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# Bandgap Extremization: Some Exact Results

## 1 Introduction

Over the past decade, the design and study of photonic bandgap materials have attracted a lot of attention . The design process often involves extremization of a bandgap with respect to variations in the dielectric constant profile in the material, subject to certain constraints. Materials so designed are expected to find use in optical communication. The theoretical work in this field lies in two broad areas: exact results that prove existence and provide bounds  and numerical algorithms that provide optimal designs . In this paper we present a variational argument that provides criteria that the optimal design must satisfy, illustrated by two examples. (The calculations presented here are for quantum-mechanical bandgaps; however, the results are applicable also to the scalar Helmholtz equation - relevant for photonic band structure calculations - as indicated later.) The first example leads us to a maximum contrast rule: if the potential is allowed to vary over a range of values, the optimal configuration is a combination of the largest and smallest values. The second example starts with a constraint on the second moment of the potential energy and leads to a sufficient (but not necessary) relationship between the wavefunction and the potential that - rather surprisingly - are satisfied by the solution we obtain. We verify the criteria and examine their consequences in one-dimension. Our exact results may be used as benchmarks in testing numerical algorithms and as tests for sharpness of proposed bounds.

We begin with the Schrödinger equation

$$^2\psi +v\psi =ϵ\psi .$$
(1)
Upon imposing appropriate boundary conditions on the wavefunction $`\psi `$, this selects the energy eigenvalues $`ϵ_n`$ and eigenfunctions $`\psi _n`$. We assume $`v`$ to be real, and thus we can choose $`\psi _n`$ to be real. The index $`n=0,1,2,\mathrm{}`$ orders the energy levels, so $`ϵ_{n+1}ϵ_n`$. In one dimension with $`\psi `$ real, this index $`n`$ can be taken to be the number of nodes in the wavefunction, or equivalently the winding number in the $`\psi \psi ^{}`$ phase plane. In this paper - especially when we perform explicit calculations - we shall henceforth assume one dimension unless otherwise stated.

We now wish to consider the following sort of question: What potential $`v`$ \- subject to constraints - gives a maximum $`ϵ_n`$ for a particular state $`n`$? More elaborate questions will be considered shortly.

What type of constraints on the potential are we interested in? Since adding a constant $`v(\stackrel{}{r})v(\stackrel{}{r})+v_0`$ gives the trivial extension $`ϵ_nϵ_n+v_0`$, the first constraint on $`v`$ should probably be to fix the average of $`v`$, so

$$v=𝑑\tau v(\stackrel{}{r})=v_1.$$
(2)
The next constraint should limit the overall deviations from the average, and two reasonable choices might be to fix:

1. the second moment, so

$$v^2=𝑑\tau v^2(\stackrel{}{r})=v_2.$$
(3)
2. the maximum contrast, so

$$v_{max}v(\stackrel{}{r})v_{min}.$$
(4)

In general, we assume a set of $`J`$ constraints of the form

$$G_j[v]=𝑑\tau g_j[v]=v_j,j=1,2,\mathrm{},J.$$
(5)
(The maximum contrast constraint can be cast into this form by an appropriate limiting $`g[v]`$; however, as we shall see, there are more direct methods.)

Now suppose we have solved the Schrödinger equation (1). We now make a small perturbation of the form

$$v(\stackrel{}{r})v(\stackrel{}{r})+\delta v(\stackrel{}{r}).$$
(6)
We evaluate the effect of this perturbation on the energy eigenvalue, to first order:

$$\delta ϵ_n\delta v_n.$$
(7)
If we seek $`ϵ_n`$ to be an extremum then we require our original state to satisfy

$$0=\delta v_n=𝑑\tau \delta v\psi _n^2$$
(8)
for any allowed variation $`\delta v`$. As an example of constraints, let us fix the first and second moments of $`v`$; then we require

$`0`$ $`=`$ $`{\displaystyle 𝑑\tau \delta v}`$ (9)
$`0`$ $`=`$ $`{\displaystyle 𝑑\tau v\delta v}.`$ (10)
Thus, (8) can be satisfied in general if

$$\psi _n^2=\alpha +\beta v,$$
(11)
or

$$v=a+b\psi _n^2.$$
(12)
This allows us to close the equations by solving the non-linear Schrödinger equation

$$^2\psi _n+[a+b\psi _n^2]\psi _n=ϵ_n\psi _n.$$
(13)
The solution of the Schrödinger problem with the maximum contrast constraint is even easier, since we see from (8) that to maximize $`ϵ_n`$ we must choose

$$v=\{\begin{array}{c}v_{max},\text{ where }\psi _n^2>\varphi ^2\hfill \\ v_{min},\text{ where }\psi _n^2<\varphi ^2.\hfill \end{array}$$
(14)
The constant $`\varphi `$ is chosen by imposing the first moment constraint.

In general, then, $`\delta v_n=0`$ is satisfied by choosing

$$\psi _n^2=\underset{j=1}{\overset{J}{}}\alpha _j\frac{dg_j[v]}{dv}.$$
(15)
This equation can be inverted for $`v`$, giving $`v=h[\psi _n^2|\alpha ]`$, where $`\alpha `$ represents the set of $`J`$ parameters $`\alpha _j`$. We then solve appropriate non-linear equations:

$$^2\psi _n+h[\psi _n^2|\alpha ]\psi _n=ϵ_n\psi _n.$$
(16)
In this paper, we wish to maximize not the energy eigenvalues of the Schrödinger equation itself, but rather the energy bandgap between two levels, subject to constraints on the potential similar to previously. However, the constraints on the average of $`v`$ is not really necessary, since we consider only bandgaps. (Note that the indices on $`\psi `$ no longer refer to their ordering. In fact, we usually require that $`\psi _2`$, $`\psi _1`$ refer to consecutive eigenstates $`\psi _{n+1}`$, $`\psi _n`$, and so for periodic boundary conditions in one dimension, these wavefunctions - the band edges \- will have exactly the same number of nodes.) Thus, requiring the bandgap to be an extremum with respect to constrained variations of $`v`$, we now have the following three coupled equations:

$`^2\psi _2+v\psi _2`$ $`=`$ $`ϵ_2\psi _2`$ (17)
$`^2\psi _1+v\psi _1`$ $`=`$ $`ϵ_1\psi _1`$ (18)
$`\psi _2^2\psi _1^2`$ $`=`$ $`{\displaystyle \underset{j=1}{\overset{J}{}}}\alpha _j{\displaystyle \frac{dg_j[v]}{dv}}.`$ (19)
Again, we can invert to find $`v`$, and rewrite the problem as two coupled non-linear Schrödinger equations

$`^2\psi _2+h[\psi _2^2\psi _1^2|\alpha ]\psi _2`$ $`=`$ $`ϵ_2\psi _2`$ (20)
$`^2\psi _1+h[\psi _2^2\psi _1^2|\alpha ]\psi _1`$ $`=`$ $`ϵ_1\psi _1.`$ (21)
These equations are no longer quite so simple. We now consider our previous examples, in one dimension.

## 2 Two examples

### 2.1 Maximum contrast constraint

Without loss of generality, we reformulate the maximum contrast constraint as $`v_0v(x)0`$. Then returning directly to (7), we find

$$\delta (ϵ_2ϵ_1)=𝑑x[\psi _2^2\psi _1^2]\delta v0$$
(22)
with no constraint on the average of $`v`$. Clearly the solution is

$$v(x)=\{\begin{array}{cc}\hfill v_0,\text{if}& \psi _2^2(x)>\psi _1^2(x)\hfill \\ \hfill 0,\text{if}& \psi _2^2(x)<\psi _1^2(x).\hfill \end{array}$$
(23)
Furthermore, we fix $`v(x)`$ to be periodic with period $`L`$, and designate $`\psi _1`$ and $`\psi _2`$ as each having one node per period (of $`v(x)`$). In other words, the two selected wavefunctions are at the band edges with Bloch wave vector $`k=\frac{\pi }{L}`$. The sole adjustable parameter left in the potential is the width of the ‘barrier’ of height $`v_0`$, which we call $`2A`$ ($`0AL/2`$). Thus, we have:

$$v(x)=\{\begin{array}{cc}\hfill 0:& A<x<A\hfill \\ \hfill v_0:& A<x<LA\hfill \end{array}$$

extended periodically. Symmetry dictates that $`\psi _1`$ has nodes at $`x=mL`$ and $`\psi _2`$, at $`x=(n+\frac{1}{2})L`$ (or vice versa) where $`m,n`$ are integers. Therefore,

$$\psi _1(x)=\{\begin{array}{cc}\hfill \mathrm{cos}(k_1x):& A<x<A\hfill \\ \hfill a_1\mathrm{sinh}[\kappa _1(x\frac{L}{2})]:& A<x<LA\hfill \end{array}$$

and

$$\psi _2(x)=\{\begin{array}{cc}\hfill \mathrm{sin}(k_2x):& A<x<A\hfill \\ \hfill a_2\mathrm{cosh}[\kappa _2(x\frac{L}{2})]:& A<x<LA\hfill \end{array}$$

both extended periodically. Here $`k^2+\kappa ^2=v_0`$ and $`a_i`$ are constants that ensure matching at the boundaries and may be eliminated to give:

$$y_1\mathrm{tan}y_1=\sqrt{\frac{\eta ^2}{\alpha ^2}y_{1}^{}{}_{}{}^{2}}\mathrm{coth}\left(\left(\alpha 1\right)\sqrt{\frac{\eta ^2}{\alpha ^2}y_{1}^{}{}_{}{}^{2}}\right)$$
(24)
and

$$\frac{\mathrm{tan}y_2}{y_2}=\frac{1}{\sqrt{\frac{\eta ^2}{\alpha ^2}y_{2}^{}{}_{}{}^{2}}}\mathrm{coth}\left(\left(\alpha 1\right)\sqrt{\frac{\eta ^2}{\alpha ^2}y_{2}^{}{}_{}{}^{2}}\right)$$
(25)
where $`y_ik_iA`$, $`\alpha L/2A`$ and $`\eta \sqrt{v_0}L/2`$. The variables to be solved for are $`y_1,y_2`$ and $`\alpha `$. A third equation is provided by (23) which implies that $`\psi _1^2(x)=\psi _2^2(x)`$ at $`x=A`$ (and $`x=LA`$):

$`\mathrm{cot}^2y_1\left(1{\displaystyle \frac{\left(\alpha 1\right)y_{1}^{}{}_{}{}^{2}}{\frac{\eta ^2}{\alpha ^2}y_{1}^{}{}_{}{}^{2}}}\right){\displaystyle \frac{\mathrm{cot}y_1}{y_1}}\left(1+{\displaystyle \frac{y_{1}^{}{}_{}{}^{2}}{\left(\frac{\eta ^2}{\alpha ^2}y_{1}^{}{}_{}{}^{2}\right)}}\right)`$ (26)
$`=`$ $`\mathrm{tan}^2y_2\left(1{\displaystyle \frac{\left(\alpha 1\right)y_{2}^{}{}_{}{}^{2}}{\frac{\eta ^2}{\alpha ^2}y_{2}^{}{}_{}{}^{2}}}\right)+{\displaystyle \frac{\mathrm{tan}y_2}{y_2}}\left(1+{\displaystyle \frac{y_{2}^{}{}_{}{}^{2}}{\left(\frac{\eta ^2}{\alpha ^2}y_{2}^{}{}_{}{}^{2}\right)}}\right).`$
The solutions to these equations are displayed in the figures. Fig.1 is a simultaneous plot of $`\rho _1(A)`$, $`\rho _2(A)`$ and $`(ϵ_2ϵ_1)L^2/4`$ against $`\alpha `$ at $`\eta =5`$. Consistent with expectation, the energy difference is an extremum (maximum, in this case) when $`\rho _1(A)=\rho _2(A)`$, at $`\alpha =3.136`$; Fig.2 is a simultaneous plot of $`\psi _1`$, $`\psi _2`$ and $`v(x)`$ for this set of parameter values. Fig.3 shows $`\eta ^2(=v_0L^2/4)`$ against $`1/\alpha (=2A/L)`$. The breaks in the plot are a consequence of poor convergence of the numerical routine used as $`\kappa _2`$ and then $`\kappa _1`$ switch from imaginary to real with increasing $`\eta `$. Fig.4 shows $`ϵ_1L^2/4`$, $`ϵ_2L^2/4`$ and (for reference) $`v_0L^2/4`$ against $`v_0L^2/4`$. Finally, Fig.5 shows the energy difference (times $`L^2/4`$) in this case as well as for the potential $`v(x)=v_0\mathrm{cos}^2\frac{\pi x}{L}`$ for the same Bloch states, for comparison. (The latter has analytical eigenfunctions in terms of Mathieu functions.) As might be expected, the difference is larger with our optimized choice of potential.

### 2.2 Second moment constraint

The equations we are to solve are

$`\psi _2^{\prime \prime }+v\psi _2`$ $`=`$ $`ϵ_2\psi _2`$ (27)
$`\psi _1^{\prime \prime }+v\psi _1`$ $`=`$ $`ϵ_1\psi _1`$ (28)
$`\psi _2^2\psi _1^2=\alpha v.`$ (29)
We proceed with a roundabout strategy to solve these coupled equations by first solving the pair of coupled equations:

$`\psi ^{\prime \prime }+v\psi `$ $`=`$ $`ϵ\psi `$ (30)
$`\psi ^2`$ $`=`$ $`\beta v.`$ (31)
This is equivalent to the single equation

$$\psi ^{\prime \prime }\psi ^3/\beta +ϵ\psi =0,$$
(32)
which is (13) is one dimension. Suppose we find two such solutions with the same $`v`$, yet independent. Then we also have a solution to (27), with $`\alpha =\beta _2\beta _1`$. Clearly this gives a solution, but is it possible? The answer, as we demonstrate explicitly below, is yes.

We anticipate a periodic potential (with period $`L`$) and further impose the condition that the two energy eigenstates we seek are at the band edges, with period $`2L`$ for both. (The eigenfunctions may, then, be chosen to be real.) The solutions to (32) have remarkable properties , one of which is exploited here. The equation may be solved in terms of the (periodic) Jacobian elliptic functions sn or cn. (The third possibility, dn, turns out not to be appropriate.) We may now specifically require that the period of the potential be $`L`$. We finally obtain:

$`\psi _2(x)`$ $`=`$ $`{\displaystyle \frac{k}{\sqrt{L(1\text{E}/\text{K})}}}\text{sn}({\displaystyle \frac{2\text{K}x}{L}})`$
$`\psi _1(x)`$ $`=`$ $`{\displaystyle \frac{k}{\sqrt{L(1\text{E}/\text{K})}}}\text{cn}({\displaystyle \frac{2\text{K}x}{L}})`$
$`{\displaystyle \frac{(ϵ_2ϵ_1)L^2}{4}}`$ $`=`$ $`(k\text{K})^2`$ (33)
where E and K are the complete elliptic integrals of modulus $`k`$. Note that $`v`$ is linearly related to both $`\psi _1^2`$ and $`\psi _2^2`$. Defining $`\sigma ^2\frac{1}{L}_0^L𝑑x(v^2v^2)`$, we have

$$\sigma L^2=8\text{K}^2\sqrt{\frac{2(1+k^2)(1\text{E}/\text{K})k^23(1\text{E}/\text{K})^2}{3}}.$$
(34)
It is, perhaps, useful to think of the whole system as being parametrized by $`k`$. The suitably scaled energy difference and strength of the potential (as $`\sigma `$) may be easily obtained from equations (33) and (34), respectively. Fig.6 shows $`(ϵ_2ϵ_1)L^2/4`$ against $`\sigma L^2`$. For comparison, the same quantities for a sinusoidal potential and the optimized potential in the previous example are also plotted. As expected, our optimized potential gives the largest energy difference.

## 3 Conclusion

We have discussed strategies for bandgap extremization subject to two very different, but realistic, constraints on the potential energy function. Our conclusions, in both cases, are illustrated by one-dimensional examples. It is worthwhile pointing out that the variational argument in the first example applies explicitly in any dimension. The second relies on the serendipitous existence of two solutions to the equations (27) in one dimension. Whether this stroke of luck can be replicated in higher dimensions is, to our knowledge, an open question.

We acknowledge useful discussions with Graeme Milton and David Dobson. This work was supported in part by a grant from the U. S. National Science Foundation.


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# TRANSIENT PHENOMENA AND OUTBURSTS FROM GALACTIC BLACK-HOLE CANDIDATES

## 1 Before RXTE: spectral/timing states

Transient black hole candidates (TBHC) are the most important laboratories where we can study accretion onto black holes. The main reasons are two: first, there is a very limited number of bright persistent systems; second, transients go through a large range of mass accretion rate during their outbursts, therefore allowing us to study how the accretion properties change with accretion rate. In the case of persistent sources, they show rare state transitions (if any), and even when they do it is not clear what their dependence on accretion rate is (see e.g. ).

Before the launch of the Rossi X-ray Timing Explorer (RXTE), a relatively small number of systems was known (see  for a review). From these sources, a general “canonical” paradigm for the spectral/timing properties of TBHC had emerged (see ). Although there were notable exceptions, this paradigm was a good starting point for theoretical modeling. Four separate states were identified, which will be described here according to the behavior in the 2-20 keV band:

* Low/Hard State (LS): the energy spectrum can be described by a single power law with a photon index $`\mathrm{\Gamma }`$1.6. In addition, sometimes a weak disk-blackbody (DBB) component with kT$`<`$1 keV is observed, contributing less than a few percent to the detected flux. The Power Density Spectrum (PDS) is characterized by a strong band-limited noise with a break frequency below 1 Hz and a large fractional variability (30-50%). A low-frequency $`<`$1 Hz QPO is sometimes observed.
* Intermediate State (IS): the energy spectrum can be decomposed in two components: a power law with $`\mathrm{\Gamma }`$2.5 and a clearly detectable DBB with kT$``$1 keV. The PDS shows a band-limited noise with a break frequency higher than the LS (1-10 Hz) and a fractional variability of 5-20%. Sometimes a 1-10 Hz QPO is observed.
* High/Soft State (HS): the energy spectrum is dominated by a DBB component with kT$``$1 KeV, with the power-law component either below detection or extremely weak and steep ($`\mathrm{\Gamma }`$ 2–3). Very weak noise is detected in the PDS, in the form of a power-law with a few % of fractional variability.
* Very High State (VHS): the energy spectrum is a combination of a DBB (kT$``$1-2 keV) and a power law ($`\mathrm{\Gamma }`$ 2.5). The PDS can be of two types: either a band-limited noise similar to that of the IS, or a power-law, sometimes with a QPO. This state was observed only in two sources: the transient GS 1124-68 and the persistent source GX 339-4.

The dependence of these states and their transitions on increasing accretion rate was determined mostly by the only transient system that had shown all four of them, GS 1124-68 : LS–IS–HS–VHS. As one can see from the description above, the IS is very similar to the VHS, both in energy and timing characteristics. What was believed to be different between them is the value of the accretion rate: the VHS was observed at very high accretion rates, while the IS was observed much later in the outburst of GS 1124-68, after a long period of HS, and therefore at lower accretion rate (see ).

Despite the exceptions, a transient was expected to have a fast-rise/exponential-decay light curve (reflecting the time history of accretion rate), lasting a few months, possibly with one or more re-flares, undergo a number of state transitions in the sequence outlined above following accretion rate changes, and return to quiescence after a period of a few weeks to months, until the next outburst. Once again, the prototypical source would be GS 1124-68.

## 2 The RXTE “outburst”

With the advent of RXTE at the end of 1995 , our view of TBHC has been changed and widened. Thanks to the All-Sky Monitor (ASM) on board RXTE , we have been able to discover promptly both new transients and new outbursts of known ones. The flexibility of the mission allowed the accumulation of a vaste and valuable database of pointed observations with the narrow field instruments on board, covering the wide range 2-200 keV. In particular, the large collecting area of the PCA instrument  yielded high signal-to-noise data for timing and spectral analysis, and the availability of the RXTE archive on-line made these datasets easily accessible to the community. This resulted in a real “outburst” both of new sources and of publications on the subject.

In the rest of the paper, I will concentrate on the results on a few major systems and show how these have changed our overall picture. My approach will be mostly on the phenomenological side.

## 3 XTE J1550-564

This transient was discovered in September 1998 with RXTE and its outburst lasted until May 1999 (see  and references therein). Two more outbursts were detected in 2000 and 2001, but I will concentrate on the 1998/1999 one. As one can see from Fig. 1, the light curves in the PCA and HEXTE instruments look quite different, indicating large spectral changes.

A complete spectral analysis of these data can be found in . However, the second part of this outburst (after MJD 51139, see Fig. 1) was analyzed in terms of color-color diagrams (CCD) by , showing in a model-independent way the spectral evolution of the system. In Fig. 2 the CCD of XTE J1550-564 from  is shown. The colors are defined in such a way that the diagram preserves linearity, meaning that the sum of two models will result in a position lying between the points characterizing those models. The position of disk-blackbody models with different temperatures and power-law models with different photon indices are shown. Notice that the disk-blackbody points lie on a roughly vertical line, while the power-law line is much more inclined. This means that changes in the parameters of the two models are almost decoupled in this diagram. In Fig. 2, panel B refers to the times after MJD 51259, when the PCA gain was changed. Looking at panel A, we can follow the evolution the spectral distribution and, assuming the spectrum can be approximated with the sum of these models, we can have an idea of the state transitions.

At the beginning of the outburst the points are away from the DBB line, indicating the presence of a substantial amount of power law. Being the total flux relatively low, we can tentatively call this an IS. Then the source moves very close to the DBB line and slowly moves up, increasing the temperature of the DBB component: a HS. What follows is the flaring which can be seen in the HEXTE light curve in Fig. 1, corresponding to large deviations from the DBB line: VHS excursions. Overall, the evolution can be deconvolved in this way: the temperature of the soft component first increases then decreases smoothly, moving the source firs up then down in the diagram. The power law component changes in intensity in a rather uncorrelated way, bringing first the source close to the DBB line (small power-law contribution), then moving it away repeatedly during the flares. Looking at the timing properties, we see a PDS typical of a HS when the source is close to the DBB line, and extremely complex power density spectra, dominated by multi-peaked QPOs, when the contribution of the power law increases, strengthening the state identification. At the very beginning and at the very end of the outburst, when the power-law component dominates the flux, the PDS is characteristic of the LS .

What we have seen above is not what the simple picture of state transitions driven by accretion rate would predict. There are state transitions, but they seem to be decoupled from accretion rate. Figure 3 shows a schematic description of this (from ). While changes in the accretion rate are naturally responsible for variations in the temperature of the soft component (corresponding to large changes in detected flux), the power law component moves along different branches and transitions to the VHS can happen at different values of the accretion rate. On the contrary, the LS appears only at the beginning and at the end of the outburst, suggesting a connection to low accretion rates.

## 4 Spectral/timing states II

What shown above has important consequences for the picture of spectral/timing states. The first, already mentioned, is that state transitions in BHC are not driven only by mass accretion rate: a second independent parameter is needed. It is not in the scope of this paper to discuss physical possibilities for what this second parameter is. In GS 1124-68, the transitions were relatively simple and a sequence of states was identified , while here things behaved in a more complex fashion. Other sources, like GS 2023+338 , remained in the LS despite large changes in accretion rate, indicating that this second parameter did not vary. On the contrary, in the 1996 transition of Cyg X-1, a relatively small change in accretion rate was sufficient to trigger a state transition . The second consequence is that the IS becomes indistinguishable from the VHS, since its spectral/timing properties were identical to those of the VHS, the difference being only in the range of accretion rate at which it appeared . If the VHS can be triggered at any accetion rate, no IS is needed. This brings the number of states of black hole candidates back to three.

## 5 4U 1630-47

4U 1630-47 is a bright recurrent transient system that shows an outburst roughly every 600 days (see ). Since the launch of RXTE, it has showed four outbursts; here I concentrate on the second one, during 1998. The outburst light curve is shown in Fig. 4, and the corresponding CCD (defined in a similar way to that of XTE J1550-564 above) can be seen in Fig. 5 (both figures are from ).

In the case of 4U 1630-47, all points in the CCD lie close to the power-law line. The fact that the source moves from below to above that line indicate changes in the temperature of the soft component, but we never see a state dominated by it like in the case of XTE J1550-564. This can also be seen from the complete spectral analysis in . The data from  indicate that the source was always in the VHS. During the final stages of this outburst, the source entered the LS, as expected (see ). A parallel timing analysis shows indeed that the HS seems not to be entered at any time during this outburst. As in the case of XTE J1550-564, the VHS power spectra appear to be extremely complex and difficult to interpret .

In the case of 4U 1630-47, it is difficult to extract from the CCD information about the evolution of the mass accretion rate. However, five observations during this outburst were made with BeppoSAX during the decay part of the outburst (between TJD 10864-10899): detailed spectral analysis with a DBB plus power law model indicate that the data are consistent with no variation in the mass accretion rate . Of course this result is strongly model-dependent, but it suggests that rather large changes in the timing properties (see ) can appear without being driven by strong variations in the mass accretion rate.

## 6 GRO J1665-40

GRO J1655-40 is one of the first two microquasars (see ). RXTE observed a major outburst of this source in 1996 (see ). The RXTE/ASM light curve for this outburst is shown in Fig. 6. The outburst evolution looks similar to that of XTE J1550-564, with two separate parts, the second of which looks smoother than the first. Spectrally, three states could be identified: VHS in the first part of the outburst, HS in the second, with the exception of the last PCA observations, when the source switched to the LS (). In the timing domain, things did not look that simple. The only major difference between the first and the second part of the outburst was the presence of QPO features in the former . You can see the overall shape of these PDS in Fig. 7, where four PDS at the end of the outburst are shown (from ). The typical PDS for the source, QPOs excluded, is the bottom one, with a few % fractional variability. In a month time the source moved to a HS-like PDS and then to a typical PDS for a LS (see Fig. 7).

From this, the question arises: how is the VHS defined in the PDS domain? We have given a definition in Section 1, but after that we have different and complex PDS which we classified as VHS. This will be discussed later in this paper.

## 7 Spectral/timing states III

From what we have seen, we can summarize a few points about states and state-transitions:

* The soft disk component reacts to changes in the accretion rate, the hard component (a power law in the 2-20 keV band) reacts to something else (indicated as a question mark in Fig. 8).
* The LS is observed only at the beginning and at the end of the outbursts, indicating its association with a low accretion rate
* The main difference between VHS and HS is the presence of the hard component: if it is present, significant short-term variability is observed and the source is in the VHS. If it suppressed or absent, there is little variability and the source is in the HS. As indicated above, the appearance of the hard component is driven by a second parameter whose nature is not clear.
* It must be noted that it is not at all clear that the power-law components observed in the VHS and in the HS are the same component. In order to verify this, high-energy coverage is necessary, to check for the presence/absence of a high-energy cutoff (see ). In the case of GRO J1655-40, orbit-related absorption dips were observed: during these dips, both the disk and the power-law component were heavily absorbed, and an additional weak steep power law was visible . It is possible that this component is the HS power law, which would only become detectable when the other much brighter hard component disappears.

As mentioned above, the phenomenological description of the VHS needs to be discussed. We have seen very different PDS associated to this state, which are much more complex than what shown in Fig. 8. Indeed, it would be hard to describe a typical PDS for the VHS. In the timing domain, the difference with the HS is the presence of significant variability, whether in the form of continuum components or QPOs, above the 1-2% observed in the HS. This variability is associated to the hard component and not to the softer disk component, and indeed it is not observed when the hard component is missing.

## 8 GRS 1915+105

The systems examined so far had properties that were not too different from those mentioned in Sect. 1 for a well-behaved transient: their outburst was a few months long, although more complex than a fast-rise/exponential decay, and they underwent state transitions in the course of the outburst. The original microquasar, GRS 1915+105 did not behave equally well. As an X-ray source, it appeared in the sky in 1992  and remained bright since then.

Figure 9 shows the RXTE/ASM light curve of GRS 1915+105: it shows very marked variability, like the first part of the outburst of GRO J1655-40. However, unlike in the case of GRO J1655-40 (see ), this variability extends to very low time scales . This can be seen in Fig. 10, where a few examples of RXTE/PCA light curves, binned at 1 second, are shown.

This extraordinary variability has been interpreted as due to the repeated transitions between three basic states, called states A, B and C . A scheme of transitions between these states is shown in Fig. 11 (from ). Is there a relation between these three states and the three canonical states described above? Of course, transitions as fast and repeated as those shown in Fig. 10 are not observed in any other source, but the similarities might be stronger than the differences. In order to answer, we need to examine the states of GRS 1915+105 in more detail:

* State B: The energy spectrum consists of the superposition of a strong soft thermal component (with kT$``$2 keV) and a steep hard component $`\mathrm{\Gamma }`$3. The PDS is steep, bumpy, with a total fractional variability in the 5-10% range.
* State A: The energy spectrum is similar to that of state B, but softer. This difference is attributed by  to a softer temperature of the thermal component. The PDS is a bumpy power law, with fractional rms lower than state B.
* State C: The energy spectrum is dominated by the hard component, which is considerably flatter than in the other states, with $`\mathrm{\Gamma }`$ that can be as low as 1.8. The PDS shows a band-limited noise component with a variable break frequency (between 0.07 Hz and a few Hz). A low-frequency QPO is always present, with a centroid frequency strongly correlated with count rate and spectral hardness .

As one can see, states A and B seem to have something in common with the canonical VHS, while state C shows similarities with the LS, although the dependence of the timing parameters with rate and hardness is something that was seen before in the VHS of GS 1124-68 . In addition, by combining RXTE and CGRO/OSSE data,  showed that the broad-band spectrum of GRS 1915+105 in states C and B does not show any evidence of a high-energy cutoff (see Fig. 12, unlike typical BHC in the LS (see ).

At this stage, it is difficult (and dangerous) to claim any strong association between the three states of GRS 1915+105 and the canonical states of more conventional systems. The source is extremely bright and possibly what we see is only intances of VHS at very high accretion rates.

## 9 On the timing noise in the LS and in the VHS

As discussed above, there are indications that the hard components in the LS and in the VHS are different, as a high-energy cutoff is detected in the LS, but no high-energy cutoff is detected in the VHS . However, if one looks at the properties of the band-limited noise detected in these two states, such as the correlation between flat-top and break frequency in the PDS, the VHS points lie on the high-frequency extrapolation of the LS ones (, see Fig. 13). This is difficult to understand if the two components have a different physical origins: in this case both the characteristic noise frequency and the total fractional rms (see ) must be associated either to geometrical parameters or to the thermal disk component.

## 10 Spectral/timing states: conclusions

Since the launch of RXTE, thanks to the presence of the ASM and the operational flexibility of the mission, the available X-ray data on black hole candidates, especially transient systems, as increased substantially. The picture that emerges from the analysis of this large database is at the same time simpler and more complex than the paradigm that existed before. It is more complex because the phenomenology became quite complicated. The variety of QPOs observed in XTE J1550-564 and GRS 1915+105, and the extreme structured variability of the latter are perhaps the best examples. However, it also became somewhat simpler, as the number of basic spectral/timing states is now reduced to three, despite the tremendous diversity of some timing features, and the presence of a second parameter governing state transitions (although its physical nature needs to be addressed) might yield a direct measurement of a fundamental parameter of these systems. Among all sources, GRS 1915+105 shows more variability and state-transitions than all other sources together. it might be the way to solving basic problems of accretion, but it might also turn out to be an endless complication that leads away from the solutions. However, it is important that theoretical models address the general picture described above in addition to trying to describe in extreme detail the spectral distribution of a particular state in a particular source, especially since any spectral fit to low-resolution data involves by definition a strong a priori bias.

## ACKNOWLEDGEMENTS

I thank the Cariplo Foundation for financial support.


text:
# Fragmentation of positively charged metal clusters in stabilized jellium model with self-compression *footnote **footnote *This work is dedicated to the memory of my mother, Gohar and the 68th birthday of my father, Bahram.

## I Introduction

The fragmentation of ionic metal clusters as well as other properties of metallic clusters have been extensively studied using the jellium model (JM). In this model, the discrete ions are replaced by a uniform positive charge background of density $`n=3/4\pi r_s^3`$ in which $`r_s`$ is the bulk value of the Wigner-Seitz (WS) radius of the valence electrons of the metal. The simplest geometry for the positive background is spherical which is appropriate for closed-shell clusters or large enough clusters in which the Jahn-Teller  deformation has negligible contribution. However, using this simple spherical JM, a lot of information on the properties of metal clusters has been obtained. A refined version of the JM, the stabilized jellium model (SJM), which was introduced by Perdew et. al. in 1990, has improved some drawbacks of the JM (For a recent review on SJM, see Ref.\[REFERENCES\]). In recent years, the SJM has been used to predict the properties of bulk metals , metal surfaces, metal clusters and metallic voids. The fragmentation of charged metal clusters has been also studied by Vieira et. al. using the SJM. However, since the surface effects have a large contribution in the energetics and sizes of small clusters, and also since in a fission process the competition between the surface tension and coulomb repulsion leads to the existence of a barrier, a more sophesticated use of the SJM is needed to predict the correct energetics of the clusters and the barrier heights (BH) in the study of the fragmentation processes. This method, which is called SJM with self-compression (SJM-SC), has been used to predict the equilibrium sizes and energies of charged or spin-polarized metal clusters as well as the calculation of chemical potentials of metallic clusters. The SJM-SC has been also used by Sarria et. al. to calculate the surface energies and the work functions of metals. In contrast to the JM and the SJM in which the $`r_s`$ value is borrowed from the bulk system, in the SJM-SC, the density parameter $`r_s`$ of the jellium sphere is assumed to be a free parameter which can be adjusted in such a way that a cluster with a given number of electrons and specific electronic configuration achieves its equilibrium state. The SJM-SC calculations on neutral metal clusters has shown that the equilibrium $`r_s`$ value of the jellium sphere is less than the bulk value and tends to its bulk value for infinitely large cluster. This phenomenon is called self-compression which is due to the dominant effect of surface tension in small metal clusters. However, it has been shown that charging a small metal cluster can result in an equilibrium $`r_s`$ value which is larger than the bulk value. This effect is called self-expansion. The self-expansion has been also predicted for highly polarized metal clusters. These two effects have different origins. In the former, the repulsive coulomb force dominates the surface tension whereas, in the latter, the Pauli force is responsible for the self-expansion.

In this work, using SJM-SC, we have studied the binary decay processes of positively charged Ag clusters containing up to 100 atoms in all possible channels. We have considered the following possible decay processes for singly ionized Ag clusters

$$\mathrm{Ag}_N^{1+}\mathrm{Ag}_{Np}^{1+}+\mathrm{Ag}_p^0,p=1,2,\mathrm{},N2.$$
(1)
For doubly charged clusters, the decays can proceed via two different processes. The first one is the evaporation process

$$\mathrm{Ag}_N^{2+}\mathrm{Ag}_{Np}^{2+}+\mathrm{Ag}_p^0,p=1,2,\mathrm{},N3$$
(2)
and the second one is fission into two charged products

$$\mathrm{Ag}_N^{2+}\mathrm{Ag}_{Np}^{1+}+\mathrm{Ag}_p^{1+},p=2,3,\mathrm{},[N/2]$$
(3)
In general, for the binary decay of $`Z`$-ply charged ($`Z`$ is a positive integer) cluster, we have

$$\mathrm{Ag}_N^Z\mathrm{Ag}_{Np}^{Zz_1}+\mathrm{Ag}_p^{z_1},z_1=0,1,\mathrm{},[Z/2];p=z_1+1,\mathrm{},NZ+z_11.$$
(4)
For an even value of $`Z`$ with $`z_1=Z/2`$, the range of $`p`$ reduces to $`p=z_1+1,\mathrm{},[N/2]`$. The processes for which $`z_1=0`$ ( i.e., one of the fragments is neutral), are called evaporation processes and others ( both fragments are charged) are fission processes. In evaporation processes, the negativity of the difference between total energies before and after fragmentation is sufficient to have a spontaneous decay. However, in fission processes a negative value for the difference energy is not sufficient for the fission of the parent cluster. This is because, the competition between the short-range surface tension and the long-range repulsive coulomb force may give rise to a fission barrier ( i.e., one should supply energy to overcome the barrier).

The organization of this paper is as follows. In section II we explain the method of calculating the total energies and fission barriers. To obtain the total energy of a given cluster, we solve the self-consistent Kohn-Sham (KS) equations in the density functional theory (DFT) with local spin density approximation (LSDA) for the exchange-correlation (XC) functional. To calculate the fission barrier, we use the two-touching-spheres model for the saddle configuration. In section III, we discuss the results, and finally, we conclude this work in section IV.

## II Calculational Scheme

### A Total energy of a cluster

In the context of the SJM, the average energy per valence electron in the bulk with density parameter $`r_s`$ and polarization $`\zeta `$ is given by

$$\epsilon (r_s,\zeta ,r_c)=t_s(r_s,\zeta )+\epsilon _{xc}(r_s,\zeta )+\overline{w}_R(r_s,r_c)+\epsilon _\mathrm{M}(r_s),$$
(5)
where

$$t_s(r_s,\zeta )=\frac{c_k}{r_s^2}\left[(1+\zeta )^{5/3}+(1\zeta )^{5/3}\right]$$
(6)
$$\epsilon _{xc}(r_s,\zeta )=\frac{c_x}{r_s}\left[(1+\zeta )^{4/3}+(1\zeta )^{4/3}\right]+\epsilon _c(r_s,\zeta )$$
(7)
$$c_k=\frac{3}{10}\left(\frac{9\pi }{4}\right)^{2/3};c_x=\frac{3}{4}\left(\frac{9}{4\pi ^2}\right)^{1/3}.$$
(8)
All equations throughout this paper are expressed in Rydberg atomic units. Here $`t_s`$ and $`\epsilon _{xc}`$ are the mean noninteracting kinetic energy and the exchange-correlation energy per particle, respectively. For $`\epsilon _c`$ we use the Perdew-Wang parametrization. For a $`z`$-valent metal the average Madelung energy, $`\epsilon _\mathrm{M}`$, is defined as $`\epsilon _\mathrm{M}=9z/5r_0`$, in which $`r_0`$ is the radius of the WS sphere, $`r_0=z^{1/3}r_s`$. In Eq.(5), $`\zeta =(n_{}n_{})/(n_{}+n_{})`$ in which $`n_{}`$ and $`n_{}`$ are the spin densities of the homogeneous system with total density $`n=n_{}+n_{}`$. The quantity $`\overline{w}_R`$ is the average value (over the WS cell) of the repulsive part of the Ashcroft empty core pseudopotential,

$$w(r)=\frac{2z}{r}+w_R,w_R=+\frac{2z}{r}\theta (r_cr),$$
(9)
and is given by $`\overline{w}_R=3r_c^2/r_s^3`$ where, $`z`$ is the valence of the atom, $`\theta (x)`$ is the ordinary step function which assumes the value of unity for positive arguments, and zero for negative values.

The core radius is fixed to the bulk value, $`r_c^B`$, by setting the pressure of the unpolarized bulk system equal to zero at the observed equilibrium density $`\overline{n}=3/4\pi [\overline{r}_s^B(0)]^3`$:

$$\frac{}{r_s}\epsilon (r_s,0,r_c)|_{r_s=\overline{r}_s^B(0),r_c=r_c^B}=0.$$
(10)
Here, $`\overline{r}_s^B(0)\overline{r}_s^B(\zeta =0)`$ is the observed equilibrium density parameter for the unpolarized bulk system, and takes the value of 3.02 for Ag. The derivative is taken at fixed $`r_c`$, and the solution of the above equation gives $`r_c^B`$ as a function of $`\overline{r}_s^B(0)`$

$$r_c^B[\overline{r}_s^B(0)]=\frac{1}{3}[\overline{r}_s^B(0)]^{3/2}\left\{\left[2t_s(r_s,0)\epsilon _x(r_s,0)+r_s\frac{}{r_s}\epsilon _c(r_s,0)\epsilon _M(r_s)\right]_{r_s=\overline{r}_s^B(0)}\right\}^{1/2}.$$
(11)
The SJM energy for a spin-polarized system with boundary surface is given by

$`E_{\mathrm{SJM}}[n_{},n_{},n_+]`$ $`=`$ $`E_{\mathrm{JM}}[n_{},n_{},n_+]+\left(\epsilon _M(r_s)+\overline{w}_R(r_s,r_c^B)\right){\displaystyle 𝑑𝐫n_+(𝐫)}`$ (13)
$`+\delta v_{\mathrm{WS}}(r_s,r_c^B){\displaystyle 𝑑𝐫\mathrm{\Theta }(𝐫)\left[n(𝐫)n_+(𝐫)\right]},`$
where

$`E_{\mathrm{JM}}[n_{},n_{},n_+]`$ $`=`$ $`T_s[n_{},n_{}]+E_{xc}[n_{},n_{}]`$ (15)
$`+{\displaystyle \frac{1}{2}}{\displaystyle 𝑑𝐫\varphi ([n,n_+];𝐫)\left[n(𝐫)n_+(𝐫)\right]}`$
and

$$\varphi ([n,n_+];𝐫)=2𝑑𝐫^{}\frac{\left[n(𝐫^{})n_+(𝐫^{})\right]}{\left|𝐫𝐫^{}\right|}.$$
(16)
Here, $`n=n_{}+n_{}`$ and $`n_+`$ is the jellium density. $`\mathrm{\Theta }(𝐫)`$ takes the value of unity inside the jellium background and zero, outside. The first and second terms in the right hand side of Eq.(15) are the non-interacting kinetic energy and the exchange-correlation energy, and the last term is the Coulomb interaction energy of the system. The quantity $`\delta v_{\mathrm{WS}}`$ is the average of the difference potential over the Wigner-Seitz cell and the difference potential, $`\delta v`$, is defined as the difference between the pseudopotential of a lattice of ions and the electrostatic potential of the jellium positive background. The effective potential, used in the self-consistent KS equations, is obtained by taking the variational derivative of the SJM energy functional with respect to the spin densities as

$`v_{eff}^\sigma ([n_{},n_{},n_+];𝐫)`$ $`=`$ $`{\displaystyle \frac{\delta }{\delta n_\sigma (𝐫)}}(E_{\mathrm{SJM}}T_s)`$ (17)
$`=`$ $`\varphi ([n,n_+];𝐫)+v_{xc}^\sigma ([n_{},n_{}];𝐫)+\mathrm{\Theta }(𝐫)\delta v_{\mathrm{WS}}(r_s,r_c^B),`$ (18)
where $`\sigma =,`$. By solving the KS equations

$$\left(^2+v_{eff}^\sigma (𝐫)\right)\varphi _i^\sigma (𝐫)=\epsilon _i^\sigma \varphi _i^\sigma (𝐫),\sigma =,,$$
(19)
$$n(𝐫)=\underset{\sigma =,}{}n_\sigma (𝐫),$$
(20)
$$n_\sigma (𝐫)=\underset{i(occ)}{}\left|\varphi _i^\sigma (𝐫)\right|^2,$$
(21)
and finding the self-consistent values for $`\epsilon _i^\sigma `$ and $`\varphi _i^\sigma `$, one obtains the total energy.

In our spherical JM, we have

$$n_+(𝐫)=\frac{3}{4\pi r_s^3}\theta (Rr)$$
(22)
in which $`R=(zN)^{1/3}r_s`$ is the radius of the jellium sphere, and $`n(𝐫)`$ denotes the electron density at point $`𝐫`$ in space. Using the Eq. (21) of Ref. \[REFERENCES\], this average value is given by

$$\delta v_{\mathrm{WS}}(r_s,r_c^B)=\frac{3(r_c^B)^2}{r_s^3}\frac{3}{5r_s}.$$
(23)
Applying Eq. (13) to a metal cluster which contains $`N_{}`$ spin-up, $`N_{}`$ spin-down and $`N`$ $`(=N_{}+N_{})`$ total electrons in the ground state, the SJM energy becomes a function of $`N`$, $`r_s`$, and $`r_c^B`$. The equilibrium density parameter, $`\overline{r}_s(N)`$, for a cluster in the ground state electronic configuration, is the solution of the equation

$$\frac{}{r_s}E(N,r_s,r_c^B)|_{r_s=\overline{r}_s(N)}=0.$$
(24)
Here, the derivative is taken at fixed values of $`N`$ and $`r_c^B`$. For an $`N`$-electron cluster in its ground state electronic configuration, we have solved the KS equations self-consistently for various $`r_s`$ values and obtained the equilibrium density parameter, $`\overline{r}_s(N)`$, and its corresponding energy, $`\overline{E}(N)E(N,\overline{r}_s(N),r_c^B)`$.

### B Dissociation energy and fission barrier

The dissociation energy (DE) for the general binary decay process (4), defined as the difference in the sum of total energies of the products and the total energy of the parent cluster, is given by

$$D_{z_1}^Z(N,p)=(E_{Np}^{Zz_1}+E_p^{z_1})E_N^Z,$$
(25)
In evaporation processes ($`z_1=0`$), a negative value for the DE implies that the parent cluster is unstable against that particular decay channel and therefore, the fragmentation is spontaneous. On the other hand, a positive DE in a particular decay channel means that the parent cluster is stable against the decay in that particular channel. That is, one should somehow supply energy to the system to induce the fragmentation. For processes (1) and (2) the DE becomes

$$D_0^{1+}(N,p)=(E_{Np}^{1+}+E_p^0)E_N^{1+}$$
(26)
and

$$D_0^{2+}(N,p)=(E_{Np}^{2+}+E_p^0)E_N^{2+},$$
(27)
respectively. However, in the fission processes ($`z_1>0`$) as in Eq.(3), a negative DE does not mean that the cluster would decay. It is because of the existence of a fission barrier which originates from the short-range attractive (due to binding energy) and long-range repulsive (due to coulomb repulsion) forces between the charged products. The situation is shown in Fig. 1. Any excitation above the barrier, which may be induced by collisions or radiation, will eventually make the expected decay possible. One of the main deficiencies of the JM is that it gives negative values of surface energies for $`r_s2`$. Our using of SJM-SC is expected, therefore, to give more realistic values of surface energies and barrier heights. The fission barrier $`B_{z_1}^Z(N,p)`$ is approximated by the Coulomb interaction $`E_c`$ of two touching spheres (i.e., the fission products) and the DE as

$$B_{z_1}^Z(N,p)=D_{z_1}^Z(N,p)+E_c$$
(28)
For the Coulomb interaction between the two fission products we take into account their polarizabilities. The interaction energy of two charged conducting spheres can be calculated numerically using image charge method. An equally good but much simpler approach is the use of the analytical expression for the interaction between charges $`z_1`$ and $`z_2`$ with polarizabilities $`\alpha _1`$ and $`\alpha _2`$ at a distance $`s`$

$$E_{1,2}^{\mathrm{pol}}(s)=\frac{A_2}{A_4}\frac{2z_1z_2}{s}\frac{\alpha _1}{s^3}\frac{1}{A_4}\frac{z_2^2}{s}\frac{\alpha _2}{s^3}\frac{1}{A_4}\frac{z_1^2}{s}.$$
(29)
Here $`A_j`$ is given by

$$A_j=1\frac{j\alpha _1\alpha _2}{s^6},$$
(30)
and the polarizability of a conducting sphere (i.e., the metal cluster) with radius $`R`$ is  $`\alpha =R^3`$. An other formula which was used  for the Coulomb interaction of two touching conducting spheres is given by

$$E_{1,2}=\frac{2z_1z_2}{R_1+R_2+2\delta R}$$
(31)
where, for silver, the value $`\delta R=0.94`$ takes the polarizability into account. The BH’s for small clusters, obtained from this formula, are somewhat smaller than those we obtained using Eqs. (29), (30). Koizumi et. al. have calculated the barrier heights for the fission of doubly charged silver clusters using a shape function in the LDM with shell correction.

## III Results and discussion

After an extensive self-consistent SJM-SC calculations, we have calculated the equilibrium $`r_s`$ values and the energies of Ag$`{}_{}{}^{Z}{}_{N}{}^{}`$ ($`Z`$=0,1,2,3,4) for different cluster sizes $`(1N100)`$. To show the main differences in the equilibrium $`r_s`$ values of these clusters, which are appreciable for relatively small clusters, we have plotted, in Fig. 2, the corresponding $`\overline{r}_s(N)`$ values only up to $`N=34`$. As is obviously seen in the figure, the neutral and singly ionized clusters are self-compressed for all values of $`N`$. This is because of the dominant effect of the surface tension. However, for multiply charged clusters, the $`\overline{r}_s(N)`$ values cross the bulk border (i.e., $`r_s=3.02`$) at some $`N`$ which we show it by $`N_0`$. Our results show that, in general, for larger values of charging, the self-expansion persists up to larger values of $`N_0`$. That is, $`N_0^{2+}<N_0^{3+}<N_0^{4+}<\mathrm{}`$. For example, here we have obtained the values of 7, 17, 23 for $`N_0^{2+},N_0^{3+},N_0^{4+}`$, respectively. This means that, for larger charging values, the coulomb repulsion between excess charges dominates the surface tension up to larger values of $`N_0`$. It is also clearly seen in Fig. 2 that for clusters with the same numbers of electrons but different numbers of atoms, $`N`$, the following inequality holds

$$\overline{r}_s^0(N)<\overline{r}_s^{1+}(N+1)<\overline{r}_s^{2+}(N+2)<\overline{r}_s^{3+}(N+3)<\mathrm{}.$$
(32)
For Ag$`{}_{}{}^{4+}{}_{N}{}^{}`$ clusters, we could not find any solution of the Eq. (24) for $`N=5`$. That is, the single remaining electron is not able to bind the 5 constituent ions to each other in the Ag$`{}_{}{}^{4+}{}_{5}{}^{}`$ system. However, the solutions of $`\overline{r}_s^{4+}(6)=14.76`$ and $`\overline{r}_s^{3+}(4)=29.0`$ have been obtained for Eq. (24) which are so large that one can not realize the corresponding bound states experimentally and we ignore these bound states.

Figure 3 shows the equilibrium energies per atom in electron-volts for Ag$`{}_{}{}^{0}{}_{N}{}^{}`$, Ag$`{}_{}{}^{1+}{}_{N}{}^{}`$, Ag$`{}_{}{}^{2+}{}_{N}{}^{}`$, Ag$`{}_{}{}^{3+}{}_{N}{}^{}`$, and Ag$`{}_{}{}^{4+}{}_{N}{}^{}`$ with different cluster sizes ($`1N34`$). For comparison, we have also plotted the bulk value ($`\epsilon =7.89eV`$) by a dashed line. As is seen, by increasing the charge of a given $`N`$-atom cluster, the coulomb repulsion between the excess charge induces an inflation in the cluster (see Fig. 2) and therefore, the density of the material in the cluster decreases which, in turn, leads to a smaller binding energies.

In Fig. 4(a) we have plotted the DE’s of the most favored decay channels for the process $`\mathrm{Ag}_N^{1+}\mathrm{Ag}_{Np}^{1+}+\mathrm{Ag}_p^0`$. By definition, the DE is minimum in the most favored channel. We have shown the most favored value of $`p`$ by $`p^{}`$. The solid small square symbols show the most favored values $`p^{}`$ on the right vertical axis whereas, the corresponding DE’s, $`D_0^{1+}(N,p^{})`$, are shown on the left vertical axis by large open squares. The dashed line is the result of a fitting to the quantal DE’s. As is seen, the magority of the clusters have positive DE’s and therefore, they are stable against the spontaneous decay. However, the remaining clusters have negative DE’s and accorgingly, they decay into smaller fragments. Clusters close to the closed-shell ones, decay by emitting a monomer or dimer. On the other hand, clusters that are far from being a closed-shell, can break into two fragments each of which are close or identical to closed-shell ones. For example, Ag$`{}_{}{}^{1+}{}_{3}{}^{}`$ emits a neutral monomer and the remaining is a singly charged dimer, Ag$`{}_{}{}^{1+}{}_{44}{}^{}`$ emits an Ag$`{}_{}{}^{0}{}_{8}{}^{}`$ which is a closed-shell and the remaining is Ag$`{}_{}{}^{1+}{}_{36}{}^{}`$ which is close to a closed-shell, and finally, Ag$`{}_{}{}^{1+}{}_{80}{}^{}`$ emits Ag$`{}_{}{}^{0}{}_{20}{}^{}`$ and the situation is similar to the latter one. Except for the closed-shell singly ionized cluster Ag$`{}_{}{}^{1+}{}_{69}{}^{}`$, all other closed-shell singly ionized clusters, Ag$`{}_{}{}^{1+}{}_{N}{}^{}`$ ($`N`$=3, 9, 19, 21, 35, 41, 59, 91, 93) are stable against the spontaneous decay. The dashed fitted line which resembles the result of liquid-drop model (LDM) calculations ( see Fig. 4 of Ref. \[REFERENCES\]), predicts that all singly ionized clusters are stable and the asymptotic value of DE is constant and equal to $`0.20eV`$.

Figure 4(b) compares the experimental dissociation energies with the monomer DE’s $`D_0^{1+}(N,1)`$, dimer DE’s $`D_0^{1+}(N,2)`$, and the most favored DE’s $`D_0^{1+}(N,p^{})`$. As is seen, the most favored fragments are somewhere monomers, somewhere dimers and somewhere none of them. The general trend of the calculated monomer dissociation energies is similar to the experimental one and has a better agreement with the experiment than the other two DE’s. That is, from $`N=3`$ to $`N=4`$ the energy decreases; from $`N=4`$ to $`N=9`$ the energy increases in the mean; a decrease on going from 9 to 10; an increase from 10 to 21; and finally, a decrease from $`N=21`$ to $`N=22`$ and again increasing from $`N=22`$. However, our results lack the odd-even staggering because, it originates from the nonspherical shapes for the jellium. Resorting to non-spherical shapes also decreases the pronounced shell effects. The relative smallness of our calculated DE’s can be explained in terms of the details of the experimental setup. If the experiment starts using neutral Ag<sub>N</sub> clusters, then the equilibrium $`r_s`$ values would be smaller than the bulk value (see the $`Z=0`$ plot in Fig. 2), and therefore, the total energies would be more negative (see the $`Z=0`$ plot in Fig. 3). Now, irradiating the parent neutral cluster with a high power laser beam would lead to the ionization of the neutral cluster. If the photons also interact with the ionized cluster before the ionized cluster achieves its relaxed state, then the equilibrium $`r_s`$ value of the ionized cluster would be less than the relaxed value (In our calculations we have used the relaxed values at all steps.), and therefore, the magnitude of the total energy of the ionized parent cluster would be larger. This fact would lead to larger values of the DE’s. Comparing the experimental data with our results we conclude that the photo-dissociation occurs before the relaxation of the parent ionized cluster is completed. The other extreme is that we consider the ‘sudden’ approximation in which we assume that the relaxation time for the ionized cluster is infinite and the cluster undergoes the dissociation without changing the volume (i.e., the saturation approximation which is used in nuclear fragmentations and ordinary jellium calculations for clusters). In reality, neither of these extreme ‘relaxed’ or ‘sudden’ approximations are at work but something in between.

In Fig. 5(a) we have shown the most favored products Ag$`{}_{}{}^{0}{}_{p^{}}{}^{}`$ and the dissociation energies $`D_0^{2+}(N,p^{})`$ for the decay of Ag$`{}_{}{}^{2+}{}_{N}{}^{}`$ via evaporation channel. For this process, as in singly ionized case, the dashed fitted line predicts no spontaneous decays and shows a higher constant asymptotic DE as $`0.40eV`$. The most favored products are mainly monomers, dimers and octamers.

Figure 5(b) shows the barrier heights $`B_{1+}^{2+}(N,p^{})`$ for the most favored channels of the process $`\mathrm{Ag}_N^{2+}\mathrm{Ag}_{Np}^{1+}+\mathrm{Ag}_p^{1+}`$. By definition, the most favored fission channel has a minimum value for the BH. As is seen, some of the BH’s are negative. The negativity of a BH means that we need no energy to supply the system to initiate the fission. The dashed line which shows the mean behavior of BH intersects the zero line at $`N_a^{\mathrm{mean}}29`$ (the mean appearance size). This means that on the average, all Ag$`{}_{}{}^{2+}{}_{N}{}^{}`$ clusters with $`N<29`$ are unstable against spontaneous fission. The values of $`p^{}`$ show that most of the emitted fragments are closed-shell Ag$`{}_{}{}^{1+}{}_{N}{}^{}`$ clusters with $`N=3,9,21`$.

In Fig. 5(c) we have compared the most favored decays of Figs. 5(a) and 5(b). It is clearly seen that in a certain size range, the fission and evaporation definitly start their competition. Our quantal results in Fig. 5(c) show that in the size range $`21N26`$ the evaporation dominates the fission which is in good agreement with the Katakuse et. al. experimental results that reveal fission for $`N22`$. However, our result is slightly larger than the Krückeberg et. al. experimental data which show that the fission occurs for $`N16`$. This difference in the experimental results depends on the details of the experiment. For $`N>26`$, our results show that fission dominates again. To estimate the size range at which evaporation completely dominates the fission, we simply find the intersection point of the two mean behaviors (dashed lines) in Figs. 5(a) and 5(b). A simple calculation gives this mean critical value as $`N_c^{\mathrm{mean}}50`$. That is, in an induced fragmentation experiment of Ag$`{}_{}{}^{2+}{}_{N}{}^{}`$ clusters, the evaporation dominates the fission for $`N>50`$.

In Fig. 5(d) we have compared the most favored values $`D_0^{2+}(N,p^{})`$ and $`B_{1+}^{2+}(N,p^{})`$ with the experimental threshold energies. Here, also we have smaller DE’s and BH’s compared to the experiment. One reason for this behavior is that the equilibrium volume of the parent cluster is not equal to the sum of the equilibrium volumes of the product clusters (i.e., the ‘relaxed’ approximation) but is larger. The larger value of the equilibrium $`r_s`$ leads to a smaller magnitude of the initial energy and therefore, by Eq. (28) to a smaller barrier heights. In other words, the energy needed to deform the parent cluster toward the fission ( In deformation the surface area increases.) is partly paied as a result of self-expansion of the parent cluster. Our calculations show that in almost all decay channels, the sum of volumes of the decay products is smaller than that of the parent cluster which can be explained by the fact that in smaller clusters the surface effect is higher than that in larger clusters. The calculated results for the most favored values of DE’s at $`N=9`$ and $`N=10`$ are very close to the experimental values. The most favored products at $`N=9`$ and $`N=10`$ are neutral dimer and monomer, respectively (see Fig. 5(a)).

In Fig. 5(e) we have compared the calculated monomer DE’s $`D_0^{2+}(N,1)`$ and the singly charged trimer BH’s $`B_{1+}^{2+}(N,3)`$ with the experiment. Here also the difference is appreciable.

In Fig. 6(a) we have plotted the $`p^{}`$ and the $`D_0^{3+}(N,p^{})`$ for different cluster sizes. The situation is similar to other previous evaporation processes. Here also the asymptotic behavior of the fitted line predicts no decay and has a constant value of about $`0.50eV`$.

In Fig. 6(b), we have plotted the BH’s $`B_{1+}^{3+}(N,p^{})`$ for the most favored channel of the binary fission of the process $`\mathrm{Ag}_N^{3+}\mathrm{Ag}_{Np}^{2+}+\mathrm{Ag}_p^{1+}`$. Here, the fission products with smaller charge are more or less the same as those in the fission of Ag$`{}_{}{}^{2+}{}_{N}{}^{}`$ clusters. The mean behavior dashed line intersects the zero axis at $`N_a^{\mathrm{mean}}53`$. The slope of this line is larger than that of Fig. 5(b).

Figure 6(c) compares the most favored decays of Figs. 6(a) and 6(b). To our knowledge, there is no experimental results in the literature on the decay of Ag$`{}_{}{}^{Z}{}_{N}{}^{}`$ with $`Z3`$. It is seen that at $`N=38`$, evaporation dominates and from $`N=39`$ to $`N=42`$ evaporation and fission are equally probable. From $`N=43`$ to $`N=58`$, except for $`N=54`$, fission dominates again. From $`N=59`$ to $`N=67`$ the evaporation process overcomes and so on. To obtain the mean critical value, we find the intersection point of the two mean behaviors (dashed lines) in Figs. 6(a) and 6(b) which results in the value $`N_c^{\mathrm{mean}}80`$.

Fig. 7(a) plots the $`p^{}`$ and the $`D_0^{4+}(N,p^{})`$ for the evaporation processes of Ag$`{}_{}{}^{4+}{}_{N}{}^{}`$. In this figure, one notes the unstability of two smallest sized Ag$`{}_{}{}^{4+}{}_{7}{}^{}`$, Ag$`{}_{}{}^{4+}{}_{8}{}^{}`$ and the stability of almost all others against the evaporation. The fitted dashed line predicts no evaporation and has the asymptotic value of $`0.75eV`$. The evaporation products are seen to be mostly neutral dimers and a few monomers and octamers.

In Fig. 7(b) we have plotted the $`p^{}`$ and the $`B_{1+}^{4+}(N,p^{})`$ as functions of $`N`$. We see that at $`N=21`$ the BH becomes positive for the first time. The dashed line shows the mean behavior of the fission barries. This fitted line has crossed the zero axis at $`N_1^{\mathrm{mean}}74`$. That is, on the average, the Ag$`{}_{}{}^{4+}{}_{N}{}^{}`$ clusters are stable against the charge-asymmetric fission channel for $`N>74`$. The most favored charged products are mostly magic clusters, Ag$`{}_{}{}^{1+}{}_{N}{}^{}`$ with $`N=3,9,21`$.

The results of charge-symmetric binary fission of Ag$`{}_{}{}^{4+}{}_{N}{}^{}`$ for most favored decays are shown in Fig. 7(c). The smallest positive BH occurs at $`N=22`$. The mean behavior (the dashed line) intersects the zero line at $`N_2^{\mathrm{mean}}51`$.

In Fig. 7(d) we have compared the results for the three different decay processes of Ag$`{}_{}{}^{4+}{}_{N}{}^{}`$. It is seen that these clusters smaller than $`N50`$ are highly unstable. As is seen from the figure, it is difficult to specify the competitions for the quantal values. However, to give quantitative values, we have compared the fitted lines in Fig. 7(e). It is seen that for $`N<20`$ the charge-symmetric fission is the dominant spontaneous decay process but, for $`20<N<51`$ the dominant spontaneous fission process changes to the charge-asymmetric one. For $`51<N<73`$ the only spontaneous fission decay process is the charge-asymmetric one. Clusters larger than $`N_a^{\mathrm{mean}}73`$ are stable against any spontaneous decay process. In an induced fragmentation experiment of Ag$`{}_{}{}^{4+}{}_{N}{}^{}`$ clusters, the dominant process for $`73<N<107`$ is charge-asymmetric fission, and for $`N`$ larger than $`N_c^{\mathrm{mean}}=107`$ the evaporation process dominates. To summarize, for smaller clusters the charge-symmetric fission is dominant, and larger clusters prefer to decay via a charge-asymmetric fission process.

Besides the most favored quantities which are strongly related to the stability of the charged cluster and were explained in the above lines, it is also interesting to calculate the DE’s and BH’s for a process in which the fragment products are specified. Consider the process $`\mathrm{Ag}_N^Z\mathrm{Ag}_{N1}^Z+\mathrm{Ag}^0`$ in which one of the products is a neutral monomer. We have calculated the dissociation energies $`D_0^Z(N,1)`$ for all values of $`Z`$=1, 2, 3, 4 and $`N100`$. The calculated values show pronounced shell effects as in previous figures of the most favored channels. However, the mean behaviors have asymptotic constant values. For $`Z=1,2,3,4`$, these asymptotic values in electron-volts are 0.95, 1.00, 1.08, 1.15, respectively. This means that the monomer evaporation from a singly charged cluster needs a smaller energy than from a doubly charged and so on. The same analysis for the dimer evaporation in the process $`\mathrm{Ag}_N^Z\mathrm{Ag}_{N2}^Z+\mathrm{Ag}_2^0`$ shows also constant asymptotic mean behaviors for the $`D_0^Z(N,2)`$. The obtained values in electron-volts are 0.49, 0.59, 0.72, 0.87 for $`Z`$=1, 2, 3, 4, respectively. This means that, as in the monomer evaporation, the detachment of a dimer from singly ionized cluster is easier than from a doubly ionized cluster and so on. However, comparing the dissociation energies for monomer and dimer evaporation (keeping the charge constant) shows that atomic evaporation needs more energy than dimer evaporation.

Now, we consider the fission processes $`\mathrm{Ag}_N^Z\mathrm{Ag}_{N2}^{Z1}+\mathrm{Ag}_2^{1+}`$ and $`\mathrm{Ag}_N^Z\mathrm{Ag}_{N3}^{Z1}+\mathrm{Ag}_3^{1+}`$ in which one of the fission products is a singly ionized dimer or a singly ionized trimer. The mean behaviors of the BH’s for these processes are plotted in Fig. 8. As is seen, the energy needed to detach a singly ionized dimer decreases by increasing the charge of the parent cluster. This behavior should be contrasted to the behavior in the monomer or dimer evaporations. We recall that in the monomer or dimer evaporation, the dissociation energy increases by increasing the charge of the parent cluster.

It is now easy to find the mean sizes at which atomic evaporation process dominates the fission into singly ionized dimer or trimer for each charging value of the parent cluster. In doubly charged silver clusters, the monomer evaporation dominates the singly charged dimer and trimer detachments at $`N=11`$ and $`N=31`$, respectively. The corresponding numbers for triply charged clusters are 21 and 66. For parent clusters Ag$`{}_{}{}^{4+}{}_{N}{}^{}`$, the numbers $`N=38`$ and $`N=120`$ have been obtained. To summarize, by increasing the charge of the parent cluster the competition occurs at larger values of $`N`$.

## IV Conclusion

In this work, we have studied the fragmentations of multiply charged silver clusters taking into account the structural relaxations of the neutral and charged parent as well as daughter clusters. To calculate the relaxed-state sizes and energies of the clusters we have employed the stabilized jellium model with self-compression using a spherical geometry for the jellium background. Using these relaxed-state radius and energy for the clusters, we have calculated the dissociation energies and barrier heights for evaporation and fission processes in all possible channels. For the barrier heights, we have used the two-touching-spheres model with taking into account the polarizabilities of the two charged products. Comparison of our most favored results with the experimental data shows that our results lie under the experimetal results but, the critical size for the competition of the evaporation and the fission of doubly charged silver clusters is predicted in good agreement with the experiment. This comparison also reveals that the fragmentation processes mostly occur before the complete relaxation of the charged parent clusters. That is, in the above-mentioned experiments the structural relaxation time is larger than the average time elapsed for the fragmentation of the ionized parent cluster. Having the initial (just after ionization) and the relaxed sizes $`r_{s,\mathrm{ini}}^Z`$, $`r_{s,\mathrm{rela}}^Z`$ of a $`Z`$-ply ionized cluster, one may choose an $`r_{s,\mathrm{frag}}^Z`$ value ($`r_{s,\mathrm{ini}}^Zr_{s,\mathrm{frag}}^Zr_{s,\mathrm{rela}}^Z`$) for the ionized cluster (just before the fragmentation) such that the calculated values coincides the experimental ones. Then using a linear interpolation it is possible to calculate the relative fragmentation time for an ionized cluster. In ordinary jellium model calculations, the assumption

$$r_s^0(N)=r_s^Z(N)=r_{s,\mathrm{ini}}^Z(N)=r_{s,\mathrm{frag}}^Z(N)=r_{s,\mathrm{rela}}^Z(N)=r_{s,\mathrm{bulk}}$$
(33)
is used. It should be mentioned that for exact matching of the calculated and experimental values one should use non-spherical shapes.

We have obtained the asymptotic DE’s for the most favored channels in evaporation processes by fitting a simple curve on the quantal results. The result shows that the asymptotic values increase by increasing the charge of the parent cluster. In the case of Ag$`{}_{}{}^{4+}{}_{N}{}^{}`$, we have shown that for relatively small clusters the charge-symmetric fission process is dominant and then, before dominating the evaporation process the charge-asymmetric fission process overcomes. In general, the critical size (at which the evaporation dominates the fission) increases by increasing the charge of the parent cluster. The results show that the neutral $`p`$-mer dissociation energy increases by increasing the charge of the parent cluster; and for a given charged parent, the atomic evaporation needs more energy than a dimer evaporation. Finally, it has been shown that the energy needed for the detachment of a singly charged dimer or singly charged trimer decreases by increasing the charge of the parent cluster. However, for a given parent cluster, the detachment of a singly charged trimer is easier than that of a singly charged dimer.

Acknowledgement

The author would like to thank John P. Perdew for the useful discussions and comments during this work. He also thanks Adam Kiejna for providing me with his recent review article on the stabilized jellium model.