}_2`$ pairs. The calculated optical band gaps are 0.9, 5.5, and 1.4 eV for $`\mathrm{CN}_2`$, $`\mathrm{SiN}_2`$ and $`\mathrm{GeN}_2`$, respectively.
Common to all three nitrides is the strong bonding between group IV element $`p`$ states and those of nitrogen, which leads to bonding and antibonding bands in the energy regions \[-12:-6\] and \[5:9\] eV for $`\mathrm{CN}_2`$, \[-10:-4\] and \[10:15\] eV for $`\mathrm{SiN}_2`$, and \[-9:0\] and \[5:18\] eV for $`\mathrm{GeN}_2`$, respectively. Since the nitrogen atoms are coordinated by three group IV atoms this bonding is rather isotropic and, hence, involves both the $`2p_\sigma `$ and $`2p_\pi `$ states in the same manner with the ratio of 1:2 of their partial DOS reflecting their respective weight. Except for the carbon compound the unoccupied antibonding bands are dominated by the group IV element $`p`$ states, whereas the N $`2p`$ orbitals show a larger contribution to the bonding bands.
Differences between the three compounds, which cause, in particular, the spread in calculated optical band gaps, can be traced back mainly to the different influence of two additional types of bonding. These are, respectively, the bonding between the group IV element $`s`$ and the N $`2sp`$ states as well as the strong $`\sigma `$\- and $`\pi `$-type overlap within the nitrogen pairs. The former leads to considerable contributions of the C/Si/Ge $`s`$ states to the second group of bands as well as to the lower edges of the valence and conduction bands. Across the series, $`s`$-$`p`$ hybridization of the group IV element decreases and, on going from C to Ge, the bonding and antibonding bands involving the $`s`$ states are lowered in energy relative to the bands derived from the group IV element $`p`$ states. This effect is already visible for $`\mathrm{SiN}_2`$ and becomes most obvious for $`\mathrm{GeN}_2`$, where it leads to the substantial decrease of the optical band gap.
To the contrary, the $`\sigma `$\- and $`\pi `$-type overlap within the $`\mathrm{N}_2`$ pairs causes splitting of the $`2p_\sigma `$ and $`2p_\pi `$ states into bonding and antibonding bands. In the partial DOS, those N $`2p`$ states, which are subject to overlap within the pairs, can be easily identified by the smaller C/Si/Ge contributions in the respective energy range. However, due to the large N-N distance in both $`\mathrm{SiN}_2`$ and $`\mathrm{GeN}_2`$, this bonding/antibonding splitting is rather weak in these two nitrides. This is contrasted by the situation in $`\mathrm{CN}_2`$, where the close coupling of the nitrogen atoms leads to strong splitting into bonding and antibonding bands showing up in the energy intervals from \[-6:0\] and \[8:12\] eV, respectively. To conclude, the N $`2p`$ states are subject to two different types of bonding, namely, that inside the pairs and that with the group IV element $`sp`$ states. The bonding and antibonding states resulting from both types of chemical bonds end up in different energy regions. In particular, for $`\mathrm{CN}_2`$ the bonding bands resulting from N-N $`2p`$ overlap are higher in energy than the bands growing out of C/Si/Ge $`sp`$-N $`2p`$ overlap. As a consequence, the optical band gap is considerably reduced as compared to $`\mathrm{SiN}_2`$.

## 4 Conclusions

First principles calculations for the dinitrides $`\mathrm{CN}_2`$, $`\mathrm{SiN}_2`$ and $`\mathrm{GeN}_2`$ in assumed pyrite-type structures result in stable crystals. A bulk modulus of $`B_0`$ = 405 eV is calculated for $`\mathrm{CN}_2`$, which thus can be regarded as an ultra hard material. The electronic structures of all three nitrides are governed by three different types of bonding. Overlap of the C/Si/Ge $`s`$ and $`p`$ orbitals with the N $`2p`$ states lead to the formation of bonding and antibonding bands, which give rise to the valence and conduction groups of bands, respectively. In both groups, the C/Si/Ge $`s`$ derived states are found at the lower band edge. Lowering of the $`s`$ states relative to the $`p`$ states due to decreasing $`s`$-$`p`$ hybridization across the series C-Si-Ge results in a depression of the optical band gap of $`\mathrm{GeN}_2`$ as compared to that of $`\mathrm{SiN}_2`$. Close coupling within the $`\mathrm{N}_2`$ pairs especially in $`\mathrm{CN}_2`$ gives rise to a third type of bonding, namely $`\sigma `$\- and $`\pi `$-type overlap of the N $`2p`$ states. The resulting bonding and antibonding bands are found at the upper edges of the valence and conduction bands of $`\mathrm{CN}_2`$ and again lead to a strong decrease of the optical band gap as compared to $`\mathrm{SiN}_2`$.

## Acknowledgements

We are grateful to Profs. K.-J. Range and J. Etourneau for a lot of fruitful discussions, continuous interest, and support of this work. R. W. and V. E. gratefully acknowledge the kind hospitality of the ICMCB and the University Bordeaux 1. R. W. acknowledges financial support by the Training and Mobility Network ”New carbon based ultra hard Materials”, 1997-2002 ”FMRX-CT97-0103 (DG 12-MSPS)”. This work was supported by the Deutsche Forschungsgemeinschaft through SFB 484, Augsburg. Calculations were done on the Regatta IBM P690 of the M3PEC intensive numerical computations facility of the University Bordeaux 1.


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# Stored Light and Released Fiction

## I Introduction

Our attention was attracted to paper  by our colleague who decided to use the results of this work to “trap, store, and release” the object beam in a telescopic system. Being aware of our experience in magneto-optics and optical pumping in alkali vapors, he asked us to comment about experimental details of this publication. So, we had to thoroughly examine this paper. The result of this examination was rather unexpected: it became evident that the authors claims on the light storage have very little to do with real physical processes in the system.

## II Experimental

Recall that, in the work under consideration, rubidium atoms (in zero magnetic field) were excited by a laser tuned to the transition $`5^2S_{1/2}`$, $`F=25^2P_{1/2}`$, $`F^{}=1`$. The authors considered the exciting field as consisting of two coherent beams with orthogonal circular polarizations, namely, a strong $`\sigma _+`$-polarized “control” beam and a weaker $`\sigma _{}`$-polarized “signal” beam, which was turned on for a few tens of microseconds. After passing through the cell with Rb vapors, the two circularly polarized beams were detected by separate photodetectors. It is important that these two beams were treated independently, i.e., the $`\sigma _+`$-component at the exit of the medium was always attributed to the control beam ($`\sigma _+`$-polarized at the entrance), while the $`\sigma _{}`$-component, to the signal beam ($`\sigma _{}`$-polarized at the entrance). This approach contains a simple and fatal error that makes all the authors interpretation inadequate.

As experimentalists, we will analyze the observations described in  in general terms on the basis of simplest physical considerations to make the experimental situation as transparent as possible. We will leave aside the vast theoretical background of  for the reason that we strongly doubt about correctness of the simplest model (the three-level $`\mathrm{\Lambda }`$-scheme) used by the authors in the situation when the studied atomic line comprises 16 levels, with 11 of them being directly involved into the game through radiative and collisional processes. In addition, the strong fields used in the experiment connect 8 of these levels, thus making approximate methods inapplicable.

## III The picture of the observations

In fact, the authors examined a response of the atomic system to a pulsed modulation of the pumping circularly polarized beam, namely, during a time interval of 10 - 30 $`\mu `$s the beam was polarized elliptically. In the fundamentally nonlinear experiment (which we deal with), the medium excited by an elliptically polarized beam, with a distinguished direction in the plane of the wavefront, loses its axial symmetry (initially provided by the absence of external magnetic fields and by the axial circularly polarized pump), the circularly polarized waves cease to be eigenwaves of the medium, and the authors approach, which implies mutual independence of the circularly polarized waves in the medium, becomes invalid. Now, the “control” $`\sigma _+`$-polarized beam will detect the elliptic anisotropy of the vapor. It means that the beam will exhibit elliptic birefringence and dichroism (the latter being most important), and its polarization state will vary upon its propagation through the medium. At the exit of the medium, the “control” beam will prove to be elliptically (rather than circularly) polarized and, being decomposed into the basis circular polarizations, will contribute to the signal of the second detector which is supposed to detect the “signal” $`\sigma _{}`$-polarized beam. The same is valid for the “signal” beam, which will be detected by both detectors also. This is, briefly, what the authors observe.

## IV Three “surprising” stages of the experiment

In more detail, the mechanism of the observed polarization dynamics looks as follows (stages 1, 2, and 3 are indicated in the figure).

Stage 1. The medium, preliminary oriented by the strong “control” beam, is subjected to a pulse of elliptically polarized excitation, which renders the medium partially aligned. In view of relatively small duration of the “signal” pulse (as compared with the spin alignment time constant), the degree of alignment continuously increases during the pulsewidth (as the integral of the pulse energy), as well as does the fraction of the “control” beam detected in the “signal” channel. This process evidently has nothing in common with the “reduction of the light group velocity” in the medium. The growth of the signal in stage 1 reflects not the shape of the leading edge of the “signal” pulse, but rather the process of accumulation of the spin alignment. The transparency of the medium for the circularly polarized beam starts to slowly move toward its transparency for the light of elliptic polarization.

Stage 2. The light is turned off, and the alignment, thus accumulated or, more exactly, all the accumulated polarization moments remain stored in the system, relaxing with a characteristic time of about 1 ms. No energy is stored in the system and there are no grounds to be surprised that no output signal is observed as long as the light is off.

Stage 3. After the dark pause (stage 2), the “control” beam goes on detecting the residual elliptic anisotropy of the medium (partially relaxed during the pause), which is revealed, as before, in the nonorthogonality of the two circular polarizations in the medium and in branching of a fraction of the “control” beam into the “signal” channel. Now, however, the control beam, bringing strong orientation to the system, destroys the alignment much faster than it occurred in the darkness. The shape of the tail observed after the dark pause has nothing to do with that of the signal pulse. This tail reflects dynamics of the alignment destruction under the action of the control beam. This is why the duration of this tail will, in particular, depend on the control beam power, and the authors will never be able to “store” any other part of the pulse than its exponential-like tail. It may also seem curious for the authors interpretation that the total amount of the light emerging from the cell when the “stored” pulse is being “released” is smaller than when the “release” is over. This fact can be easily verified experimentally.

Thus, when we take into account the fact that the elliptically polarized light makes the medium elliptically anisotropic, all the observations became absolutely natural and trivial.

## V What is really stored

In a sense, the control beam, turned on after the pause, indeed reads out the information about the relative phase and energy of the signal beam. This information is stored in the magnitude and azimuth of the alignment and determines the phase and amplitude of the wave projected to the signal channel. But, first, the authors do not measure the phase of the signal wave and, second, what has it got to do with the storage of light ? The sense of this term the authors unambiguously explain in the fragment: A pulse of light which is several kilometers in free space is compressed to a length of a few centimeters and then converted into spin excitation of a vapor of Rb atoms. After a controllable time, the process is reversed and the atomic coherence is converted back into a light pulse . In our opinion, the experiment  is so simple that it does leave any room for this kind of speculations. Note, in addition to all the aforesaid, that the atomic coherence carries no energy in the absence of magnetic field: the acquired spin excitation means just a sort of spatially uniform spin anisotropy of the medium. As one can easily see, in the authors terminology, any quarter-wave plate stores circularly polarized light that can be released by irradiating it with circularly polarized light of opposite handedness. We do not find this language sensible.

## VI Conclusion

The interpretation of the results presented in  contains evident errors, and the reported experimental data (which, in themselves, seem quite correct) provide no evidence for the light “trapping, storage, and release”. In our opinion, this paper not only misleads the reader, but also arouses suspicion about other publications pertaining to the storage of light stream. This why we considered adequate evaluation of this paper important.