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# References

Quasiparticle dispersion and lineshape in a strongly correlated liquid with the fermion condensate

M.Ya. Amusiaa,b, V.R. Shaginyanc, 111E–mail: vrshag@thd.pnpi.spb.ru

$`^a`$The Racah Institute of Physics, Hebrew University, Jerusalem 91904, Israel;

$`^b`$Physical-Technical Institute, Russian Academy of Science, K-21 St. Petersburg, Russia;

$`^c`$ Petersburg Nuclear Physics Institute, Russian Academy of Science, Gatchina, 188350 Russia

## Abstract

A model of a strongly correlated electron liquid based on the fermion condensation (FC) is applied to the consideration of high temperature superconductors in its superconducting and normal states. Within our model the appearance of FC presents a boundary, separating the region of strongly interacting electron liquid from the region of strongly correlated electron liquid. We show that at temperatures $`TT_c`$ the quasiparticle dispersion in systems with FC can be presented by two straight lines, characterized by effective masses $`M_{FC}^{}`$ and $`M_L^{}`$, respectively, and intersecting near the binding energy which is of the order of the superconducting gap. This same picture persists in the normal state being modified only by the presence of the quasiparticle width. We argue that this strong change of the quasiparticle dispersion can be enhanced in underdoped samples due to strengthening the FC influence. The single particle excitation width and lineshape are also studied.

PACS: 71.27.+a, 74.20.Fg, 74.25.Jb

Keywords: Strongly correlated electrons; Phase transitions; Electronic structure

Recent discovery of a new energy scale for quasiparticle dispersion in Bi2Sr2CaCu2O8+δ in the superconducting and in normal states  have brought new insight to the physics of high temperature superconductors (HTS), imposing serious constraints upon the theory of HTS. The newly discovered additional energy scale manifests itself as a break in the quasiparticle dispersion near $`(5070)`$meV, which results in a drastic change of the quasiparticle velocity . Such a behavior is definitely different from what one could expect in a normal Fermi liquid. Moreover, this behavior can hardly be understood in the frame the marginal Fermi liquids (MFL) theory, because central conclusions of MFL theory are that the single-particle self energy has unimportant momentum dependence and there exists the only relevant energy scale which is defined by temperature $`T`$ of the normal state .

To describe a correlated liquid a conventional way can be used, assuming that the correlated regime corresponds to the noninteracting Fermi gas by adiabatic continuity in the same way as in the framework of the Landau normal Fermi liquid theory. A question is in order at this point: is it possible? Most likely the answer is negative. Thus, having in mind to attack the above-mentioned problem we direct our attention to a model in the frame of which a strongly correlated liquid is separated from conventional Fermi liquid by a phase transition related to the onset of FC . The aim of our Letter is to show that without any adjustable parameters the energy scale for quasiparticle dispersion is naturally explained within the presented model. Our Letter is organized as follows. First of all we focus on the general features of Fermi systems with FC. After that, we describe the quasiparticle dispersion and lineshape. Finally, we summarize the main results of our Latter.

Let us start by considering the key points of the FC theory. FC is related to a new class of solutions of the Fermi-liquid-theory equation ,

$$\frac{\delta (F\mu N)}{\delta n(p,T)}=\epsilon (p,T)\mu (T)T\mathrm{ln}\frac{1n(p,T)}{n(p,T)}=0,$$
(1)
for the quasiparticle distribution function $`n(p,T)`$, which depends on the momentum $`p`$ and temperature $`T`$. Here $`F`$ is the free energy, and $`\mu `$ is the chemical potential, while,

$$\epsilon (p,T)=\frac{\delta E[n(p)]}{\delta n(p,T)},$$
(2)
is the quasiparticle energy, being a functional of $`n(p,T)`$ just like the energy $`E[n(p)]`$ and the other thermodynamic functions. Eq. (1) is usually presented in the form of the Fermi-Dirac distribution,

$$n(p,T)=\left\{1+\mathrm{exp}\left[\frac{(\epsilon (p,T)\mu )}{T}\right]\right\}^1.$$
(3)
In homogeneous matter and at $`T0`$, one gets from Eqs. (1),(3) the standard solution $`n_F(p,T0)\theta (p_Fp)`$, with $`\epsilon (pp_F)\mu =p_F(pp_F)/M_L^{}`$, where $`p_F`$ is the Fermi momentum, and $`M_L^{}`$ is the generally used effective mass ,

$$\frac{1}{M_L^{}}=\frac{1}{p}\frac{d\epsilon (p,T=0)}{dp}|_{p=p_F}.$$
(4)
It is implied that $`M_L^{}`$ is positive and finite at the Fermi momentum $`p_F`$. As a result, the $`T`$-dependent corrections to $`M_L^{}`$, to the quasiparticle energy $`\epsilon (p)`$, and other quantities, start with $`T^2`$-terms. But this solution is not the only one possible. There exist “anomalous” solutions of Eq. (1) associated with the so-called fermion condensation . Being continuous and satisfying the inequality $`0<n(p)<1`$ within some region in $`p`$, such solutions $`n(p)`$ admit a finite limit for the logarithm in Eq. (1) at $`T0`$ yielding,

$$\epsilon (p)=\frac{\delta E[n(p)]}{\delta n(p)}=\mu ,p_ipp_f.$$
(5)
Equitation (5) leads to the minimal value of $`E`$ as a functional of $`n(p)`$ when in system under consideration a strong rearrangement of the single particle spectra can take place. We see from Eq. (5) that the occupation numbers $`n(p)`$ become variational parameters: the solution $`n(p)`$ takes place if the energy $`E`$ can be lowered by alteration of the occupation numbers. Thus, within the region $`p_i<p<p_f`$, the solution $`n(p)`$ deviates from the Fermi step function $`n_F(p)`$ in such a way that the energy $`\epsilon (p)`$ stays constant while outside this region $`n(p)`$ coincides with $`n_F(p)`$. As a result, the standard Kohn-Sham scheme for the single particle equations is no longer valid beyond the point of the FC phase transition . Such a behavior of systems with FC is clearly different from what one expects from the well known local density calculations. Therefore these calculations are hardly applicable to describe systems with FC. As to the quasiparticle formalism, it is applicable to this problem since, as it will be demonstrated, the damping of single particle excitations is not large compared to their energy . It is also seen from Eq. (5) that a system with FC has the well-defined Fermi surface. The new solutions, according to Eq. (1), within the interval occupied by the fermion condensate have at low $`T`$ the shape of the spectrum $`\epsilon (p,T)`$ linear in T ,

$$\epsilon (p,T)\mu (T)=T\mathrm{ln}\frac{1n(p)}{1(1n(p))}T(12n(p))T<<T_f.$$
(6)
We note that at $`TT_f`$ the occupation numbers $`n(p)`$ are approximately independent of $`T`$, being given by Eq. (5). Here $`T_f`$ is the quasi-FC phase transition temperature above which FC effects become insignificant ,

$$\frac{T_f}{\epsilon _F}\frac{p_f^2p_i^2}{2M\epsilon _F}\frac{\mathrm{\Omega }_{FC}}{\mathrm{\Omega }_F},$$
(7)
where $`\mathrm{\Omega }_{FC}`$ stands for the condensate volume, $`\epsilon _F`$ for the Fermi energy, and $`\mathrm{\Omega }_F`$ for the volume of the Fermi sphere. One can imagine that at $`T>0`$ dispersionless plateau $`\epsilon (p)=\mu `$ given by Eq. (5) is slightly turned counter-clockwise about $`\mu `$. As a result, the plateau is just a little tilted and rounded off at the end points. If $`TT_f`$, then according to Eqs. (1) and (6) the effective mass $`M_{FC}^{}`$ related to FC is given by,

$$\frac{p_F}{M_{FC}^{}}\frac{2T}{p_fp_i}.$$
(8)
To obtain Eq. (8) an approximation for the derivative $`dn(p)/dp1/(p_fp_i)`$ is used. Then, having in mind that $`p_fp_ip_F`$, the following estimates for the effective mass $`M_{FC}^{}`$ are obtained,

$$\frac{M_{FC}^{}}{M}\frac{N(0)}{N_0(0)}\frac{T_f}{T},$$
(9)
that show the temperature dependence of the effective mass. Here $`M`$ denotes the bare electron mass, $`N_0(0)`$ is the density of states of noninteracting electron gas, and $`N(0)`$ is the density of states at the Fermi level. Multiplying both sides of Eq. (8) by $`p_fp_i`$ we obtain the energy scale $`E_0`$ separating the slow dispersing low energy part, related to the effective mass $`M_{FC}^{}`$, from the faster dispersing relatively high energy part, defined by the effective mass $`M_L^{}`$,

$$E_02T.$$
(10)
It is seen from Eq. (10) that the scale $`E_0`$ does not depend on the condensate volume. Consider HTS compounds, then it is suggested that FC arises around the van Hove singularities, causing as it follows from Eqs. (8) and (9), the large density of states and the large value of the difference $`p_fp_i`$ at the singularities. Then, the volume and difference depend on the point of the Fermi surface, say, on the angle $`\varphi `$ along the Fermi surface, nonetheless, the magnitude $`E_0`$ remains constant, being independent of the angle. This differs essentially from the case for the effective mass $`M_{FC}^{}`$, that can be strongly dependent upon the angle through the difference $`p_f(\varphi )p_i(\varphi )`$, as it is seen from Eq. (8). It is pertinent to note that outside the FC region the single particle spectrum is insignificantly affected by the temperature, being defined by the ordinary effective Landau mass $`M_L^{}`$, given by Eq. (4), however calculated at $`pp_i`$ instead of at $`p=p_F`$. Thus, we come to the conclusion that a system with FC is characterized by two effective masses: $`M_{FC}^{}`$ that is related to the single particle spectrum at low energy scale, and $`M_L^{}`$ dealing with the spectrum at higher energy scale. These two effective masses manifest itself as a break in the quasiparticle dispersion, which can be approximated by two straight lines intersecting at the energy $`E_0`$. This break is observed at temperatures $`TT_f`$, and, as we will see below, at $`TT_c`$, when the superconducting state is grounded on the FC state. In this case the occupation numbers in the momentum area occupied by the fermion condensate are slightly disturbed by the superconducting pairing correlations so that effective mass $`M_{FC}^{}`$ becomes large but finite even at $`T=0`$. Note that at comparatively low temperatures FC and the superconductivity go together due to remarkable peculiarity of the FC phase transition. Indeed, this transition is related to spontaneous breaking of gauge symmetry: at $`T=0`$ the superconductivity order parameter $`\kappa (p)=\sqrt{n(p)(1n(p))}`$ has a nonzero value over the region occupied by the fermion condensate, while the gap $`\mathrm{\Delta }`$ may vanish .

It is seen from Eq. (5) that at the point of FC phase transition $`p_fp_ip_F`$, while the effective mass and the density of states, as it follows from Eqs. (5),(9), tend to infinity. One can conclude that at $`T=0`$ the beginning of the FC phase transition is connected to the absolute growth of $`M_{FC}^{}`$. The onset of the charge density-wave instability in a many electron system, such as electron liquid, which takes place as soon as the effective inter-electron constant reaches its critical value $`r_{cdw}`$, is to be preceded by the unlimited growth of the effective mass . In a simple liquid, the effective constant turns out to be proportional to the dimensionless average distance $`r_sr_0/a_B`$ between particles (electrons or holes) of system in question, with $`r_0`$ being the average distance, and $`a_B`$ is the Bohr radius. The physical reason for this growth is the contribution of the virtual charge density fluctuations to the effective mass. Note that the excitation energy of these fluctuations become very small if $`r_sr_{cdw}`$. Thus, when $`r_sr_{cdw}`$, FC can take place. So, the standard Fermi liquid behavior can be strongly disturbed and completely broken by strong charge fluctuations as soon as the insulator regime is approached in a continuous fashion. Let us remind that the charge-density wave instability takes place in three-dimensional (3D)  and two-dimensional (2D) electron liquids  at sufficiently high $`r_s`$. As soon as $`r_s`$ reaches its critical value the FC phase transition takes place. Thereafter, the condensate volume turns out to be proportional to $`r_s`$ as well as $`T_f/\epsilon _Fr_s`$ . Thus, we can accept a simple model relating systems with FC to strongly correlated metals: we suggest that the effective coupling constant $`r_s`$ increases with decreasing doping. This proposal assumes that both quantities $`T_f`$ and condensate volume $`\mathrm{\Omega }_{FC}`$ are increasing with decreasing doping. Thus, these are higher in underdoped samples comparatively to overdoped ones. Then, FC serves as a stimulating source of new phase transitions which lift the degeneracy of the spectrum. For example, FC can generate the spin density wave phase transition, or antiferromagnetic one, thus leading to a variety of the system’s properties. The superconducting phase transition is also aided by FC. The simple consideration presented above explains extremely large variety of HTS properties. In order to analyze the quasiparticle dispersion and lineshape at $`TT_c`$, we are going to investigate the situation when the superconductivity wins the competition with the other phase transition up to the critical temperature $`T_c`$.

We now discuss the origin of two effective masses $`M_L^{}`$ and $`M_{FC}^{}`$ in the superconducting state resulting in the nontrivial quasiparticle dispersion and in a change of the quasiparticle velocity. As we will see below our results are in a reasonably good agreement with experimental data . To simplify the discussion let us put $`T=0`$. The ground state energy $`E_{gs}`$ of a system in the superconducting state is given by the formula,

$$E_{gs}[\kappa (𝐩)]=E[n(𝐩)]+E_{sc}[\kappa (𝐩)],$$
(11)
where the occupation numbers $`n(𝐩)`$ are connected to the order parameter $`\kappa (𝐩)=\sqrt{n(𝐩)(1n(𝐩))}`$. The second term $`E_{sc}[\kappa _p]`$ on the right hand side of Eq. (11) is defined by the superconducting contribution which in the simplest case is of the form,

$$E_{sc}[\kappa _p]=V_{pp}(𝐩_1,𝐩_2)\kappa (𝐩_1)\kappa (𝐩_2)\frac{d𝐩_1d𝐩_2}{(2\pi )^4}.$$
(12)
Consider a 2D liquid on a simple square lattice which is in the superconducting state with d-wave symmetry of the order parameter $`\kappa (𝐩)`$. In such a case, the long-range component in momentum space of particle-particle interaction $`V_{pp}`$ is repulsive. The sort-range component is relatively dominant and attractive at the small momenta . Then, we suppose that FC arises near the Van Hove singularities, causing, as it follows from Eq. (9), large density of states at these points . Under such circumstances, as a first approximation we assume the different regions of the maximal value $`\mathrm{\Delta }_1`$ of the gap $`\mathrm{\Delta }`$ are disconnected . Therefore, we can approximate the particle-particle interaction by its short-range component, it is assuming that $`V_{pp}(q)V_2\delta (q)`$. Varying $`E_{gs}`$ given by Eq. (11) with respect to $`\kappa (𝐩)`$ one finds,

$$(\epsilon (𝐩)\mu )\mathrm{\Delta }(𝐩)\frac{12n(𝐩)}{2\sqrt{n(𝐩)(1n(𝐩))}}=0.$$
(13)
Here $`\epsilon (𝐩)`$ is defined by Eq. (2), and,

$$\mathrm{\Delta }(𝐩)=V_{pp}(𝐩,𝐩_1)\sqrt{n(𝐩_1)(1n(𝐩_1))}\frac{d𝐩_1}{4\pi ^2}.$$
(14)
A few remarks are in order at this point. If $`V_20`$, then $`\mathrm{\Delta }(𝐩)0`$, and Eq. (13) reduces to,

$$\epsilon (𝐩)\mu =0,\mathrm{if}\mathrm{\hspace{0.17em}\hspace{0.17em}\hspace{0.17em}0}<n(𝐩)<1;\kappa (𝐩)0,$$
(15)
producing FC solutions, defined by Eq. (5) . Taking into account Eq. (15), we come to the conclusion that if $`V_2`$ is sufficiently small, then in the first order in $`V_2`$ the function $`\kappa (𝐩)`$ is defined by Eqs. (5),(15). The gap $`\mathrm{\Delta }`$ is given by Eq. (14), while $`n(𝐩)`$ is fixed by Eq. (5), and as it is seen the gap is linear in the coupling constant of the particle-particle interaction .

As soon as coupling constant $`V_2`$ becomes finite but small, plateau $`\epsilon (𝐩)\mu =0`$ is slightly tilted and rounded off at the end points. As a result, taking into account the $`\delta `$-like shape of the particle-particle interaction, one gets from Eqs. (13) and (14),

$$\epsilon (𝐩)\mu \frac{V_2}{2}(12n(𝐩)),$$
(16)
which allows to estimate the effective mass,

$$\frac{p_F}{M_{FC}^{}}\frac{V_2}{p_fp_i}\frac{2\mathrm{\Delta }_1}{p_fp_i}.$$
(17)
Now, one can directly conclude from Eq. (17),

$$E_0\frac{(p_fp_i)p_F}{M_{FC}^{}}2\mathrm{\Delta }_1.$$
(18)
Note that calculations in the frame of a simple model land additional support to the presented consideration . Eq. (17) allows to estimate effective mass $`M_{FC}^{}`$ connected to the region occupied by FC at temperatures $`TT_c`$. Outside this region the effective mass is defined by $`M_L^{}`$, being roughly independent of the pairing correlations and temperature. It is seen from Eq. (18), that again this time at $`TT_c`$, the quasiparticle dispersion can be presented by two straight lines characterized by two effective masses, $`M_{FC}^{}`$ and $`M_L^{}`$, respectively, and intersecting near binding energy $`E_02\mathrm{\Delta }_1`$. The break separating the faster dispersing high energy part, related to mass $`M_L^{}`$ from the slower dispersing low energy part defined by $`M_{FC}^{}`$, is likely to be more pronounced in underdoped samples at least because of the rise of temperature $`T_f`$, since the lower is the doping, the higher is $`T_f`$. We remind that in accordance with our assumption the condensate volume $`\mathrm{\Omega }_{FC}`$ is growing with the underdoping. It was also suggested that FC arises near the van Hove singularities, while the different areas of FC overlap only slightly. Therefore, it follows from Eq. (17), that as one moves from the node of the gap towards its maximal value $`\mathrm{\Delta }_1`$, that is from minimal value of $`\mathrm{\Omega }_{FC}(\varphi )`$ towards the maximal one, the ratio $`M_{FC}^{}/M_L^{}`$ grows in magnitude, transforming the dispersion kink into a distinct break. In fact, suggesting that temperature $`T_f`$ depends on the angle $`\varphi `$ along the Fermi surface, that is $`T_f(\varphi )`$, and taking into account that $`T_f`$ reaches its maximal value at the fermion condensate area, one can arrive at the same conclusion. The dispersions above $`T_c`$ exhibit the same structure except that effective mass $`M_{FC}^{}`$ is governed by Eq. (8) rather then (17), and both the dispersion and break are disguised partly by the quasiparticle width. Thus, one can conclude that there also exists a new energy scale at $`TT_f`$ defined by $`E_0`$ and closely related to $`T_f`$ .

Now let us turn to the quasiparticle excitations with the energy $`E(\varphi )=\sqrt{\epsilon ^2(\varphi )+\mathrm{\Delta }^2(\varphi )}`$. At temperatures $`T<T_c`$ these are typical excitations of the superconducting state. Here we are going to perform a qualitative treatment of processes contributing to the width $`\gamma `$. Within the frame of this analysis, we can take gap $`\mathrm{\Delta }0`$, considering excitations at the node of the gap. Then, our treatment holds for both $`TT_c`$ and $`T_cT`$. For definiteness, we consider the decay of a particle implying that momentum $`p>p_F`$. Then, the width $`\gamma (p,\omega )`$ is given by ,

$$\gamma (p,\omega )=2\pi \left|\frac{V(q)}{ϵ(q,\omega _{pq})}\right|^2n(𝐤)(1n(𝐤+𝐪))\delta (\omega _{pq}+\omega _{kq})\frac{d𝐪d𝐤}{(2\pi )^4},$$
(19)
with $`ϵ(q,\omega _{pq})`$ being the complex dielectric constant, and $`V(q)/ϵ`$ is the effective interparticle interaction. Here $`𝐪`$ and $`\omega _{kq}=\epsilon (𝐤+𝐪)\epsilon (𝐤)`$ are the transferred momentum and energy, respectively, and $`\omega _{pq}=\omega \epsilon (𝐩𝐪)`$ is the decrease in the energy of the quasiparticle as a result of the rescattering processes: quasiparticle with energy $`\omega `$ decays into two quasiparticles $`\epsilon (𝐩𝐪)`$ and $`\epsilon (𝐤+𝐪)`$ and quasihole $`\epsilon (𝐤)`$. The transferred momentum $`q`$ must satisfy the condition,

$$p>|𝐩𝐪|>p_F.$$
(20)
Eq. (19) gives the width as a function of $`p`$ and $`\omega `$, while the width of a quasiparticle of energy $`\epsilon (p)`$ is given by $`\gamma (p,\omega =\epsilon (p))`$. Estimating the width given by Eq. (19) with the limitation (20) and $`\omega _{pq}T`$, one finds for normal Fermi liquids

$$\gamma (p,\omega =\epsilon (p))\left(M_L^{}\right)^3T^2.$$
(21)
In the case of FC one could estimate $`\gamma 1/T`$ upon using Eqs. (9) and (21) . This estimate were correct if the dielectric constant is small, but it is not the case since $`ϵM_{FC}^{}`$. Now in the event of FC one has,

$$\gamma (p,\omega =\epsilon (p))\frac{\left(M_{FC}^{}\right)^3T^2}{\left(M_{FC}^{}\right)^2}T\frac{T_f}{\epsilon _F},$$
(22)
here $`\epsilon _F`$ is the Fermi energy . Calculating $`\gamma (p,\omega )`$ as a function of $`p`$ at a constant value of $`\omega `$, the same result is obtained for the width that is given by Eq. (22) when $`\omega =\epsilon (p)`$. The calculated function can be fitted with a simple Lorentzian, since quasiparticles and quasiholes engaged in the decay process are also located in the vicinity of the Fermi level provided $`\omega \epsilon _FT`$. Thus, the well-defined excitations exist at the Fermi surface even in the normal state . This result is in accord with the experimental findings determined from the scans at constant binding energies, (momentum distribution curves or MDCs) . On the other hand, considering $`\gamma (p,\omega )`$ as a function of $`\omega `$ at constant $`p`$, one can check that the quasiparticles and quasiholes contributing to $`\gamma (p,\omega )`$ may have the energy of the same order of the magnitude. Then, when $`\omega \epsilon _FT`$, the function is of the same Lorentzian form, otherwise the shape of the function at high $`\omega `$ is disturbed by high energy excitations that hardly can be considered as well defined quasiparticles or quasiholes. Then the special form of the quasiparticle dispersion, characterized by the two effective masses, should be taken into consideration. In view of the fact that the contribution of these excitations related to effective mass $`M_L^{}`$ is enhanced by the presence of FC, and taking into account the background at high $`\omega `$, one can conclude that the peak inevitably has a broadening which can hardly be interpreted as standard width defined by either Eqs. (21) or (22). On the other hand, one may follow the procedure suggested in , using the Kramers-Krönig transformation to construct the imaginary part of the self-energy starting with the real one. As a result, the lineshape of the quasiparticle peak as a function of $`\omega `$ possesses a complex peak-dip-hump structure directly defined by the existence of two effective masses $`M_{FC}^{}`$ and $`M_L^{}`$, that give rise to the quasiparticle dispersion approximated by two straight lines. Under these conditions the lineshape is of non-Lorentzian, which coincides with observational data obtained from constant momentum scans (EDCs) . It is worth to note that our consideration shows that it is the spectral peak obtained from MDCs that provides important information on the existence of well-defined excitations at the Fermi level and their width . The detailed numerical results will be presented elsewhere.

In summary, we have discussed a model of a strongly correlated electrons which has the FC phase transition and applied it to a consideration of high temperature superconductors. The FC transition fulfills the role of a boundary, separating the regions of strongly interacting electrons and strongly correlated electrons. At $`TT_c`$ the quasiparticle dispersion in systems with FC can be represented by two straight lines, characterized by effective masses $`M_{FC}^{}`$ and $`M_L^{}`$, respectively, and intersecting near binding energy $`E_0\mathrm{\Delta }_1`$. We have also shown that this effect persists at $`T_fTT_c`$. It is argued that this strong change of the quasiparticle dispersion at $`E_0`$ can be enhanced in underdoped samples because of strengthening the FC influence. The single particle excitations and their width $`\gamma `$ are also studied. It is demonstrated that well-defined excitations with $`\gamma T`$ exist at the Fermi level even in the normal state. This result is in line with the experimental findings derived from scans at constant binding energies. As to the dispersion of the quasiparticle peak obtained from constant momentum scans, it has a complex peak-dip-hump structure directly related to the existence of two effective masses $`M_{FC}^{}`$ and $`M_L^{}`$, that determine the quasiparticle velocity showing a break near the binding energy $`E_1`$.

This research was funded in part by the Russian Foundation for Basic Research under Grant No. 98-02-16170.


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# Untitled Document

Temperature, Pressure & Solvent Dependence of Positronium Acceptor Reactions

Debarshi Gangopadhyay, Bichitra Ganguly & Binayak Dutta-Roy

Saha Institute of Nuclear Physics, I/AF Bidhannagar, Calcutta 700 064, India

S.N. Bose National Centre for Basic Sciences, III/JD Bidhannagar, Calcutta 700 098

PACS No.: 82.55.+e,71.60.+z, 78.70.Bj

## Abstract

Positronium (Ps) reaction rates ($`\kappa `$) with weak Acceptors (Ac) leading to the formation of Ps-Ac Complexes show several intriguing features: non-monotonic temperature dependence of $`\kappa `$ (departing from the usual Arrhenius paradigm), considerable variability of $`\kappa `$ with respect to different solvents, and anomalies in response to external pressure at ambient temperature (large changes of $`\kappa `$ in some media and hardly any in others). We explain all these phenomena, introducing the novel concept of a critical surface tension, which unifies observations in diverse non-polar solvents at different temperatures and pressures.

The Positronium (Ps) atom, as the ‘lightest isotope of hydrogen’, enters into various chemical reactions, amongst which we shall concentrate here on those with diamagnetic organic compounds (equipped with a suitable low-lying molecular orbital) such that a Positronium-Acceptor (Ps-Ac) Complex can form in the presence of some solvent (S).

The observed rate constant ($`\kappa `$) for a given Acceptor depends on the solvent and for a given solvent varies in a rather remarkable manner with temperature ($`T`$), namely:

$``$ $`\kappa `$ increases with $`T`$ at low temperatures,

$``$ $`\kappa `$ reaches a maximum at $`T=T_0`$ (the turnover temperature),

$``$ $`\kappa `$ decreases with increasing $`T`$ above $`T_0`$.

This is shown in Fig.1 for the case of the weak Acceptor nitrobenzene in different solvents.

This unusual phenomenon , first observed by Goldanskii and his group  at Moscow, and subsequently by Hall, Madia and Ache , is in sharp contrast with the normal trend in activated chemical processes where $`ln\kappa `$ versus $`1/T`$ (the inverse temperature) yields a straight line with negative slope, as the rate is proportional to the Maxwell-Boltzmann probability factor $`\mathrm{exp}(E^{}/k_BT)`$ where $`k_B`$ is the Boltzmann constant and $`E^{}`$ is the activation energy or barrier height to be overcome by thermal agitation. Possible prefactors are generally taken to be mildly dependent on temperature.

Another dramatic observation  pertains to the variation of the rate constant for Ps-Ac Complex formation with external pressure at ambient temperature, which shows surprisingly strong solvent dependence. Thus, for instance, with nitrobenzene as the Acceptor and hexane as the solvent the rate constant $`\kappa `$ was found to be enhanced by a factor of almost thirty as the pressure was increased to $``$ 1000 kg/cm2, while with benzene as the solvent the same rate manifested only small variation over the same pressure range. This feature is depicted in Fig.2. Kobayashi  conjectured that this could indicate a difference in reaction mechanism in cases which do and those which do not show marked pressure dependence, and that a correlation could be sought with the corresponding solvent dependence of the turnover temperature.

The objective of this letter is to put forward a heuristic model which captures the essence of all these puzzling aspects of Positronium reactions outlined above, through a remarkably simple and reasonably accurate semi-quantitative description. As we shall see, the widely used bubble model for Ps-annihilation in liquids provides a suitable setting for the purpose at hand. This was proposed by Ferrel  to account for the observed largeness of the ortho-Positronium (o-Ps) pick-off lifetime, whereby the positron in o-Ps seeks out an electron in the surrounding medium with opposite spin (not its partner in o-Ps which is in a spin triplet state) to decay into two gammas. He suggested that due to the repulsive interaction between o-Ps and the atoms of the surrounding liquid, the Positronium pushes away the molecules of the liquid and gets self-trapped in a cavity or bubble. The decreased probability for the positron to find an electron (of the surrounding medium) in its immediate vicinity leads to the lengthening of the pick-off lifetime. For simplicity he took the trapping potential to be an infinitely repulsive spherical well of radius $`R`$. The resulting quantal zero-point energy of Ps with mass $`2m`$ ( $`m`$ being the electron mass) is $`E_0=\frac{\pi ^2\mathrm{}^2}{4mR^2}.`$ This exerts an outward ‘pressure’ viz. $`\frac{E_0}{R}`$ to be balanced by the contractile forces of compression due to the surface tension ($`\sigma `$) of the fluid, thereby minimizing the total energy $`E_{tot}=E_0+4\pi R^2\sigma `$ viz. $`\frac{E_{tot}}{R}=\frac{2\pi ^2\mathrm{}^2}{4mR^3}+8\pi \sigma =0`$ resulting in a bubble of radius $`R_0=(\frac{\pi \mathrm{}^2}{16m\sigma })^{1/4}=(12.445)/\sigma ^{1/4}`$Å , where $`\sigma `$ is measured in dynes/cm ( .624$`\times `$ 10 -4 eV/Å2). This model was further developed by Tao  and by Eldrup et al.  employing again the infinite spherical well but describing the picked-off electrons as forming a thin layer uniformly coating the inner surface of the bubble. Though such a description has been criticised on account of the infinite repulsion  or the unrealistic nature of the sharpness of the bubble edge , nevertheless as a first approximation the model does rather well in explaining the observables in the case of pure solvents (lifetime and angular correlation of decay gammas).

In this framework the formation of the Ps-Ac Complex within the cavity results, through the restriction on the motion of the Positronium due to its binding to the Acceptor, in a release of the outward ‘uncertainty pressure’ and accordingly the bubble begins to shrink under the influence of the surface tension. As the bubble wall approaches the Positronium (bound to the Acceptor with some energy $`E=B`$ where $`B`$ is the binding energy), the increasing proximity of the solvent molecules leads (because of the augmented repulsive energy) to a reduction of the binding, until at some radius $`R_b`$ of the bubble the Ps-Ac bond is broken viz. $`B=0`$. To raise the status of this contention  to at least a semi-quantitative level let us consider the Positronium to be subjected to an attractive potential $`V(r)`$ due to the Acceptor, while it also feels the infinite repulsion due to the solvent located at the bubble wall at a distance $`R`$. Taking the potential $`V(r)`$ to be a spherical well  of depth $`V_0`$ and range $`a`$ viz. $`V_0\mathrm{\Theta }(aR)`$ where $`\mathrm{\Theta }`$ is the step function, the relevant Schrödinger equation for the centre-of-mass motion of Ps is

$$\left[\frac{\mathrm{}^2}{4m}\frac{d^2}{dr^2}V_0\right]u=Bu\mathrm{for}r<a$$
$`(1a)`$
$$\left[\frac{\mathrm{}^2}{4m}\frac{d^2}{dr^2}\right]u=Bu\mathrm{for}r>a$$
$`(1b)`$
with $`\psi =u/r`$. The appropriate boundary conditions are $`u(r=0)=0`$ and $`u(r=R)=0`$, while $`u`$ and its derivative must be continuous at $`r=a`$, yielding the eigenvalue condition

$$k\mathrm{tan}\kappa a=\kappa \mathrm{tanh}k(Ra)$$
$`(2)`$
where $`k=\sqrt{\frac{4mB}{\mathrm{}^2}}`$ and $`\kappa =\sqrt{\stackrel{~}{g}^2k^2}`$ with $`\frac{4mV_0}{\mathrm{}^2}=\stackrel{~}{g}^2`$. The bond breaking radius $`R_b`$, viz. where $`k=0`$, is thus given by

$$R_b=a\left[1\frac{\mathrm{tan}\stackrel{~}{g}a}{\stackrel{~}{g}a}\right].$$
$`(3)`$
Since in the leading approximation (adopted by us) the effect of the solvent is represented by an infinite repulsion (tantamount to a boundary condition forcing $`\psi `$ to vanish at $`R`$), the radius $`R_b`$ depends only on the characteristics of the Acceptor vis a vis its affinity for the Positronium, and is, to that extent, same for all solvents. However, we must also consider the fact that the Ps-Ac-bubble system would equilibrate at some radius $`R_{min}`$ at which the total energy is a minimum, namely,

$$\frac{}{R}[B+4\pi R^2\sigma ]=0.$$
$`(4)`$
This leads to

$$R_{min}=(\frac{1}{8\pi \sigma })(\frac{\mathrm{}^2}{4m})(\frac{1}{a^4})\frac{6\zeta ^4}{(\zeta \mathrm{tan}\zeta )(3\zeta 3\mathrm{tan}\zeta +3\zeta \mathrm{tan}^2\zeta 2\mathrm{tan}^3\zeta )}$$
$`(5)`$
where $`\zeta \stackrel{~}{g}a`$. Whether the Ps-Ac-bubble system will be stable or not will depend on whether $`R_{min}`$ is greater than or lesser than the bond-breaking radius $`R_b`$.

A big step forward is made possible by our recognition that in leading approximation $`R_b`$ is essentially solvent independent, while solvent dependence enters through $`R_{min}`$ and that too only through $`\sigma `$. As the surface tension of the solvent is a function of temperature, the equilibrium radius of the bubble (with Ps-Ac inside) depends on temperature only through $`\sigma `$ viz. $`R_{min}(T)=R_{min}[\sigma (T)]`$. As $`T`$ is decreased, $`\sigma `$ increases and by virtue of eq.(4) and more explicitly eq.(5), $`R_{min}`$ decreases. When $`R_{min}`$ becomes less than $`R_b`$ the Ps-Ac-bubble system is no longer stable. Clearly there is a critical value of $`\sigma `$, say $`\sigma _{cr}`$, at which $`R_{min}[\sigma _{cr}]=R_b`$, marking the watershed beyond which the Ps-Ac-bubble system destabilises. The value of $`T`$ at which $`\sigma `$ attains the value $`\sigma _{cr}`$ depends on the particular solvent, but $`\sigma _{cr}`$ does not, but is, in the leading order, a property of the Acceptor under consideration. We argue that the turnover temperature $`T_0`$ is the temperature at which, for the solvent at hand, $`\sigma (T_0)=\sigma _{cr}`$. Indeed at sufficiently high temperature where $`\sigma (T)<\sigma _{cr}`$, a large negative change in enthalpy occurs as the reactants \[Ps in a bubble of radius $`R_0=(\frac{\pi \mathrm{}^2}{16m\sigma })^{1/4}`$ and the Acceptor\] react to form the product \[Ps-Ac Complex in bubble\] with the radius having shrunk to $`R_{min}`$. This makes it a down-hill reaction, since for weak Acceptors the activation energy is expected to play a sub-dominant role and also the effect of solvent viscosity is negligible (because the complex is protected by the bubble from the buffetting by the solvent molecules). It is thus basically the negative activation volume that is responsible for the anti-Arrhenius behaviour for $`T>T_0`$. On the other hand for $`T<T_0`$ when $`\sigma (T)>\sigma _{cr}`$ the Ps-Ac-bubble system is unstable, the Ac is squeezed out of the bubble and the formation of the Complex must of necessity take place in the milieu of the solvent accompanied by the continual impact of the solvent molecules. As such, following Kramers  the role of the medium would be said to belong to the Smolochowski regime, with the dependence of the rate constant on the viscosity ($`\eta `$) varying as $`\frac{1}{\eta }D`$ (where $`D`$ is the diffusion coefficient of the liquid, the last step being a consequence of the Einstein-Stokes relation). In view of the smallness of the activation energy for weak Acceptors, we would therefore expect that $`\kappa \mathrm{exp}[E_\eta /k_BT]`$, where $`E_\eta `$ is the activation energy associated with the process of diffusion. The reaction in this region would be diffusion controlled and would exhibit a normal Arrhenius behaviour. This enables us to make the important prediction that $`\sigma (T_0)=\sigma _{cr}`$ and that it is approximately solvent independent. In order to confront this with experiment, we have plotted in Fig.3, $`\sigma (T)`$ against $`TT_0`$ for various solvents (for which data is available with nitrobenzene as the Acceptor).

It is indeed highly gratifying to note that while $`T_0`$ differs widely from solvent to solvent, and also the values of the surface tension $`\sigma `$ at a given temperature for different solvents have a substantial spread, nevertheless $`\sigma (T_0)=\sigma _{cr}`$ for the solvents under consideration lie in a rather narrow range, namely, $`\sigma _{cr}=26\pm 2`$ dynes/cm.

Armed with this value of $`\sigma _{cr}`$ we are now in a position to access the Ps-Ac interaction parameters which, as we shall discuss below, are unfortunately not available from any other source. Being led by the estimates of other authors  let us fix the range of the interaction to be $`a`$ = 1.5 Å , and determine $`\stackrel{~}{g}`$ by putting, in accordance to our discussions above, $`\sigma =\sigma _{cr}`$ and $`R_{min}=R_b`$ \[refer eq.(3)\]. This immediately yields the value $`\stackrel{~}{g}`$ =1.25 Å-1 which corresponds to the Ps-Ac binding energy (the Acceptor being nitrobenzene) $`B_0=0.18eV`$. Note that $`B_0`$ signifies the basic binding in the absence of the solvent, namely, $`B_0=Lim_R\mathrm{}B`$, which implies vide eq.(2), the well-known result: $`\kappa \mathrm{cot}\kappa a=k`$ the eigenvalue condition for a spherical well. Unfortunately there is no direct measurement of this binding energy $`B_0`$, and the approaches based on first principles  are beset with huge theoretical uncertainties. However, using our methodology we have now completely tied down the model and shall proceed to show how this explains all the main observed features,

In order to find the slope of the $`ln\kappa `$ versus $`1/T`$ plot in the higher temperature anti-Arrhenius region we recognise that this is nothing but the activation free energy, the major contribution to which come from the change in Enthalpy arising from the shrinkage of the bubble from its value given by $`R_0`$ to the size determined by $`R_{min}`$, viz. $`4\pi R_{min}^2\sigma 4\pi R_0^2\sigma `$ where, of course the radii are functions of temperature through the surface tension. To this must be added the change in the Ps-Ac binding due to the approach of the bubble wall from $`R_0`$ to $`R_{min}`$. The resulting behaviour (appropriately normalized) is depicted in Fig.1 for the case of Ps nitrobenzene reaction in heptane, for instance, as a solvent. The slope obtained through our model corresponds to $``$ 0.15 eV which agrees very well with the experimental value. The part of the plot in the Arrhenius regime is also shown by using the value of the activation energy for diffusion ($`E_\eta `$). Fig.1 demonstrates that the main aspect of the temperature dependence of the rate has been captured in a satisfactory manner.

Apart from providing an interpretation of the temperature dependence of the reaction as set forth above, this simple model is also able to furnish an explanation of the observed variation with the external pressure (P). In view of the small compressibility of liquids one would hardly expect any appreciable activation volume when $`T<T_0`$ as the reaction occurs in the solvent itself. However, for $`T>T_0`$ due to the involvement of the bubble a large $`\mathrm{\Delta }V^{}`$ (activation volume) becomes possible and hence a significant pressure dependence can occur, in view of the basic Polyani relationship:

$$\left(\frac{ln\kappa }{P}\right)_T=\frac{\mathrm{\Delta }V^{}}{k_BT}$$
$`(6)`$
between the effect of external pressure on the rate of a chemical reaction and the activation volume of the reaction (namely, the difference between the volume of the activated complex and the volume of the reactants). To obtain quantitative estimates it is to be noted that the initial volume viz. Ps in the bubble without the Ac must be found now by minimizing the total energy, namely $`E_{tot}=\frac{\mathrm{}^2}{4mR^2}+4\pi R^2\sigma +\frac{4\pi }{3}R^3P`$ with respect to $`R`$ and thereby obtain $`R_0(P)`$. Here $`P`$ is measured in kgwt/cm2 (=$`.613\times 10^6`$ eV/Å3). Similarly the equation determining the equilibrium radius \[$`R_{min}(P)`$\] with Ps-Ac inside the bubble must be appropriately modified, so that in place of eq.(4), we now have

$$\frac{}{R}\left(B+4\pi R^2\sigma +\frac{4\pi }{3}R^3P\right)=0$$
$`(7)`$
Equipped with $`R_0(P)`$, $`R_{min}(P)`$ and $`B[R(P)]`$ the variation of the rate constant with pressure can be readily calculated.

Consider the two typical cases depicted in Fig.2 out of the many taken from the experimental studies of Kobayashi . All these experiments were performed at ambient temperature ($`T_{expt}=19\pm 1^oC`$). With nitrobenzene as the Acceptor and benzene as the solvent we note that there is no significant effect of pressure on the reaction rate. This is quite consistent with the model in view of the fact that the turnover temperature in this case  is considerably above $`T_{expt}`$ and hence one is working in the Arrhenius region where the pressure effect is expected to be small. On the other hand when the solvent is hexane, the experiment was performed in the regime where the Ps-Ac-bubble system is stable (as the turnover temperature here is -53$`{}_{}{}^{o}C`$), and accordingly the reaction rate responds appreciably to external pressure. Indeed the enhancement of the rate by a factor of about thirty in our model is even in quantitative agreement with the experimental results of Kobayashi. Using the experimental value of the surface tension of hexane at $`T_{expt}`$ ($`\sigma `$ 19 dynes/cm), the model indicates the behaviour shown in Fig.2 with appropriate over-all normalization.

Above a critical pressure the Ps-Ac-bubble system destabilizes and the rate versus pressure curve levels off. Except for the fact that there is a somewhat precocious onset of the Arrhenius regime the general experimental trend is captured very well indeed considering the approximations involved.

We may thus conclude that the simple model we have proposed effectively accounts for the temperature, pressure and solvent dependence of Ps-Ac Complex formation reactions. Of cardinal importance for our discussion has been the introduction of the notion of the critical surface tension ($`\sigma _{cr}`$) which enables us to semiquantitatively account for most observations and also to make the important qualitative remark: that for any solvent at a temperature such that its surface tension is smaller than $`\sigma _{cr}`$ the reaction rate decreases with increasing temperature and is also significantly affected by external pressure, while otherwise it is the other way around.

 O.E. Mogensen, Positronium Annihilation in Chemistry (Springer- Verlag, 1995).
 V.I. Goldanskii et al., Dokl. Acad. Nauk. 203 (1972) 870.
 E. Hall, W.J. Madia & H.J. Ache, Radiochem. Radioanal. Lett. 23 (1975) 283.
 Y. Kobayashi, Chem. Phys. Lett. 172 (1990) 307.
 Y. Kobayashi, Chem. Phys. 150 (1991) 453.
 R.A. Ferrel, Phys. Rev. 16 (1957) 108.
 S.J. Tao, J. Chem. Phys. 56 (1972) 5499.
 M. Eldrup, D. Lightbody & J.N. Sherwood, Chem. Phys. 63 (1981) 51.
 L.O. Roellig, Positron Annihilation, ed. A.T. Stewart & L.O. Roellig (Academic Press, N.Y.) p 127.
 T.B. Daniel & R. Stump, Phys. Rev. 115 (1959) 1599.
 T. Mukherjee, B. Ganguly & B. Dutta-Roy, J. Chem. Phys. 107 (1997) 7467.
 D. Gangopadhyay et al., J. Phys. Cond. Matt. 11 (1999) 1463.
 A similar two potential model was suggested in A.P. Buchikin, V.I. Goldanskii & V.P. Shantarovich, Dokl. Acad. Nauk. 212 (1973) 1356 and in A.I. Ryzhkov & V.P. Shantarovich, Mat. Sci. Forum 105-108 (1992) 1699. However, with both potentials having finite depths there were too many parameters to give the model predictive power or provide a deeper insight.
 The detailed form of the binding potential hardly matters. We have checked that with a Dirac delta potential $`V(r)=g\delta (ra)`$, the results are very similar. It must however be mentioned that even though the general trends in each of these models essentially remain the same detailed values are often very sensitively dependent on the numerical values of parameters.
 H.A. Kramers, Physica 7 (1940) 284.
 V.I. Goldanskii & V.P. Shantarovich, Appl. Phys. 3 (1974) 335. The range 1.5 Å represents the distance between the active centres i.e. electron of Ps and that of C+ ion.
 D.M. Schrader & C.M. Wang, J. Phys. Chem. 80 (1976) 2507.
 Indications are already there in reference 2 but very careful measurements recently made in our laboratory place the turnover temperature for Ps-nitrobenzene reaction with benzene as a solvent at $`33\pm 3^oC`$.


text:
# The Schmidt Measure as a Tool for Quantifying Multi-Particle Entanglement

## Abstract

We present a measure of quantum entanglement which is capable of quantifying the degree of entanglement of a multi-partite quantum system. This measure, which is based on a generalization of the Schmidt rank of a pure state, is defined on the full state space and is shown to be an entanglement monotone, that is, it cannot increase under local quantum operations with classical communication and under mixing. For a large class of mixed states this measure of entanglement can be calculated exactly, and it provides a detailed classification of mixed states.

Quantum entanglement is a still not fully understood feature of quantum mechanics. The nature of quantum correlations has been a central issue of long-lasting debates on the interpretation of quantum mechanics. With the emergence of quantum information theory, however, a more pragmatic approach to entanglement has become appropriate. Entanglement, in this context, is typically conceived as a resource for certain computational and communicational tasks. Terms like “entanglement distillation” – a process in which dilute entanglement is transformed into a more suitable form – already suggests that emphasis is put on the usefulness of quantum entanglement. In the spirit of this development, the conditions on any functional that is to quantify the degree of entanglement  have been formulated in terms of its behaviour under certain local quantum operations that can be implemented by remotely located parties.

For bi-partite systems several measures of mixed state entanglement have been proposed , each supplemented with a different physical interpretation. In the case of a multi-partite system  a single number giving the amount of entanglement is not sufficient: it has been shown that several “kinds of entanglement” have to be distinguished, and the quantification of the entanglement of such multi-partite quantum systems is essentially an open problem.

In this paper we introduce a functional – in the following referred to as Schmidt measure – that gives an account on the degree of entanglement of a multi-partite system with subsystems of arbitrary dimension. We will proceed as follows. Firstly, the measure of entanglement will be defined for pure states, employing a natural generalization of the Schmidt rank for bi-partite systems. The definition will then be generalized to the domain of mixed states, and we will show that this definition is consistent with conditions every entanglement measure has to satisfy. This entanglement measure provides the tool for a classification of the entanglement inherent in multi-particle states. Several partitions  of the composite systems in subsystems will be considered. Also, the connection to best separable approximations as studied in Ref.  will be established.

In Ref.  a certain class of multi-qubit states has been introduced, the so-called $`N`$-party cluster states $`|\varphi _N\varphi _N|`$. It has been demonstrated that the minimal number of product terms is given by $`2^{N/2}`$, if one expands $`|\varphi _N`$ in product states of $`N`$ qubits. The need for a quantification of the entanglement of such states was the motivation for the investigations of this paper. The observation concerning the minimal number of product states is related to the findings of Ref. , in which such numbers have first been considered: it has been shown that there are two classes of tripartite entangled pure states of three qubits which cannot be transformed into each other with nonvanishing probability, the so-called W state  and the GHZ state  being representatives. One has three and the other one has two product states in the minimal decomposition in terms of product states. This statement is also made stronger in that it is pointed out that this minimal number of product terms can never be increased by means of invertible local operations. Building upon these observations one can define an entanglement monotone on the entire state space, containing the mixed states, of an arbitrary multi-partite system.

Consider an $`N`$-partite quantum system with parties $`A_1,\mathrm{},A_N`$ holding quantum systems with dimension $`d_1,\mathrm{},d_N`$, that is, the state space of the composite system is given by $`𝒮()`$, where $`=^{d_1}\mathrm{}^{d_N}`$. Any $`|\psi `$ can be written in the form

$$|\psi =\underset{i=1}{\overset{R}{}}\alpha _i|\psi _{A_1}^{(i)}\mathrm{}|\psi _{A_N}^{(i)},$$
(1)
where $`|\psi _{A_j}^{(i)}^{d_j}`$, $`j=1,\mathrm{},N`$, $`\alpha _i`$, $`i=1,\mathrm{},R`$ with some $`R`$. Let $`r`$ be the minimal number of product terms $`R`$ in such a decomposition of $`|\psi `$. The Schmidt measure is now defined as $`P(|\psi \psi |)=\mathrm{log}_2r`$ . In case of a bi-partite system with parties $`A_1`$ and $`A_2`$ the minimal number of product terms $`r`$ is given by the Schmidt rank of the state. The Schmidt measure could be conceived as a generalization of the Schmidt rank to multi-partite systems in a similar way as the Schmidt number applies its concept to mixed states .

Once $`P`$ is defined for pure states one can extend the definition to the full state space in a natural way. This is done by using a convex roof construction : For a $`\rho 𝒮()`$ let

$$P(\rho )=\mathrm{min}\underset{i}{}\lambda _iP(|\psi _i\psi _i|),$$
(2)
where the minimum is taken over all possible convex combinations of the form $`\rho =_i\lambda _i|\psi _i\psi _i|`$ in terms of pure states $`|\psi _1\psi _1|,|\psi _2\psi _2|,\mathrm{}`$, with $`0\lambda _i1`$ for all $`i`$.

In the subsequent paragraph we will show that the Schmidt measure for mixed states defined in Eq. (2) qualifies for being an entanglement monotone in the sense of Ref. ( see also Ref. ). That is, $`P`$ is a proper measure of entanglement satisfying the following conditions:

* $`P0`$, and $`P(\rho )=0`$ if $`\rho `$ is fully separable .
* $`P`$ is a convex functional,

$$P(\lambda \rho _1+(1\lambda )\rho _2)\lambda P(\rho _1)+(1\lambda )P(\rho _2)$$
(3)
for all $`\lambda [0,1]`$ and all $`\rho _1,\rho _2𝒮()`$.
* $`P`$ is monotone under local generalized measurements: Let $`\rho `$ be the initial state, and let one of the parties perform a (partly selective) local generalized measurement leading to the final states $`\rho _1,\mathrm{},\rho _n`$ with respective probabilities $`p_1,\mathrm{},p_n`$. Then $`P(\rho )_{i=1}^np_iP(\rho _i)`$.

The physical interpretation of condition (i) is obvious. In condition (ii) part of the distinction between classical and quantum correlations is incorporated. If one mixes states in the sense that one dismisses the classical knowledge of what preparation procedure has actually been applied, the entanglement must not increase. Condition (iii) ensures that the expected entanglement does not grow when a selective generalized measurement is performed. In particular, condition (iii) leads to an invariance under local unitary operations, that is, $`P(U\rho U^{})=P(\rho )`$ for all $`\rho 𝒮()`$ and all local unitary operators $`U`$. An implication of (ii) and (iii) together is that $`P(\mathrm{\Lambda }(\rho ))P(\rho )`$ for all $`\rho 𝒮()`$ and all completely positive trace-preserving maps $`\mathrm{\Lambda }:𝒮()𝒮()`$ corresponding to a local quantum operation. These conditions (i) – (iii) that formalize the intuitive properties of an entanglement measure go back to Refs.  and .

Proposition. – $`P`$ is an entanglement monotone fulfilling the conditions (i) – (iii).

Proof: Condition (i) follows immediately from the definition. Due to the convex roof construction $`P`$ is also a convex functional: let $`\rho _1`$ and $`\rho _2`$ be states from $`𝒮()`$, and let $`\rho _1=_j\mu _j|\varphi _j\varphi _j|`$ and $`\rho _2=_j\eta _k|\phi _k\phi _k|`$ be the two decompositions for which the respective minima in Eq. (2) are attained. Then $`_j\lambda \mu _j|\varphi _j\varphi _j|+_k(1\lambda )\eta _k|\phi _k\phi _k|`$ is a valid decomposition of $`\rho \lambda \rho _1+(1\lambda )\rho _2`$, but it is not necessarily the optimal one. Hence, $`P(\lambda \rho _1+(1\lambda )\rho _2)\lambda P(\rho _1)+(1\lambda )P(\rho _2)`$.

To see that $`P`$ satisfies also condition (iii) we proceed in several steps. The local measurement can be assumed to be performed by party $`A_1`$. Any final state $`\rho _j`$, $`j=1,2,\mathrm{}`$, in a local generalized measurement can be represented with the help of Kraus operators $`E_{ij}`$, $`i,j=1,2,\mathrm{}`$, as

$$\rho _j=\frac{_iE_{ij}\rho E_{ij}^{}{}_{}{}^{}}{p_j}$$
(4)
with $`p_j=\mathrm{tr}[_iE_{ij}\rho E_{ij}^{}{}_{}{}^{}]`$, $`_{ij}E_{ij}^{}E_{ij}=I`$. As the sum over $`i`$ corresponds to a mixing which – due to the convexity property – reduces the Schmidt measure, it suffices to consider final states of the form $`\rho _j=E_j\rho E_{j}^{}{}_{}{}^{}/p_j`$ with $`p_j=\mathrm{tr}[E_j\rho E_{j}^{}{}_{}{}^{}]`$. The trace-preserving property of the quantum operation reads as $`_jE_j^{}E_j=I`$. For any pure state $`|\psi \psi |𝒮()`$

$$P(E_j|\psi \psi |E_{j}^{}{}_{}{}^{}/\mathrm{tr}[E_j|\psi \psi |E_{j}^{}{}_{}{}^{}])P(|\psi \psi |)$$
(5)
for all $`j=1,2,\mathrm{}`$. This can be seen as follows. Let $`|\psi =_{i=1}^r|\psi _{A_1}^{(i)}\mathrm{}|\psi _{A_N}^{(i)}`$ be the decomposition of $`|\psi `$ into products as in Eq. (1) with the minimal number of terms $`r`$. Then $`E_j`$ is either invertible, and then $`E_j|\psi `$ has the same minimal number of product terms $`r^{}=r`$, or it is not invertible, such that $`r^{}r`$. Moreover, if Eq. (5) holds for pure states $`|\psi \psi |`$, it is also valid for arbitrary states $`\rho 𝒮()`$: Let $`\rho =_k\lambda _k|\psi _k\psi _k|`$ be the optimal decomposition of $`\rho `$ belonging to the minimum in Eq. (2), then

$`P(\rho )`$ $`=`$ $`{\displaystyle \underset{k}{}}\lambda _kP(|\psi _k\psi _k|)`$ (6)
$``$ $`{\displaystyle \underset{k}{}}\lambda _kP\left(E_j|\psi _k\psi _k|E_j^{}/\mathrm{tr}[E_j|\psi _k\psi _k|E_j^{}]\right)`$ (7)
$``$ $`P\left(E_j\rho E_j^{}/\mathrm{tr}[E_j\rho E_j^{}]\right)`$ (8)
for all $`j=1,2,\mathrm{}`$. The statement of condition (iii) follows from the fact that $`_jp_jP(E_j\rho E_j^{}/\mathrm{tr}[E_j\rho E_j^{}])_jp_jP(\rho )=P(\rho )`$.

The Schmidt measure can indeed be used as a functional appropriately quantifying the entanglement of a given state of a $`N`$-partite quantum system. It cannot be increased on average under LOCC and it distinguishes between classical and quantum correlations . The Schmidt measure is normalized, in that $`P(|\psi \psi |)=1`$ for all states $`|\psi \psi |`$ of the form $`|\psi =(|0_1\mathrm{}0_N+|1_1\mathrm{}1_N)/\sqrt{2}`$. The functional is also (fully) additive on pure states: If the parties $`A_1,\mathrm{},A_N`$ share two $`N`$-partite quantum systems in the states $`|\psi _1\psi _1|`$ and $`|\psi _2\psi _2|`$, respectively, then $`P(|\psi _1\psi _1||\psi _2\psi _2|)=P(|\psi _1\psi _1|)+P(|\psi _2\psi _2|)`$. In particular, $`P(|\psi \psi |^n)=nP(|\psi \psi |)`$ for $`n`$ copies of the same state $`|\psi \psi |`$. Let $`\rho 𝒮()`$ be a fully separable state , then the stronger statement $`P(\rho ^n|\psi \psi |^n)=nP(|\psi \psi |)`$ is also true .

Although the Schmidt measure of a mixed state is defined via a minimization over all possible realizations of the state, it can be calculated exactly for a quite large class of states. This is mainly due to the fact that it is a coarse grained measure. All terms that appear in Eq. (2) are logarithms of natural numbers weighted with respective probabilities.

This fact allows for a detailed classification of multi-particle entangled states. The following investigations will be restricted to the multi-qubit case, meaning that $`=(^2)^N`$. Clearly, in a multi-partite setting a single number for the entanglement of the whole system is not sufficient to account for the possible entanglement structures. As in Ref.  we consider arbitrary partitions of the $`N`$-partite system with parties $`A_1,\mathrm{},A_N`$ into $`k`$ parts, $`k=2,\mathrm{},N`$. A division of the original system into $`k`$ parts will be called a $`k`$-split. These parts are taken to be a system on their own with a certain higher dimension when $`P`$ is evaluated. In notation such a division will be marked with brackets. For a, say, three-party system the 3-split $`A_1A_2A_3`$ and the three 2-splits $`(A_1A_2)A_3`$, $`(A_2A_3)A_1`$, and $`(A_3A_1)A_2`$ are possible. In this classification the Schmidt measure will also be furnished with an index indicating the respective split. For each $`k`$-split the Schmidt measure does not increase on average in the course of a LOCC operation. This does not imply, however, that the Schmidt measure with respect to the reduced state of some of the parties must not increase on average under such operations.

Pure states. – For pure states the definition given in Eq. (1) can be easily applied. Take, e.g., as in Ref.  the three party W-state with state vector

$$|\text{W}=(|100+|010+|001)/\sqrt{3}.$$
(9)
$`P_{A_1A_2A_3}(|\text{W}\text{W}|)=\mathrm{log}_23`$, while the three party GHZ state, $`|\text{GHZ}=(|000+|111)/\sqrt{2}`$, gets the value $`P_{A_1A_2A_3}(|\text{GHZ}\text{GHZ}|)=1`$. Hence, in the 3-split $`P`$ distinguishes the GHZ state, the W state and product states (value 0) . Other splits with $`k=2`$ reveal further information and give rise to the full classification. Table I shows the values of the Schmidt measure with respect to all possible splits for some pure states of a four-partite system.

Mixed states. – In mixed quantum states both quantum entanglement and classical correlations may be present. In order to calculate the Schmidt measure of a mixed state a minimization over decompositions of the state is required. Upper bounds of $`P`$ follow immediately from the definition: If $`\rho =\eta _i|\psi _i\psi _i|`$ is any not necessarily optimal decomposition of a state $`\rho 𝒮()`$, then $`_i\eta _iP(|\psi _i\psi _i|)`$ is an upper bound of $`P(\rho )`$. For many states $`P`$ can however be fully evaluated. Consider, e.g., two parties $`A_1`$ and $`A_2`$ sharing two qubits in the Werner state

$$\rho _\text{W}(\lambda )=\lambda |\psi ^{}\psi ^{}|+(1\lambda )I/4,$$
(10)
with $`|\psi ^{}=(|01|10)/\sqrt{2}`$, $`0\lambda 1`$. As all pure states in the range of $`\rho _\text{W}(\lambda )`$ have Schmidt measure 0 or 1, one has to identify in any decomposition $`\rho _\text{W}(\lambda )=_i\eta _i|\psi _i\psi _i|`$ the terms with Schmidt measure 0 (product states) or 1 (entangled states). Hence, the Schmidt measure is given by $`P(\rho _\text{W}(\lambda ))=1s`$, where $`s`$ is the weight of the separable state that can be maximally subtracted from $`\rho _\text{W}(\lambda )`$ while maintaining the semi-positivity of the state, and therefore ,

$$P(\rho _\text{W}(\lambda ))=\{\begin{array}{cc}\frac{3}{2}\lambda \frac{1}{2},\hfill & \text{ for }1/3<\lambda 1\text{,}\hfill \\ 0,\hfill & \text{for }0\lambda 1/3\text{.}\hfill \end{array}$$
(11)
In other words, $`P`$ is just given by the weight of the inseparable state in the best separable decomposition in the sense of Ref. . As follows from the observation that the Schmidt rank of all states in the range of any state from $`𝒮(^2^2)`$ is smaller or equal to 2, this statement holds for all mixed states of two parties holding qubits. As a corollary we find that the parameter of the best separable decomposition in $`2\times 2`$ systems is an entanglement monotone.

For more than two parties several different entanglement classes can be distinguished. The Schmidt measure is again defined for all possible $`k`$-splits, $`k=2,\mathrm{},N`$. If the $`N`$-partite system is separable with respect to a particular $`k`$-split, the value of the corresponding Schmidt measure is 0. Since not only condition (i) of the conditions of the entanglement monotone is satisfied, but also the stronger statement that $`P(\rho )=0`$ iff $`\rho `$ is fully separable, the Schmidt measure with respect to a certain split gives an account on the separability of the state taking this split. For three qubits, e.g., the classes of so-called one-qubit biseparable states, two-qubit biseparable states, three-qubit biseparable states, and fully separable states  can be distinguished. However, the Schmidt measure reveals more structure, since the entanglement – if present – is also quantified. As an example, consider the state

$`\rho (\lambda ,\mu )`$ $`=`$ $`\lambda |\varphi _{A_1A_2}^+|0_{A_3}0_{A_3}|\varphi _{A_1A_2}^+|`$ (12)
$`+`$ $`\mu |\varphi _{A_2A_3}^+|0_{A_1}0_{A_1}|\varphi _{A_2A_3}^+|`$ (13)
$`+`$ $`(1\lambda \mu )|\varphi _{A_3A_1}^+|0_{A_2}0_{A_2}|\varphi _{A_3A_1}^+|,`$ (14)
$`|\varphi ^+=(|00+|11)/\sqrt{2}`$, $`0\lambda ,\mu 1`$. For $`\lambda =\mu =1/3`$ this state reduces to the three-party molecule state $`\rho _\text{M}`$ studied in Ref. . The Schmidt measure $`P_{A_1A_2A_3}(\rho _\text{M})=1`$ is equal to the Schmidt measure of the state where $`A_1`$ and $`A_2`$ hold a $`|\varphi ^+\varphi ^+|`$ state and $`A_3`$ is in the state $`|00|`$, as the mere classical ignorance of which parties are actually holding the Bell state cannot increase the amount of entanglement (compare also Ref. ). In Table II the values of the Schmidt measures of all splits of the states $`\rho (\lambda ,\mu )`$, $`\rho _\text{M}`$, and $`\rho _\text{G}(\lambda )=\lambda |\text{GHZ}\text{GHZ}|+(1\lambda )|000000|`$, $`0\lambda 1`$, are shown.

To summarize, we have proposed a new functional which quantifies the entanglement of quantum systems shared by $`N`$ parties in possibly mixed states. It has the property to be an entanglement monotone, implying that it does increase on average under LOCC operations. Surprisingly, it turns out to be analytically computable for a large class of states, and it leads to a detailed classification of states. It is the hope that this measure of entanglement provides a helpful pragmatic tool for investigating the rich structure of multi-particle entanglement.

We would like to acknowledge fruitful discussions with M.B. Plenio, W. Dür, G. Vidal, and D. Bruß at the Benasque Center for Science (BCS). One of us (HJB) enjoyed interesting discussions with L. Hardy and C. Simon during an earlier visit at Oxford University. We would also like to thank M.B. Plenio for critically reading the manuscript. This work has been supported in part by the DFG and the European Union (IST-1999-11053, IST-1999-13021, IST-1999-11055).