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# Simulation of Cu-Mg metallic glass: Thermodynamics and Structure

## I Introduction

Metallic glasses Greer (1995); Johnson (1999) have generated considerable scientific interest since they were discovered 40 years ago, due to their unusual magnetic and mechanical properties, as well as wear and corrosion resistance, and their glass-forming ability per se. This interest has substantially increased since the discovery of the so-called bulk metallic glasses (BMGs) or bulk amorphous alloys, by Inoue Inoue et al. (1991) and Johnson.Peker and Johnson (1993) The ability to create samples with thicknesses in the mm or cm range, rather than $`\mu `$m thick ribbons, greatly increases the applicability of the materials, as well as the range of measurements that can be performed on them. This is particularly true in the case of mechanical testing, and recently measurements of properties such as fracture toughness, fracture morphology and crack-tip plasticity have been made.Fedorov and Ushakov (2001); Flores and Dauskardt (2001); Schneibel et al. (2001); Gilbert et al. (1997)

The mechanisms of plastic deformation are of particular interest in metallic glasses in view of the fact that there are no obvious topological defects which might play a role analogous to crystal-dislocations, allowing slip to take place in small increments. Thus metallic glasses tend to have very high flow stresses.Greer (1995) A complete understanding of plastic deformation must include the following two parts: (i) detailed knowledge of the elementary events that constitute plastic flow and (ii) a practical continuum theory which uses this knowledge to make predictions of macroscopic behavior (a recent such theory is the so-called Shear Transformation Zone (STZ) theoryFalk and Langer (1998); Langer and Pechenik (2003)). The motivation for the present work is a desire to tackle item (i) using the tools of modern materials simulations, specifically: realistic potentials, system sizes as large as feasible and necessary, and sophisticated analysis and visualization techniques. The first step, addressed in this paper, is to create appropriate interatomic potentials, generate glassy configurations, and study the thermodynamics and structure of the system, in order to understand it as a glass-forming one. Simulations of mechanical properties will be presented in future publications. The phrase “realistic potentials” refers to contemporary potentials commonly used for metals, including effective medium or embedded atom-type potentials, or pseudopotential-based pair potentials, as opposed to Lennard-Jones potentials, which are commonly used (with two components) to model metallic glasses. Kob and Andersen (1995a, b); Sastry et al. (1998); Utz et al. (2000); Lacks (2001); Varnik et al. (2003) Such potentials are especially useful because they allow quantitative comparison with experiments of properties such as glass transition temperature, and, later, mechanical properties.

In this paper we present molecular dynamics simulations of the binary alloy CuxMg1-x. Mg-based BMGs such as Mg60Cu30Y10Inoue et al. (1991); Busch et al. (1998); Wert et al. (2001); Wolff et al. (2003) are of interest because their weight is low, being dominated by Mg, but their strength can be comparable to high-strength steel. We have chosen to study the binary alloy because (i) it is simpler to optimize a potential for two species than for three and (ii) it is easier to study dependence on a single composition-parameter than on two. Our intent to use realistic potentials necessitates an attempt to create as realistic a glass as possible with those potentials. It is thus important to characterize the system as a glass-forming and alloying one as completely as possible.

The Cu-Mg equilibrium phase diagram is shown in Fig. 1. Experimentally it forms a glass over a range of compositions from 9–42 at. % (complete glass formation over 12–22 %, which includes the eutectic composition 14.5 %).Sommer et al. (1980) It is not a BMG, since it can only be formed by melt-spinning at high cooling rates. The cooling rates in the simulations are necessarily even higher and allow glassy configurations to be created over almost the entire range of compositions. It is worth studying the experimentally inaccessible states as part of the process of detecting trends in material properties as a function of composition; it is the crystal-nucleation timescale, lying between the simulation and experimental timescales, which makes the difference between crystalline and amorphous phases—if just a few orders of magnitude gain in cooling rate could be experimentally realized, there is reason to believe these states would be as stable as the actual glassy configurations currently realizable by experiment.

Because the crystallization rates are high, there are limited experimental measurements of the thermodynamic properties of Mg-Cu glasses, and thus it is of interest to study these in the simulations before moving on to mechanical properties. In the process we find some interesting results regarding structural changes in the super cooled regime (steady growth of icosahedral order and evidence of restructuring thermodynamics). Additionally we make some observations on the question of the fragility of this system. The next section will discuss some aspects of the theory of glass formation in alloys, as applied to the Cu-Mg system. Section III will discuss simulation methods, including the fitting of the interatomic potential. Sections IV and V discuss characterization of the glass transition and of structural properties respectively. The last section is the discussion.

## II Glass formation in the Mg-Cu system

One approach to the theory of metallic glass formation is based on pseudopotential-derived interatomic pair potentials,Hafner (1980, 1987) and emphasizes the coincidence of bond lengths with potential minima. We will not be using such potentials; in fact many aspects of glass formation are purely geometrical (packing of spheres) and phase-energeticHafner (1980) (comparison with competing crystalline phases). Frank and Kasper Frank and Kasper (1958, 1959) pointed out that many complex intermetallic structures can be understood in terms of tetrahedral close-packing of spheres. Examples of so-called Frank-Kasper (FK) phases include the Laves phases (C14, C15, C36) and $`\mu `$, $`\chi `$ and $`\sigma `$ phases. The high packing fraction and coordination numbers suggest directional bonding does not play a role. The closest packing of spheres of equal size is achieved with a tetrahedron (79%), but tetrahedra cannot fill space—the best one can do is make an icosahedron out of twenty slightly distorted tetrahedra, but this cannot be repeated periodically, so in crystals one has the fcc (e.g. Cu, $`a=3.61`$Å) and hcp (e.g. Mg, $`a=3.21`$Å, $`c=5.21`$Å) structures, with 74% packing.

In the Cu-Mg system there is indeed a Laves phase, Cu2Mg. This is not surprising given that the ideal Laves packing is achieved with a radius ratio of 1.225 (Ref. Hafner, 1987, p.59), which is close to that of Mg and Cu (1.256 using the Goldschmidt radii, based on nearest neighbor distances of the pure metals). This phase is quite stable simply because having a majority of smaller atoms allows a greater packing fraction. On the other hand Mg2Cu, with the larger atoms in the majority, is not as stable an alloy.Hafner (1980) Mg-Cu is in a class of metallic glass formers which include simple metal-transition metal binary alloys and are characterized by a Laves phase when the small atom (Cu) is in the majority, and a glass when the larger atom is. In Cu2Mg the Cu atoms have CN12 icosahedral coordination and the Mg atoms are 16-coordinated, surrounded by so-called Frank-Kasper 16-hedra (more specifically, Friauf polyhedra).

Glass formation in a binary alloy appears to be favored by the same criteria that favor the formation of FK phases: large, negative heats of formation, non-directionality of bonding, and a tendency to maximize packing fraction. In general one finds that for compositions between intermetallics (for example near eutectics), where the equilibrium phase diagram shows a two-phase mixture, the amorphous phase is more stable than any single crystalline phase. In the region of the phase diagram where FK phases appear, glass formation typically loses out in the competition experimentally, presumably because the nucleation of the Laves phase is rather easy. In the Cu-Mg system, the region of experimental glass formation is on the Mg-rich side, where the competing crystalline phase, Mg2Cu, is quite complex (48 atoms in the unit cell).

## III Simulation methods

### III.1 Potentials

The interatomic potential we use is the effective medium theory (EMT),Jacobsen et al. (1987, 1996) fit to data obtained from density functional theory (DFT) calculations and experiment. This has previously been applied to fcc metals, in particular late transition and noble metals and has been of great use in studying mechanical properties of crystalline metals.Schiøtz et al. (1999); Schiøtz and Jacobsen (2003) As Mg crystallizes in hcp with an almost ideal $`c/a`$-ratio of $`1.624`$ (ideal is $`\sqrt{8/3}=1.633`$), indicating little directional bonding, we might expect it to be reasonably well described by an appropriately optimized EMT potential.

EMT uses seven parameters for each element. A set of parameters for Cu exists but these have been optimized for simulations of pure, crystalline Cu (where for example particular attention was paid to the stacking fault energy, which is of no concern in amorphous materials). For the amorphous alloys, it is important that the formation energies are reasonable, in particular that they are negative (otherwise the system will simply separate into regions of pure Cu and regions of pure Mg).

Thus we have (re-)fit the parameters of both elements, taking into account basic properties such as lattice constants, cohesive energies and elastic constants of the pure elements, as well as the formation energies of the two intermetallic compounds, Mg2Cu and Cu2Mg. Due to the near-ideal hcp packing of Mg, its structure differs from fcc only at the second neighbor level. For simplicity, and because the EMT potential is formulated in terms of fcc packing, we used calculated properties of fcc Mg in the fitting, except that the cohesive energy was corrected using the experimental hcp value and the calculated fcc-hcp difference ($`23meV`$/atom), calculated differences in cohesive energy being expected to be more accurate than calculated cohesive energies themselves.

The optimized EMT coefficients are shown in table 1 and the target and fitted values of the fitting properties are shown in table 2. Note that for the orthorhombic Mg2Cu, the experimental $`b/a`$ and $`c/a`$ were used, as well as the experimental values of the internal coordinates. The alloy formation energies are well-represented. Unlike pair potentials based upon pseudopotentials, the present form of the EMT potentialJacobsen et al. (1996) does not incorporate the Friedel oscillations, and the idea that stability of intermetallic compounds is determined by the matching of minima of pair potentials to interatomic distancesHafner (1980) does not play a role; the fact that EMT parameters can be chosen to give the correct formation energies of the intermetallic compounds appears to be most important.

### III.2 Molecular dynamics

We simulated the cooling of systems of 2048 atoms from the liquid state (above the melting point) down to zero temperature. The compositions ranged from pure Mg to pure Cu, and are labeled by the percentage of Cu. For most simulations we used 21 compositions, increasing in steps of 5% from 0 (pure Mg). The initial state was an fcc lattice with the sites occupied at random by Cu or Mg atoms in accordance with the overall composition. There was no initial heating phase; the first stage in the cooling run set the temperature to a value well above the melting point (values ranged from 1392 K for Mg ($`T_m=923K`$) to 1857 K for Cu ($`T_m=1358K`$)), making the crystal melt immediately. Two rates of cooling were used; differing in the amount of simulation time at each temperature. Cooling took place in steps of $`35K`$; the procedure at each temperature stage was as follows: (i) a small number of steps, corresponding to $`0.6ps`$ (the MD time-step was $`2fs`$), of constant-volume Langevin thermalization was carried out in order to approximately thermalize the system to the new temperature; (ii) the dynamics was switched to constant-pressure (NPT) dynamics and the system was simulated for an initial equilibration time of $`6ps/12ps`$; (iii) the system was simulated for a longer time $`40ps/120ps`$ during which thermal averages of various quantities of interest were taken. This time also contributed to the equilibration of the system. The overall cooling rates were thus close to $`0.72K/ps`$ ($`7.2\times 10^{11}K/s`$) and $`0.25K/ps`$ ($`2.5\times 10^{11}K/s`$). The NPT dynamics used was a combination of Nose-Hoover and Parrinello-Rahman dynamics, proposed by Melchionna.Melchionna et al. (1993); Melchionna (2000); Holian et al. (1990); Di Tolla and Ronchetti (1993) We turned off shearing, allowing only volume fluctuations, because the liquid state cannot support a shear stress and fluctuations in the periodic box sometimes lead to extreme angles between box vectors and thus problems with the neighbor-locating algorithm. The pressure was zero or a small positive value (this was necessary in some cases when the initial temperature was above the boiling point of pure Mg). For each cooling rate the simulations were run twice with different random number seeds (affecting the distribution of species in the initial lattice and the Langevin dynamics used when the temperature is changed; the NPT dynamics does not use random numbers).

During the averaging period, the pressure, volume, kinetic and potential energies were recorded and averaged. For the purposes of structural analyses so too was the radial distribution function (RDF), both total and separated into contributions from Mg-Mg, Cu-Cu and Mg-Cu. At the end of the averaging time the current configuration was saved, as well as a configuration obtained from it by direct minimization (quenching) using the MDmin minimization algorithm. At a later time the saved configurations from selected temperatures were used for further simulation at that temperature to gather further dynamical and structural information such as diffusion constants and thermally averaged common neighbor analysis (CNA).

Our cooling rates are as slow as in other recent simulations of amorphous metals,Hui et al. (2002); Qi et al. (1999); Posada-Amarillas and Garzon (1996); Lewis (1989) but they are of course larger than experimental rates by several orders of magnitude. In order to check that our results are not significantly affected by this difference, we have cooled one composition, 15% Cu at several faster rates and one slower one. Fig. 2 shows $`T_g`$ and the enthalpy at $`T=0`$ for these runs. The methods of calculating $`T_g`$ are explained in the next section; only one (intercept) could be used for the very fast runs. It is pretty clear that for the cooling rates used in the main simulation, the dependence of $`T_g`$ on cooling rate has become smaller than the uncertainty in determining $`T_g`$. The enthalpy shows a definite slope still at the lowest cooling rate, amounting to about $`1meV`$ per order of magnitude cooling rate, which is rather small; also one would expect the curve to flatten out more at even smaller rates. The one significant difference we notice is that crystallization at the Cu-rich end happens at lower Cu-concentrations for slower cooling: the 90% Cu system crystallizes in one run at $`0.25K/ps`$ but not at all at $`0.72K/ps`$.

## IV Glass transition

We see glass transitions in almost all compositions, the exceptions being the pure elements and 95% Cu, which crystallize in fcc/hcp structures (also 90% Cu in one out of two runs at $`0.25K/ps`$). The first evidence that a glass transition takes place upon cooling appears in the enthalpy versus temperature curve, which shows a change in slope (inset in Fig 3). This suggests a way to determine $`T_g`$ by breaking the curve into two pieces, fitting a straight line to each, and intersecting the two lines obtained. We call this the “intercept-method”. It turns out that this tends to underestimate $`T_g`$ as can be seen by looking at the derivative of the enthalpy, the specific heat (Fig 3), obtained from centered differences. The $`T_g`$ ends up at the leftmost part of the steep part of the curve, whereas one would expect any reasonable definition of $`T_g`$ to be roughly in the center of the transition region (defined as the steep part). Thus we compute $`T_g`$ as the temperature at which the specific heat is changing fastest by taking derivatives again and simply choosing the maximum. This method necessarily yields a $`T_g`$ equal to one of the simulation temperatures, but since the transition region is a few times wider ($`150200K`$) than the temperature step in the simulation, one cannot expect to do better (experimentally one sees widths of some tens of $`K`$, see for example Ref. Busch et al., 1995). In cases where we have two different enthalpy curves for the same system cooled identically but from different starting configurations we average the two enthalpy curves before applying the method, as this gives a smoother $`c_P`$ curve.

The $`T_g`$ we get for 15% Cu is $`350K`$ which is remarkably similar to the experimental value of $`380K`$ reported by Sommer et al.Sommer et al. (1980) In runs where crystallization took place, a large spike in the specific heat appeared, corresponding to a step or latent heat in the enthalpy curve. Before looking at the composition dependence of $`T_g`$, we notice that the temperature dependence of $`c_P`$ is quite similar in form to experimental specific heat curves of Zr41.2Ti13.8Cu12.5Ni10.0Be22.5 reported by Busch et al. Busch et al. (1995) and of fluorozirconate and tellurite glasses reported by Lin and Navrotsky;Lin and Navrotsky (1997, 1998) there is an increase in specific heat in the supercooled liquid region compared to the high-temperature liquid region. For the tellurites, Lin and Navrotsky identified the source of this as specific structural rearrangements that take place in the liquid prior to the glass transition. We will see in the next section what evidence there is for structural rearrangements in the Cu-Mg supercooled liquid.

Fig. 4 shows $`T_g`$ and $`\mathrm{\Delta }c_P`$, the heat capacity jump (obtained by roughly determining the transition region as the peak in the derivative of $`C_P`$ and taking the difference of $`C_P`$ on either side of the peak) for different compositions and cooling rates. $`T_g`$ rises roughly linearly with increasing fraction of Cu, which presumably reflects a general increase in energy scale as we go from the weakly cohesive (low melting point) Mg to the more strongly cohesive Cu. The fluctuations towards the Cu-rich end are due to the mid-point method’s difficulty handling the somewhat less clean $`c_P`$-data there. The fluctuations in $`\mathrm{\Delta }c_P`$ are also due to the imperfect $`c_P`$-data. Nevertheless, it seems clear that $`\mathrm{\Delta }c_P`$ has the value of roughly $`1.5k_B`$ per atom, independent of concentration. This is a relatively small amount, which is typical of so-called “strong” glass-formers, which include most BMGs.Busch (2000) In particular the Mg65Cu25Y10 shows a jump of the same order (actually $`2k_B/\text{at.}`$).Busch et al. (1998) However, we should be careful about inferring strong-liquid behavior from this measurement; binary alloys typically are not strong glass-formers, Johnson (1999) and below we shall see evidence of fragile-liquid behavior in the diffusivity. The apparent small jump of $`C_P`$ may be a consequence of the width of the transition.

As a partial means of determining how good, meaning how stable or well-annealed, the final configurations are, we consider their enthalpies. We have seen already how the final enthalpy depends on cooling rate (Fig. 2); we now compare to the equilibrium phases, for different compositions. Fig. 5 shows the formation enthalpies as a function of composition. The formation enthalpy is the enthalpy minus the appropriate linear combination of the pure elements’ enthalpies. The appropriate quantity to compare to, also shown in Fig. 5, is the formation enthalpy of the corresponding crystalline phase, which in general is a two-phase mixture (so, e.g., between 33% Cu and 66% Cu it is an appropriate weighting of the formation enthalpies of Cu2Mg and Mg2Cu). We notice that the glass formation enthalpy follows quite closely the crystalline one, being 1–4 $`kJ/mol`$ higher (the exceptions being at 0, 95% and 100% Cu where the system did in fact crystallize). This is quite small and typical of easy glass formers.Johnson (1986, 1999); Greer (1995) For the 15%Cu composition the value $`4.2kJ/mol`$ was reported by Sommer et al. for the transformation enthalpy from the crystalline to the amorphous state, which is slightly higher than our value of $`3.53kJ/mol`$—that is, our glass at this composition appears to be a little too stable compared with experiment. This kind of discrepancy can only be due to limitations of the interatomic potential, and not to the high cooling rate. This gives us further confidence that we have created glassy structures which are more or less as stable as they can be.

For selected compositions and selected temperatures, configurations from the cooling runs were used as initial configurations for further simulations in which diffusion constants for the two atomic species were measured. An Arhennius plot for the 15% Cu composition is shown in Fig 6. There is a clear indication of a transition near $`1000/T3K^1`$, corresponding to $`T330K`$, which is consistent with the $`T_g=350K`$ obtained from the specific heat. For each composition for which diffusion constants were measured, we have fitted the high temperature part of the data to the Vogel-Fulcher (VF) law

$$D=D_0\mathrm{exp}(\frac{D^{}T_0}{TT_0})$$
(1)
where $`T_0`$ is the location of the apparent singularity and $`D^{}`$ is the so-called fragility parameter. In Fig 7 we show $`D^{}`$ and $`T_0`$ obtained from fits of the Cu diffusion constants to the VF law (the Mg values are very similar, the differences being very small compared to the differences from composition to composition). There is a reasonably clear trend towards decreasing $`D^{}`$ and increasing $`T_0`$ as the fraction of Cu increases. High values $`D^{}`$ are associated with strong glass-formers, the archetypal case of SiO2 having $`D^{}=100`$. Bulk metallic glasses are considered strongBusch (2000) with $`D^{}20`$. So-called fragile glasses have $`D^{}`$ around 2. From our diffusion data we get low fragility parameters, in the range 2–4, indicating that the Mg-Cu glasses are somewhat fragile. This is consistent with the experimental fact that this is not in fact a bulk metallic glass. The $`T_0`$ values increase as the fragility decreases, so that the apparent singularity approaches the actual glass transition temperature. These trends, reflecting greater fragility (decreasing $`D^{}`$) with increasing Cu composition, are also consistent with the fact that experimentally, amorphous Mg-Cu can only be made at all for Mg-rich compositions, since strong liquids tend to be robust against crystallization (in a strong glass former the melt viscosity is high, making the kinetics slow). Thus, our diffusion results put the binary alloy Mg-Cu at the fragile end. This seems to contradict the suggestion of strong-liquid behavior from the specific heat data. The small $`\mathrm{\Delta }C_P`$, may have a simple explanation, however, namely that it has been reduced due to the broadening of the transition in the simulations compared to what one would expect experimentally. This broadening implies that a certain amount of restructuring, that at slower cooling rates would take place above $`T_g`$, in the simulation takes place during and below $`T_g`$. The net enthalpy change (the area under the $`C_P`$ curve) is more or less the same, so the height of the curve above $`T_g`$ must be reduced to compensate. Thus we can assert that the simulations are consistent with Mg-Cu being a fragile glass-former, like most binary alloys.

## V Structural Analysis

### V.1 Radial distribution function

Fig. 8 shows the partial RDFs $`g_{\text{Mg-Mg}}(r)`$ and $`g_{\text{Cu-Cu}}(r)`$ for two compositions at two temperatures. At the higher temperature, which is the eutectic temperature for the corresponding region of the phase diagram, the system is expected to be in equilibrium, and the RDFs have the normal structure of a liquid, with nearest neighbor distances of 3.1Å for Mg and 2.6Å for Cu, which are close to their values in the bulk crystal phases of the pure elements. The lower panels in Fig. 8 show the RDFs at the respective $`T_g`$ for each composition. At 15% Cu, the first peak is prominent for both RDFs. In the Cu-rich alloy on the other hand, the first Mg-Mg peak is significantly suppressed, indicating the Mg atoms are not particularly likely to be found next to each other. This is not surprising since we expect Mg-Mg bonds to be weak compared to both Cu-Cu and Mg-Cu bonds, given the cohesive energies of the pure elements and the intermetallic compounds.

We can see a distinct splitting of the second peak in $`g_{\text{Cu-Cu}}`$ in both compositions. The splitting occurs also for $`g_{\text{Mg-Mg}}`$, but at lower temperatures (here it is also obscured, particularly in the Cu-rich compositions, by the fact that the first sub-peak is significantly higher than the second, which thus appears as a shoulder on the high-side of the first). Such a splitting is commonly associated with the glass transition, but we can see here that the splitting is already well developed at $`T_g`$ for $`g_{\text{Cu-Cu}}`$ and in fact it first occurs well above $`T_g`$. Fig. 4 shows the temperature $`T_{\text{split}}`$ at which this occurs, determined in a somewhat arbitrary manner by visual inspection of the RDFs for different temperatures, as a function of composition. The dependence on composition is rather less than that of $`T_g`$, and in fact it appears that the splitting is not related to the glass transition in a direct way. Note that what is typically observed experimentally—the combined RDF, which averages over the different components—does not show the splitting, because the location of the second peak differs for different components and the effect is washed out (see inset Fig. 8; in fact, for Mg-rich compositions, the total RDF has a split first peak due to the difference in location between Cu-Cu and Mg-Mg first peaks).

### V.2 Coordination numbers

By integrating the RDFs appropriately111That is, multiplying by $`4\pi r^2\rho _A`$, where $`\rho _A`$ is the density corresponding to which type of neighbor is being counted, and integrating until the first minimum. we can determine the partial, total and average coordination numbers, $`Z_{AB}`$, $`Z_A`$ and $`Z`$. These are shown in Fig. 9, for the zero temperature RDFs from the runs with the higher cooling rate ($`0.72K/ps`$). We have checked that virtually identical results are obtained with the lower cooling rate. The average coordination number is quite independent of composition, $`Z=12.91\pm 0.17`$. The coordination number of Mg, $`Z_{Mg}`$, is always higher than the total $`Z`$, and $`Z_{Cu}`$ always lower. Both rise as the fraction of Cu increases (their average does not because it is weighted by the concentrations). From the coordination numbers we can calculate the Spaepen-Cargill short-range order parameter Cargill III and Spaepen (1981)

$`\eta _{AB}`$ $`=Z_{AB}/Z_{AB}^{}1`$ (2)
$`Z_{AB}^{}`$ $`=c_BZ_AZ_B/Z`$ (3)
Here $`c_B`$ is the concentration of $`B`$ atoms (which we take as Cu). A positive value of $`\eta _{AB}`$ indicates a tendency for more unlike bonds than would be expected in an alloy which is completely chemically disordered. Fig. 9 shows $`\eta _{AB}`$; it is definitely positive throughout the glassy range of compositions, with an apparent maximum near the middle of the range. However while the maximum value $`\eta _{AB}`$ can ever take is unity, the maximum for a particular composition is somewhat less, and values should be normalized by the maximum before comparing different compositions. We have not done this since it is not clear what $`\eta _{AB}^{\text{MAX}}`$ is in an amorphous system, particularly in the regime of $`x_Ax_B`$ (see Ref. Cargill III and Spaepen, 1981).

### V.3 Common Neighbor Analysis

To obtain more detailed information about the local atomic structure we use Common Neighbor Analysis (CNA).Jónsson and Anderson (1988); Clarke and Jónsson (1993) The analysis assigns three indices to every pair of atoms, thus allowing a decomposition of the RDF into contributions from different types distinguished by their CNA indices. The first index is the number of neighbors that the two given atoms have in common; the second is the number of bonds among those neighbors, and the third is the size of the largest bonded cluster within the common neighbors (this last differs from the original definition,Clarke and Jónsson (1993) but agrees in all the cases of interest and is less ambiguous). The cutoff for two atoms to be considered “neighbors” or “bonded” is the position of the first minimum in the appropriate RDF. Note that the separation of the two atoms to whom the indices are assigned can be anything up to twice the nearest neighbor distance—beyond this, they cannot have any neighbors in common. Several groups have presented CNA analyses of the structure of metallic glasses.Qi and Wang (1991); Clarke and Jónsson (1993); Posada-Amarillas and Garzon (1996); Moore and Al-Quraishi (2000); He and Ma (2001); Hui et al. (2002) These all reported similar results: the first peak of the RDF is composed mostly of 555, 544 and 433 pairs, and the second peak is composed mostly of 333, 211 and 100 pairs. 555 pairs are associated with icosahedral order: in a perfect icosahedron the central atom makes a 555 pair with each of its 12 neighbors. 544 and 433 pairs are formed when one or more bonds between the outer atoms of an icosahedron are broken. 333, 211 and 100 pairs can also be associated with various pairs within a perfect icosahedron. Furthermore, the 333 and 211 pairs of the second peak combine to form the first sub-peak and the 100 pairs make the second sub-peak, when the second peak splits.

In these papers the CNA was always performed on quenched configurations, obtained by rapid minimization to local minima from finite temperature configurations; this is preferable to doing the analysis on an instantaneous configuration at finite temperature, since the distortions caused by thermal fluctuations would in that case obscure the “inherent structure”. Changes in the structure were correlated with the temperature from which the quench was made. In our analysis, we have taken an alternative approach to dealing with thermal fluctuations and have computed the full thermal averages of the contributions to the RDFs from pairs of different types. Analogous to the RDF which is itself a thermal average, we thus obtain a “radial distribution function” for Cu-Cu/Mg-Mg/Mg-Cu pairs of type 555, 333, etc., which is in fact an exact decomposition of the full RDF for the given species-pair. These averages were computed during the same runs as the diffusion constants, with starting configurations taken from the cooling runs at $`0.72K/ps`$. The CNA partial RDFs were computed every 10th major time step (starting with the 20th—after which it was assumed the full RDF had converged sufficiently to read the position of the first minima). The CNA partial RDFs each consist of a single peak from which quantities such as peak position, height and width can easily be extracted. Also computed is actual (average) number of pairs associated with such a peak, obtained by integrating the RDF against $`4\pi r^2`$ times an appropriate density. Furthermore we can see directly how these CNA-RDFs sum to give the full RDF for a given species-pair.

Fig. 10 shows the numbers of pairs in the sub-components of the first peak of the RDFs. We see the same broad picture described above, in terms of the roles played by 555, 544, 333, etc. pairs. This should not be surprising since as we shall see later icosahedral order is a dominating feature of the intermetallic alloys. In particular the number of 555 pairs grows more or less linearly as the temperature decreases from 1200 K to the glass transition temperature, beyond which it continues to increase, albeit with slightly smaller slope. The number of 421 and 422 pairs, associated with crystalline hcp and fcc order, is very small at all temperatures. The bottom right panel of Fig. 10 shows the decomposition of the first peak of the RDF into contributions from the five listed pair-types. The difference between the solid line (full RDF) and the dashed line (sum of the five listed pair-types) indicates that other types make up a noticeable fraction. This were found to include small amounts of 311, 322, 666, 533, and 532 pairs. At high temperatures when the number of 555 pairs is low, all of these types of pairs, and some others not mentioned, contribute in small amounts to make up the full coordination numbers. Thus the picture we have of the liquid structure at high temperatures is one of many (we have seen up to 15 different CNA types for nearest neighbor pairs) different local structures constantly being created and destroyed, and all contributing a little bit to the thermal average. As the temperature cools, a pair of atoms is more and more likely to be found as a 555 pair. This is independent of what species the two atoms are, and of the compositions.

Fig. 11 shows a similar analysis of the second peak. We see what others have found previously, that it is mostly made up of the 333, 211 and 100, and the first two making up the first sub-peak and the latter the second sub-peak. In fact there is only a small difference between the sum of these three contributions and the full CNA, which appears on the shorter-distance side of the peak. This small difference is due to 455, 444 and 322 pairs, which mainly occupy the region between first and second neighbor distances. At the highest temperatures (not shown), these last three pairs make up a somewhat larger contribution, and are more clearly part of the second (main) peak, but the 333, 211 and 100 are still dominant. The numbers of pairs associated with these CNA-types change relatively little with temperature: $`N_{333}`$ increases by about 30% during cooling; $`N_{211}`$ decreases by the approximately same amount, leaving their sum constant ($`N_{100}`$ is involved in this only to a small extent). It seems that 211 pairs are being transmuted to 333 pairs as the system cools. In the last section we saw that the specific heat of the supercooled liquid is higher than the high temperature liquid, and noted how such behavior in experiments, termed “restructuring thermodynamics”, has been associated with structural rearrangements that take place during cooling. In our system it is natural to assume that the rearrangements identified by CNA analysis in this and the preceding paragraph are responsible for the increased specific heat.

### V.4 Comparison with ordered structures

At this point it is interesting to see what a common neighbor analysis of the intermetallic alloys Cu2Mg and Mg2Cu yields. The results are displayed in table 3, along with the partial and total coordination numbers. The numbers of different CNA types could be separated further by the species of the second atom, but the table has already enough numbers. We see a distinct prevalence of nearest-neighbor pairs of type 555—almost all nearest neighbors are of this type, the rest being 444 and 666. It is impossible to have every nearest-neighbor pair being of the 555 type in a crystal, but it certainly seems that the crystal structures here are trying to maximize the number of 555 neighbors. Now, “icosahedral order” strictly refers to having coordination number 12, all 555; however since in a binary alloy with a distinct size difference this coordination number is only achieved for the smaller atom, and only in a certain composition range, strict icosahedral order cannot be attained, but we still choose to refer to a high number of 555 pairs as representing “icosahedral order”.

Of the second neighbor pairs only a few are of type 211, most being 333 and 100. This is also consistent with icosahedral order: 333 pairs can be associated with pairs of tetrahedra which share a face, such as adjacent tetrahedra in a perfect icosahedron (or in the 555 structure, in view of our generalized sense of “icosahedral”). 211 pairs differ from 333 pairs by the removal of one of the common neighbors. It can be supposed that the 211 pairs are defects of the icosahedral structure, just as 544 and 433 pairs are, and thus that one would expect fewer of them relative to the number of 333 pairs in a more perfectly icosahedral structure. This is consistent with the fact that the numbers of 211 pairs decreases as temperature decreases in the glassy systems. In the same table are shown corresponding figures for the amorphous alloys of closest composition to the intermetallics, except that the numbers of 555, 544 and 433 pairs have been combined under the 555 column. The numbers for the amorphous alloys agree with those from the corresponding crystalline phase to within 20 percent in most cases, the biggest difference being the reduced number of 333 pairs, compensated more or less by the increase in 211 pairs. If we were to combine the 333 and 211 figures, like we have the 555, 544 and 433 ones, we would see that the structures in the amorphous and crystalline phases are locally very similar, the differences mostly being those between “perfect” 555 pairs and “imperfect” 544 and 433 pairs, and perfect and imperfect 333 and 211 pairs respectively.

### V.5 Explanation of second peak splitting

Our analysis indicates that the contributions from various CNA-types vary smoothly with temperature. Fig. 12 shows how the positions and widths of these peaks vary. One expects the widths to decrease as temperature decreases, and this is indeed the case. Their heights increase, mostly to compensate for the narrowing: we have already seen that the true measure of the weight of a peak, the number of pairs associated with it, has only a small temperature dependence in the case of the second neighbor peaks. The splitting can now be seen as a natural consequence of this narrowing. It is also aided a little by the decrease in weight of the 211 peak, which is in the middle, and the corresponding increase of the 333 peak on the short side. Thus the splitting of the second peak does not itself indicate any kind of structural transition. It merely follows from the fact that the structure at this length scale (second neighbor distance) associated with the liquid state remains as one cools into the glass state, and the narrowing of peaks which is to be expected as thermal motion decreases.

## VI Discussion and Summary

Our main intent in simulating the cooling of Mg-Cu alloys has been to generate glassy configurations that can be considered realistic enough for simulations investigating mechanical properties. Mg-Cu is a first step towards the more technologically interesting material Mg-Cu-Y. In order to assess the realism of the simulations we have studied various aspects of the glass-forming nature of the alloys: the thermodynamics, glass transition and structure. There are three intrinsic limitations to these kinds of simulations: the interatomic potential, the system size and the timescale. We have reason to believe that the EMT interatomic potential is not a major limitation in this study. We have already discussed how much the physics of the binary amorphous alloy formation is based on size factors as well as the stability and structure of any nearby (in composition) intermetallic compounds. The fact that EMT parameters can be chosen to match quite closely the formation enthalpies of the two Mg-Cu intermetallics means that the general bonding energetics are reasonably well-represented. De Tendler et al. DeTendler et al. (1992) applied the empirical model of Miedema for alloy formation to compute the glass-forming region of the Mg-Cu system. The close agreement with experiment they found indicates that there is nothing particularly unusual about this system.

This leads to the one feature of the Mg-Cu system which is poorly described by our simulations: the extent of the glass forming region. The width of the glass-forming region is certainly a timescale-issue since the accessible timescales preclude nucleation of a crystal phase more complex than fcc; thus almost all compositions form a glassy phase upon cooling. Issues of length scale could conceivably also be relevant for the formation of the more complex Mg2Cu with its large unit cell. Of course, an advantage of being able to simulate glass-formation in a wide range of compositions is that it makes clearer that the splitting of the second peak and the glass transition are not coupled, since their dependences on temperature do not match. If one leaves aside crystallization, the fact that our results are largely independent of cooling rate, and the fact that the glass transition temperature for the eutectic composition matches the experimental one, suggest that the timescale is not otherwise a problem—until the onset of the glass transition itself of course; there the fast cooling rates lead to the broadening of the transition compared to what would be expected experimentally. This of course does not rule out the possibility that there are relaxations that take place on time scales significantly longer than those of our slowest cooling rate, yet still fast enough to take place during the experimental cooling. A possibility is that such relaxations might be associated with a length scale larger than our system size; thus our cooling rates are all slow enough to relax all structural rearrangements that are smaller than our system size, and thus we do not see any rate dependence, but perhaps we would see it in larger systems—the timescale issue and lengthscale issue would be in effect canceling each other out. However any such extra relaxations must be very low energy, because the residual enthalpies with respect to the crystal phases are as small as are measured experimentally. Another “canceling” possibility is that defects in the interatomic potential, causing energy barriers to relaxation to be lower than they should, would lead to the relaxation times being lower and thus to the simulated cooling rate being more adequate than it otherwise should be. Guerdane and Teichler Guerdane and Teichler (2001) simulated Ni-Zr and ternary Ni-Zr-Al glass formation and obtained $`T_g`$s higher than experimental ones by a few hundred Kelvin, which they explained as being due to the difference between their cooling rate ($`10^{10}K/s`$) and the experimental one, which makes it surprising that we do not see such a discrepancy. If it is indeed due to too-low relaxation barriers, this may not matter so much for the purpose of obtaining low temperature glassy configurations; however it may be relevant for future studies of plastic deformation.

###### Acknowledgements.

We thank Jim Sethna and Andrei Ruban for helpful discussion. This work was supported by the Danish Research Councils through Grant No. 5020-00-0012 and by the Danish Center for Scientific Computing through Grant No. HDW-1101-05. CAMP is sponsored by the Danish National Research Foundation.


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# Physical Baryon Resonance Spectroscopy from Lattice QCD

## 1 INTRODUCTION

There has been enormous progress in the calculation of the masses of excited baryons in quenched lattice QCD - as a consequence of improved computing resources and the development of spin and parity projection methods. At present, established fitting techniques have successfully extracted resonance masses for quark masses or (equivalently, through the Goldberger-Treiman relation) pion masses in the range $`m_\pi ^2>0.3`$ GeV2. The difficulty lies in maintaining a clear signal for the effective mass of the baryon resonance as the quarks become light. In this region the masses of the first negative and positive parity excited states obtained from standard interpolating fields follow the expectations of the naive harmonic oscillator based quark model with roughly equal spacing between the ground state nucleon, the first $`1/2^{}`$ and the first $`1/2^+`$ excited states.

Quite apart from the ordering of excited states, the chiral extrapolation of hadron masses is a topic of current interest because of the well known non-analytic behaviour with quark mass and the need to incorporate the consequent, model independent constraints of chiral symmetry. For the octet and decuplet baryons as well as the $`\rho `$-meson this problem has been studied extensively and the technique for extracting physical masses with small systematic uncertainties is well understood -. Our aim is to generalise those results to the baryon excited states currently accessible on the lattice.

## 2 CHIRAL PERTURBATION THEORY AND CHIRAL EXPANSION

In the context of the extrapolation of lattice data, chiral perturbation theory provides a functional form applicable as the quark mass vanishes or, equivalently $`m_\pi ^20`$. Goldstone boson loops play an important role in the theory as they give rise to non-analytic behavior as a function of quark mass. All hadron properties receive contributions involving these loops. For $`m_\pi <`$ 400-500 MeV, Goldstone loops lead to rapid, non-analytic variation with $`m_q`$. This non-analyticity must therefore be incorporated in any extrapolation scheme.

Chiral effective field theory gives a formal expansion of a baryon mass about the chiral limit

$$M_B=a_0+a_2m_\pi ^2+a_4m_\pi ^4+\underset{B^{}}{}\sigma _{BB^{}\pi }(m_\pi ,\mathrm{\Lambda })+\mathrm{}$$
(1)
where $`a_i`$ are the coefficients of the analytic terms, $`\mathrm{\Lambda }`$ is a parameter associated with the regularisation, and $`\sigma _{BB^{}\pi }`$ are pion-induced self-energy contributions. Here we consider $`P`$-wave pion-baryon contributions, focusing on the most important baryon states as determined by the strength of the meson-baryon coupling constants (see Ref.  for details).

Figure 1 shows the extrapolation of CSSM Lattice collaboration  data for ground-state and low-lying excited baryon states. Dashed lines represent naive linear extrapolations while solid lines incorporate the non-analytic variation with $`m_q`$. Experimental masses are shown as filled ellipses.

## 3 CONCLUSION & OUTLOOK

We have presented the first quantitative analysis of the baryon resonance spectrum from lattice QCD in which the chiral non-analytic behavior of QCD is incorporated. It is interesting to note that a small downward shift in the lattice results upon unquenching (as suggested in Ref. ) would provide remarkable agreement with experiment. The incorporation of chiral non-analytic behavior inverts the $`N\frac{1}{2}^{}(1535)`$ and $`N\frac{3}{2}^{}(1520)`$ ordering when compared to the naive linear extrapolation, in accord with experiment.

Encouraged by these early successes, work is now in progress to include additional self-energy contributions. $`S`$-wave contributions are of particular interest due to the non-analytic structure of their contributions. Ultimately, quenched chiral perturbation theory will be formulated providing the opportunity to quantitatively estimate the predictions of full QCD.


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# A Cross-media Retrieval System for Lecture Videos

## 1 Introduction

The growing number of multimedia contents available via the World Wide Web, CD-ROMs, and DVDs has made information technologies incorporating speech, image, and text processing crucial. Of the various types of contents, lectures (audio/video) are typical and a valuable multimedia resource, in which speeches (i.e., oral presentations) are usually organized based on text materials, such as resumes, slides, and textbooks. In lecture videos, image information, such as flip charts, is often also used. In other words, a single lecture consists of different types of compatible multimedia contents.

Because a single lecture often refers to several topics and takes a long time, it is useful to obtain specific segments (passages) selectively so that the audience can satisfy their information needs at minimum cost. To resolve this problem, in this paper we propose a lecture-on-demand system that retrieves relevant video/audio passages in response to user queries. For this purpose, we utilize the benefits of different media types to improve retrieval performance.

On the one hand, text has the advantage that users can view/scan the entire contents quickly and can easily identify relevant passages using the layout information (e.g., text structures based on sections and paragraphs). In other words, text contents can be used for random-access purposes. On the other hand, speech is used mainly for sequential-access purposes. Therefore, it is difficult to identify relevant passages unless target video/audio data includes additional annotation, such as indexes. Even if the target data are indexed, users are not necessarily able to provide effective queries. To resolve this problem, textbooks are desirable materials from which users can extract effective keywords and phrases. However, while textbooks are usually concise, speech has a high degree of redundancy and therefore is easier to understand than textbooks, especially where additional image information is provided.

In view of the above, we model our lecture-on-demand (LOD) system as follows. A user selects text segments (keywords, phrases, sentences, and paragraphs) that are relevant to their information needs from a textbook for a target lecture. By using selected segments, a text query is generated automatically. That is, queries can be formulated even if users cannot provide effective keywords. Users can also submit additional keywords as queries, if necessary. Video passages relevant to a given query are retrieved and presented to the user. To retrieve the video passages in response to text queries, we extract the audio track from a lecture video, generate a transcription by means of large vocabulary continuous speech recognition, and produce a text index, prior to system use. Our system is a cross-media system in the sense that users can retrieve video and audio information by means of text queries.

## 2 System Description

### 2.1 Overview

Figure 1 depicts the overall design of our lecture-on-demand system, in which the left and right regions correspond to the on-line and off-line processes, respectively. Although our system is currently implemented for Japanese, our methodology is fundamentally language independent. For the purpose of research and development, we tentatively target lecture programs on TV for which textbooks are published. We explain the basis of our system using Figure 1.

In the off-line process, given the video data of a target lecture, audio data are extracted and segmented into a number of passages. Then, a speech recognition system transcribes each passage. Finally, the transcribed passages are indexed as in conventional text retrieval systems, so that each passage can be retrieved efficiently in response to text queries. To adapt speech recognition to a specific lecturer, we perform unsupervised speaker adaptation using an initial speech recognition result (i.e., a transcription). To adapt speech recognition to a specific topic, we perform language model adaptation, for which we search a general corpus for documents relevant to the textbook related to a target lecture. Then, retrieved documents (i.e., a topic-specific corpus) are used to produce a word-based N-gram language model. We also perform image analysis to extract text (e.g., keywords and phrases) from flip charts. These contents are also used to improve our language model.

In the on-line process, a user can view specific video passages by submitting any text queries, i.e., keywords, phrases, sentences, and paragraphs, extracted from the textbook. Any queries not in the textbook can also be used. The current implementation is based on a client-server system on the Web. Both the off-line and on-line processes are performed on servers, but users can access our system using Web browsers on their own PCs.

Figure 2 depicts a prototype interface of our LOD system, in which a lecture associated with “nonlinear multivariate analysis” is given. In this interface, an electronic version of a textbook is displayed on the left side, and a lecture video is played on the right side. In addition, users can submit any text queries in the input box, which is not depicted in Figure 2. In this scenario, a text paragraph related to “discriminant analysis” was copied and pasted into the query input box, and top-ranked transcribed passages for the query were listed according to the degree of relevance (in the lower part of Figure 2). Users can select (click on) transcriptions to play the corresponding video passage.

It should be noted that unlike conventional keyword-based retrieval systems, in which users usually submit a small number of keywords, in our system users can easily submit longer queries using textbooks. Where submitted keywords are misrecognized in transcriptions, the retrieval accuracy decreases. However, longer queries are relatively robust for speech recognition errors, because the effect of misrecognized words is overshadowed by the large number of words correctly recognized.

### 2.2 Passage Segmentation

The basis of passage segmentation is to divide the entire video data for a single lecture into more than one unit to be retrieved. We call these smaller units “passages”. For this purpose, both speech and image data can provide promising clues. However, in lecture TV programs, it is often the case that a lecturer sitting still is the main focus and a small number of flip charts are used occasionally. In such cases, image data is less informative. Therefore, tentatively we use only speech data for the passage segmentation process. However, segmentation can potentially vary depending on the user query. Thus, it is difficult to predetermine a desirable segmentation in the off-line process.

Because of the above problems, we first extract the audio track from a target video and use a simple pause-based segmentation method to obtain minimal speech units, such as sentences and long phrases. In other words, speech units are continuous audio segments that do not include pauses longer than a certain threshold. Finally, we generate variable-length passages from one or more speech units. To put it more precisely, we combine $`N`$ speech units into a single passage, with $`N`$ ranging from 1 to 5 in the current implementation.

### 2.3 Speech Recognition

The speech recognition module generates word sequence $`W`$, given phone sequence $`X`$. In a stochastic framework, the task is to select the $`W`$ maximizing $`P\left(W|X\right)`$, which is transformed as in Equation (1) through the Bayesian theorem.

$$\mathrm{arg}\underset{W}{\mathrm{max}}P\left(W|X\right)=\mathrm{arg}\underset{W}{\mathrm{max}}P\left(X|W\right)P\left(W\right)$$
(1)
$`P\left(X|W\right)`$ models the probability that the word sequence $`W`$ is transformed into the phone sequence $`X`$, and $`P\left(W\right)`$ models the probability that $`W`$ is linguistically acceptable. These factors are called the acoustic and language models, respectively.

We use the Japanese dictation toolkit111http://winnie.kuis.kyoto-u.ac.jp/dictation/, which includes the Julius decoder and acoustic/language models. Julius performs a two-pass (forward-backward) search using word-based forward bigrams and backward trigrams. The acoustic model was produced from the ASJ speech database, which contains approximately 20,000 sentences uttered by 132 speakers including both gender groups. A 16-mixture Gaussian distribution triphone Hidden Markov Model, in which states are clustered into 2,000 groups by a state-tying method, is used. We adapt the provided acoustic model by means of an MLLR-based unsupervised speaker adaptation method, for which in practice we use the HTK toolkit222http://htk.eng.cam.ac.uk/.

Existing methods to adapt language models can be classified into two fundamental categories. In the first category—the integration approach—general and topic-specific corpora are integrated to produce a topic-specific language model . Because the sizes of those corpora differ, N-gram statistics are calculated using the weighted average of the statistics extracted independently from those corpora. However, it is difficult to determine the optimal weight depending on the topic. In the second category—the selection approach—a topic-specific subset is selected from a general corpus and is used to produce a language model. This approach is effective if general corpora contain documents associated with target topics, but N-gram statistics in those documents are overshadowed by other documents in resultant language models.

We followed the selection approach, because the 10M Web page corpus  containing mainly Japanese pages associated with various topics was publicly available. The quality of the selection approach depends on the method of selecting topic-specific subsets. An existing method  uses hypotheses in the initial speech recognition phase as queries to retrieve topic-specific documents from a general corpus. However, errors in the initial hypotheses have the potential to decrease the retrieval accuracy. Instead, we use textbooks related to target lectures as queries to improve the retrieval accuracy and consequently the quality of the language model adaptation.

### 2.4 Retrieval

Given transcribed passages and text queries, the basis of the retrieval module is the same as that for text retrieval. We use an existing probabilistic text retrieval method  to compute the relevance score between the query and each passage in the database. The relevance score for passage $`p`$ is computed by Equation (2).

$$\underset{t}{}f_{t,q}\frac{\left(K+1\right)f_{t,p}}{K\left\{\left(1b\right)+\frac{dl_p}{bavgdl}\right\}+f_{t,p}}\mathrm{log}\frac{Nn_t+0.5}{n_t+0.5}$$
(2)
where $`f_{t,q}`$ and $`f_{t,p}`$ denote the frequency with which term $`t`$ appears in query $`q`$ and passage $`p`$, respectively. $`N`$ and $`n_t`$ denote the total number of passages in the database and the number of passages containing term $`t`$, respectively. $`dl_p`$ denotes the length of passage $`p`$, and $`avgdl`$ denotes the average length of passages in the database. We empirically set $`K=2.0`$ and $`b=0.8`$, respectively. We use content words, such as nouns, extracted from transcribed passages as index terms, and perform word-based indexing. We use the ChaSen morphological analyzer333http://chasen.aist-nara.ac.jp/ to extract content words. The same method is used to extract terms from queries.

However, retrieved passages are not disjoint, because top-ranked passages often overlap with one another in terms of the temporal axis. It is redundant simply to list the top-ranked retrieved passages as they are. Therefore, we reorganize those overlapped passages into a single passage. The relevance score for a group (a new passage) is computed by averaging the scores of all passages belonging to the group. New passages are sorted according to the degree of relevance and are presented to users as the final result.

## 3 Experimentation

### 3.1 Methodology

To evaluate the performance of our LOD system, we produced a test collection (as a benchmark data set) and performed experiments partially resembling a task performed in the TREC spoken document retrieval (SDR) track . Five lecture programs on TV (each lecture was 45 minutes long), for which printed textbooks were also published, were videotaped in DV and were used as target lectures. Each lecture was manually transcribed and sentence boundaries with temporal information (i.e., correct speech units) were also identified manually. Each paragraph in the corresponding textbook was used as a query independently. For each query, a human assessor (a graduate student not an author of this paper) identified one or more relevant sentences in the human transcription.

Using our test collection, we evaluated the accuracy of speech recognition and passage retrieval. For the five lectures, our system used the sentence boundaries in human transcriptions to identify speech units, and performed speech recognition. We also used human transcriptions as perfect speech recognition results and investigated the extent to which speech recognition errors affect the retrieval accuracy. Our system retrieved top-ranked passages in response to each query. Note that the passages here are those grouped based on the temporal axis, which should not be confused with those obtained from the passage segmentation method.

### 3.2 Results

To evaluate the accuracy of speech recognition, we used the word error rate (WER), which is the ratio of the number of word errors (deletion, insertion, and substitution) to the total number of words. We also used test-set out-of-vocabulary rate (OOV) and trigram test-set perplexity (PP) to evaluate the extent to which our language model adapted to the target topics. We used human transcriptions as test set data. For example, OOV is the ratio of the number of word tokens not contained in the language model for speech recognition to the total number of word tokens in the transcription. Note that smaller values of OOV, PP, and WER are obtained with better methods.

The final outputs (i.e., retrieved passages) were evaluated based on recall and precision, averaged over all queries. Recall (R) is the ratio of the number of correct speech units retrieved by our system to the total number of correct speech units for the query in question. Precision (P) is the ratio of the number of correct speech units retrieved by our system to the total number of speech units retrieved by our system. To summarize recall and precision into a single measure, we used the F-measure (F).

Table 1 shows the accuracy of speech recognition (WER) and passage retrieval (R, P, and F), for each lecture. In this table, the columns “HUM” and “ASR” correspond to the results obtained with human transcriptions and automatic speech recognition, respectively. The column “+LA” denotes results for ASR combined with language model adaptation. The column “Topic” denotes topics for the five lectures.

To adapt language models, we used the textbook corresponding to a target lecture and searched the 10M Web page corpus for 2,000 relevant pages, which were used as a source corpus. In the case where the language model adaptation was not performed, all 10M Web pages were used as a source corpus. In either case, 20,000 high frequency words were selected from a source corpus to produce a word-based trigram language model. We used the ChaSen morphological analyzer to extract words (morphemes) from the source corpora, because Japanese sentences lack lexical segmentation.

In passage retrieval, we regarded the top $`N`$ passages as the final outputs. In Table 1, the value of $`N`$ ranges from 1 to 3. As the value of $`N`$ increases, the recall improves, but potentially sacrificing precision.

### 3.3 Discussion

By comparing the results of ASR and +LA in Table 1, for some cases OOV and PP increased by adapting language models. However, WER decreased by adapting language models to target topics, irrespective of the lecture.

The values of OOV, PP, and WER for lecture #1 were generally smaller than those for the other lectures. One possible reason is that the lecturer of #1 spoke more fluently and made fewer erroneous utterances than the other lecturers.

Recall, precision, and F-measure increased by adapting language models for lectures #2-5, irrespective of the number of passages retrieved. For lecture #1, the retrieval accuracy did not significantly differ whether or not we adapted the language model to the topic. One possible reason is that the WER of lecture #1 without language model adaptation (20.9%) was sufficiently small to obtain a retrieval accuracy comparable with the text retrieval . The difference between HUM and ASR was marginal in terms of the retrieval accuracy. Therefore, the effect of the language model adaptation method was overshadowed in passage retrieval.

The retrieval accuracy for lecture #1 was higher than those for the other lectures. The story of lecture #1 was organized based primarily on the textbook, when compared with the other lectures. This suggests that the performance of our LOD system is dependent of the organization of target lectures.

Surprisingly, for lectures #1 and #2, recall, precision, and F-measure of +LA were better than those of HUM. This means that the automatic transcription was more effective than human transcription for passage retrieval purposes. One possible reason is the existence of Japanese variants (i.e., more than one spelling form corresponding to the same word), such as “girisha/girishia (Greece)”. Because the language model was adapted by means of the textbook for a target lecture, the spelling in automatic transcriptions systematically resembled that in the queries extracted from the textbooks. In contrast, it is difficult to standardize the spelling in human transcriptions. Therefore, relevant passages in automatic transcriptions were more likely to be retrieved than passages in the human transcriptions.

We conclude that our language model adaptation method was effective for both speech recognition and passage retrieval.

## 4 Conclusion

Reflecting the rapid growth in the use of multimedia contents, information technologies appropriate to speech, image, and text processing are crucial. Of the various content types in this paper we focused on the video data of lectures with their organization based on textbooks, and proposed a system for cross-media on-demand lectures, in which users can formulate text queries using the textbook for a target lecture to retrieve specific video passages.

To retrieve video passages in response to text queries, we extract the audio track from a lecture video, generate a transcription by large vocabulary continuous speech recognition, and produce a text index, prior to system use.

We evaluated the performance of our system experimentally, for which five TV lecture programs in various topics were used. The experimental results showed that the accuracy of speech recognition varied depending on the topic and presentation style of the lecturers. However, the accuracy of speech recognition and passage retrieval was improved by adapting language models to the topic of the target lecture. Even if the word error rate was approximately 40%, the accuracy of retrieval was comparable with that obtained by human transcription.


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# On improving single photon sources via linear optics and photodetection

## Abstract

In practice, single photons are generated as a mixture of vacuum with a single photon with weights $`1p`$ and $`p`$, respectively; here we are concerned with increasing $`p`$ by directing multiple copies of the single photon-vacuum mixture into a linear optic device and applying photodetection on some outputs to conditionally prepare single photon states with larger $`p`$. We prove that it is impossible, under certain conditions, to increase $`p`$ via linear optics and conditional preparation based on photodetection, and we also establish a class of photodetection events for which $`p`$ can be improved. In addition we prove that it is not possible to obtain perfect ($`p=1`$) single photon states via this method from imperfect ($`p<1`$) inputs.

Single photon sources are important, for example to achieve secure quantum key distribution key  and for linear optic quantum computation LOQC , yet generating single photons remains challenging. The traditional method involves photodetection on one output mode from a nondegenerate parametric downconversion process to post-select a single photon in the correlated mode down . More recently alternative single-photon sources have been employed, including molecules mol , quantum wells well , color centers col , ions ion  and quantum dots dot . In these examples, the probability of more than one photon being produced is much lower than that for a Poissonian process, but the vacuum contribution can be quite high. Under ideal conditions, with a single mode output stable over time, the output state can be described by the density matrix

$$\widehat{\rho }_p=(1p)|00|+p|11|,$$
(1)
with $`p`$ the probability of obtaining a single photon; $`p`$ is sometimes referred to as the efficiency for producing single photons. Whereas the theoretical single-photon state corresponds to $`p=1`$, the experimental single-photon state is a mixture of the single photon with the vacuum.

Increasing the value of $`p`$ (the efficiency of producing single photons) is an increasingly important objective because of requirements for quantum optics experiments, especially those concerned with quantum information processing. Much of this effort is directed to improving sources, but here we pose the question as to whether a source of single photons with efficiency $`p`$ can be processed via linear optics and photodetection to yield fewer photons but with higher $`p`$. More specifically, would it be possible to direct $`N`$ copies of these single photon states with efficiency $`p`$ into an $`N`$-channel passive interferometer (an interferometer that involves only passive, linear optical elements) to yield an output single photon with efficiency $`p^{}>p`$ for certain photodetection records on the other outputs? If the answer is yes, then interferometry and photodetection could be employed to improve the efficiency of single-photon sources.

In fact the answer will be no, provided we consider detection results where all but one of the photons are detected. This is the most straightforward way of ensuring that the output state contains at most one photon. This restriction is necessary in most applications of linear optics quantum information processing since two-photon contributions can have unwanted side effects, e.g. allowing for certain multiphoton attacks in quantum key distribution applications. If we allow other detection results, it is possible for low-efficiency (small $`p`$) single-photon states to yield, via linear optics and conditional preparation based on photodetection, an output with a larger probability for a single photon. However, these schemes also yield non-zero probabilities for photon numbers above one.

A passive interferometer is comprised of beam splitters, mirrors, and phase shifters. Each of these elements preserves total photon number from input to output under ideal conditions. No energy is required to operate these optical elements, hence the term passive. These are also known as linear optical elements. More generally polarization transforming elements can be included, but here we are concerned only with a scalar field treatment; in fact polarization effects could be included by doubling the number of channels and treating the two polarizations in a mode as two separate channels. Mathematically, a passive interferometer transforms the amplitude operators of the incoming fields $`\widehat{𝒂}`$ via the matrix transformation $`\widehat{𝒂}^{}𝚲^T\widehat{𝒂}^{}`$ with $`\mathrm{\Lambda }\text{U}(N)`$ VogelWelsch .

In the general case we start with a supply of $`N`$ mixed states of the form (1). For additional generality we allow the different inputs to have different probabilities for finding a single photon, $`p_i`$, and we denote the maximum of these probabilities by $`p_{\mathrm{max}}`$. The initial state may be expressed as

$`\widehat{\rho }_{\text{in}}^{(N)}`$ $`={\displaystyle \underset{i=1}{\overset{N}{}}}\left[(1p_i)|00|+p_i|11|\right]`$
$`={\displaystyle \underset{𝒔}{}}P_𝒔\left({\displaystyle \underset{i}{}}(\widehat{a}_i^{})^{s_i}|0\text{h.c.}\right),`$ (2)
where $`P_𝒔`$ $`=`$ $`_ip_i^{s_i}(1p_i)^{1s_i}`$, and the vector $`𝒔`$ $`=`$ $`(s_1,\mathrm{},s_N)^T`$, ($`s_i=0,1`$), gives the photon numbers in the inputs. The interferometer transformation $`\widehat{𝒂}^{}𝚲^T\widehat{𝒂}^{}`$ results in the output state

$$\widehat{\rho }_{\mathrm{trans}}^{(N)}=\underset{𝒔}{}P_𝒔\left[\underset{i}{}\left(\underset{k}{}\mathrm{\Lambda }_{ki}\widehat{a}_k^{}\right)^{s_i}|0\text{h.c.}\right].$$
(3)
Without loss of generality, we take mode 1 to be the mode in which we wish to improve the photon statistics. We perform photodetections on the other $`N1`$ modes, and examine the final state in mode 1 conditioned on the results of these photodetections. The total number of photons detected is $`D`$, and the number of photons detected in mode $`j`$ is $`n_j`$ (see Fig. 1). It is easy to see that no better result can be obtained by performing photodetections on fewer than $`N1`$ modes; this would be equivalent to averaging over the photocounts for some of the modes. We assume ideal photodetection in this analysis in order to determine the best results possible using linear optics and photodetection.

The conditional state in mode 1 after photodetection in modes 2 to $`N`$ is

$$\widehat{\rho }_{\mathrm{out}}^{(N)}=\underset{n_1=0}{\overset{N}{}}c_{n_1}|n_1n_1|,$$
(4)
where $`n_1`$ is the photon number in the remaining output mode (rather than the number of photons detected at a photodetector). Each coefficient $`c_{n_1}`$ is given by

$$c_{n_1}=K𝒏|\widehat{\rho }_{\mathrm{trans}}^{(N)}|𝒏,$$
(5)
where $`|𝒏`$ is a tensor product of number states in each of the output modes. The normalization constant $`K`$ equals

$$K=\left[\underset{n_1=0}{\overset{N}{}}𝒏|\widehat{\rho }_{\mathrm{trans}}^{(N)}|𝒏\right]^1.$$
(6)
In order to find the expectation value in Eq. (5), we first introduce some notation. Let $`\mathrm{\Phi }_𝒔=\{i|s_i=1\}`$, $`\mathrm{\Sigma }_𝒔=_is_i`$ (so $`\mathrm{\Sigma }_𝒔`$ is the number of elements in $`\mathrm{\Phi }_𝒔`$), and let $`\mathrm{Y}_𝒔`$ be the set that consists of all vectors comprised of the elements of $`\mathrm{\Phi }_𝒔`$. In addition we use the notation $`K^{}=K/_{j=2}^Nn_j!`$ and $`\mathrm{\Sigma }_𝒏=_jn_j`$. Using this notation, $`c_1`$ is given by

$$c_1=\frac{K^{}}{n_1!}\underset{𝒔;\mathrm{\Sigma }_𝒔=\mathrm{\Sigma }_𝒏}{}P_𝒔\left|S_{𝒔,𝒏}\right|^2,$$
(7)
where

$`S_{𝒔,𝒏}`$ $`={\displaystyle \underset{𝝈\mathrm{Y}_𝒔}{}}\left(\mathrm{\Lambda }_{1,\sigma _1}\mathrm{}\mathrm{\Lambda }_{1,\sigma _{n_1}}\right)`$
$`\mathrm{}\left(\mathrm{\Lambda }_{N,\sigma _{\mathrm{\Sigma }_𝒏n_N+1}}\mathrm{}\mathrm{\Lambda }_{N,\sigma _{\mathrm{\Sigma }_𝒏}}\right).`$ (8)
In order to determine if there is an improvement in the probability of finding a single photon, we need to determine the value of $`c_1`$. However, determining $`c_1`$ requires evaluating $`K`$, which requires evaluating the expectation values in Eq. (5) for all possible values of $`n_1`$. Instead, we will consider the ratio $`c_1/c_0`$. There are three main advantages to considering this quantity:
1. The common constant $`K^{}`$ cancels, so this expression is easily evaluated analytically.
2. If $`c_1/c_0`$ is not greater than $`Rp_{\mathrm{max}}/(1p_{\mathrm{max}})`$, then it is clear that $`c_1p_{\mathrm{max}}`$. Thus we can determine those cases where there is no improvement.
3. For $`p_{\mathrm{max}}1`$, $`c_01`$ and $`Rp_{\mathrm{max}}`$. Therefore the improvement in $`c_1/c_0`$ over $`R`$ is approximately the same as the improvement in the probability of a single photon over $`p_{\mathrm{max}}`$.

Ideally, we would determine the interferometer and detection pattern such that $`c_1/c_0`$ is maximized, but this does not appear to be possible analytically. However, we can place an upper limit on $`c_1/c_0`$ in the following way. Let us express the summation for $`c_0`$ as

$$c_0=\frac{K^{}}{ND}\underset{𝒔;\mathrm{\Sigma }_𝒔=D+1}{}\underset{k;s_k=1}{}P_{𝒔^k}\left|S_{𝒔^k,𝒏^{}}\right|^2,$$
(9)
where $`s_i^k=s_i`$ except for $`s_k^k=0`$, and $`n_j^{}=n_j`$ except $`n_1^{}=0`$. The quotient of $`ND`$ takes account of a redundancy in the sum. Each alternative input $`𝒔^k`$ has $`ND`$ zeros, so there are $`ND`$ possible alternative $`𝒔`$ that give the same $`𝒔^k`$. We may reduce this quotient slightly if we take account of the possibility that some of the inputs have zero photon probability. Let there be $`NM`$ inputs with $`p_i=0`$, so the maximum total number of photons is $`M`$. If we limit the first sum in Eq. (9) to $`𝒔`$ such that $`P_𝒔0`$, then the redundancy is $`MD`$. Therefore we obtain

$`c_0`$ $`={\displaystyle \frac{K^{}}{MD}}{\displaystyle \underset{\begin{array}{c}𝒔;P_𝒔0\\ \mathrm{\Sigma }_𝒔=D+1\end{array}}{}}{\displaystyle \underset{k;s_k=1}{}}P_{𝒔^k}\left|S_k\right|^2`$
$`={\displaystyle \frac{K^{}}{MD}}{\displaystyle \underset{\begin{array}{c}𝒔;P_𝒔0\\ \mathrm{\Sigma }_𝒔=D+1\end{array}}{}}P_𝒔{\displaystyle \underset{k;s_k=1}{}}{\displaystyle \frac{1p_k}{p_k}}\left|S_k\right|^2,`$ (10)
where $`S_k=S_{𝒔^k,𝒏^{}}`$. Since we have limited the sum to terms where $`P_𝒔0`$, $`p_k`$ is nonzero, and thus the ratio $`(1p_k)/p_k`$ does not diverge. Since $`p_k`$ does not exceed $`p_{\mathrm{max}}`$, we have the inequality

$$c_0\frac{K^{}}{MD}\frac{1p_{\mathrm{max}}}{p_{\mathrm{max}}}\underset{𝒔;\mathrm{\Sigma }_𝒔=D+1}{}P_𝒔\underset{k;s_k=1}{}\left|S_k\right|^2.$$
(11)
Here we are able to omit the condition $`P_𝒔0`$ because terms with $`P_𝒔=0`$ are zero anyway. We may re-express the equation for $`c_1`$ as

$$c_1=K^{}\underset{𝒔;\mathrm{\Sigma }_𝒔=D+1}{}P_𝒔\left|\underset{k;s_k=1}{}\mathrm{\Lambda }_{1k}S_k\right|^2.$$
(12)
We therefore obtain

$$c_1K^{}\underset{𝒔;\mathrm{\Sigma }_𝒔=D+1}{}P_𝒔\underset{k;s_k=1}{}\left|S_k\right|^2.$$
(13)
Combining Eqs. (11) and (13) gives

$$\frac{c_1}{c_0}(MD)\frac{p_{\mathrm{max}}}{1p_{\mathrm{max}}}.$$
(14)
This yields an upper limit on the ratio between the one and zero photon probabilities. One application of this result is that it is impossible to get one photon with unit probability, as it would be necessary for this ratio is infinite. Another consequence of (14) is that for $`D=M1`$ (i.e. the number of photons detected one less the maximum input number) an improvement can never be achieved. This case is important because it is the most straightforward way of eliminating the possibility of two or more photons in the output mode.

In the remainder of this article, we will investigate situations in which the single-photon contribution can be enhanced. As $`MN`$, and $`D0`$, the upper limit on the improvement in $`c_1/c_0`$ is simply $`N`$. This is also the upper limit in how far $`c_1`$ can be increased above $`p_{\mathrm{max}}`$. We will now consider a scheme that gives a linear improvement in $`c_1/c_0`$, though not as high as $`N`$. In order to obtain a large value for the ratio $`c_1/c_0`$, we want the inequality in Eq. (13) to be as close to equality as possible. In turn, this means that we want the vectors $`(\mathrm{\Lambda }_{1k})`$ and $`(S_k)`$ to be as close to parallel as possible. For this, we consider the interferometer given by

$`\mathrm{\Lambda }_{21}=ϵ,`$ $`\mathrm{\Lambda }_{22}=\sqrt{1ϵ},`$
$`\mathrm{\Lambda }_{i1}=\sqrt{(1ϵ^2)/(N1)},`$ $`\mathrm{\Lambda }_{i2}=ϵ/\sqrt{N1},`$ (15)
for $`i2`$ (the values of $`\mathrm{\Lambda }_{ij}`$ for $`j>2`$ do not enter into the analysis). Here $`ϵ`$ is a small number, and we will ignore terms of order $`ϵ`$ or higher. Now let $`p_i=p_{\mathrm{max}}`$, and consider the measurement record where zero photons are detected in modes 3 to $`N`$, and $`D`$ photons are detected in output mode 2. To determine $`c_{n_1}`$, note first that $`\mathrm{\Lambda }_{22}\mathrm{\Lambda }_{2i}`$ for $`i2`$, so we may ignore those terms in the sum for $`S_{𝒔,𝒏}`$ where $`\mathrm{\Lambda }_{22}`$ does not appear. Each term has magnitude $`\mathrm{\Lambda }_{11}^{n_1}\mathrm{\Lambda }_{22}\mathrm{\Lambda }_{21}^{D1}`$ 111Here we are using $`\mathrm{\Lambda }_{21}`$ and $`\mathrm{\Lambda }_{11}`$ to indicate the values of $`\mathrm{\Lambda }_{2i}`$ and $`\mathrm{\Lambda }_{1i}`$ for $`i2`$., and there are $`D(D+n_11)!`$ such terms. Therefore, provided $`s_2=1`$,

$$S_{𝒔,𝒏}D(D+n_11)!\mathrm{\Lambda }_{11}^{n_1}\mathrm{\Lambda }_{22}\mathrm{\Lambda }_{21}^{D1},ϵ1.$$
(16)
In the summation for $`c_{n_1}`$, we have $`\left(\genfrac{}{}{0pt}{}{N1}{Dn_11}\right)`$ different combinations of inputs such that $`\mathrm{\Sigma }_𝒔=D+n_1`$ and $`s_2=1`$. Combining these results, we have

$`c_{n_1}`$ $`{\displaystyle \frac{K^{}}{n_1!}}p_{\mathrm{max}}^{D+s_1}(1p_{\mathrm{max}})^{NDs_1}`$
$`\times {\displaystyle \frac{(N1)!D^2(D+n_11)!}{(NDn_1)!}}\mathrm{\Lambda }_{11}^{2n_1}\mathrm{\Lambda }_{22}^2\mathrm{\Lambda }_{21}^{2D2}`$
$`K^{\prime \prime }\left({\displaystyle \frac{R}{N1}}\right)^{n_1}{\displaystyle \frac{(D+n_11)!}{n_1!(NDn_1)!}},`$ (17)
We have combined those factors that do not depend on $`n_1`$ into a new constant $`K^{\prime \prime }`$, and used $`\mathrm{\Lambda }_{11}1/\sqrt{N1}`$.

Using Eq. (On improving single photon sources via linear optics and photodetection) we find that

$$\frac{c_1}{c_0}R\frac{D(ND)}{N1},ϵ1.$$
(18)
The maximum improvement in the ratio $`c_1/c_0`$ is obtained for $`D=N/2`$, where $`c_1/c_0=RN^2/4/(N1)`$. The multiplying factor $`N^2/4/(N1)`$ is larger than 1 for all $`N4`$. Thus we find that, provided there are at least 4 modes, we may obtain an improvement in the ratio $`c_1/c_0`$. For $`p_{\mathrm{max}}1`$, $`c_1p_{\mathrm{max}}N^2/4/(N1)`$. For large $`N`$, the probability of a single photon increases approximately as $`N/4`$. This is linear with $`N`$, but is not quite as large as the upper limit of $`N`$.

However, there are some drawbacks to this interferometry scheme \[i.e. using the interferometer (On improving single photon sources via linear optics and photodetection)\]. The first drawback is the two-photon contribution. We find that

$$\frac{c_2/c_1}{c_1/c_0}=\frac{(D+1)(ND1)}{2D(ND)},$$
(19)
which, for $`D=N/2`$, is less than $`1/2`$, but it is close to $`1/2`$ for large $`N`$. Since this is the same ratio as for a Poisson distribution, this is equivalent to using a coherent state. The two-photon contribution can be reduced by using larger $`D`$, but this is at the expense of reducing $`c_1`$.

The second drawback is that improvements are only obtained for small $`p_{\mathrm{max}}`$. Although the improvement in the ratio $`c_1/c_0`$ is independent of $`p_{\mathrm{max}}`$, improvements in $`c_1`$ can only be obtained for values of $`p_{\mathrm{max}}`$ below $`1/2`$. That is, this method can only be used to obtain improvements in the probability of a single photon up to $`1/2`$, but not to make the probability of a single photon arbitrarily close to 1. Note that the above method only gives $`c_1>p_{\mathrm{max}}`$ for four or more modes. We will now show that it is impossible to obtain an improvement in the probability of a single photon with fewer than four modes, and for various combinations of detections with larger numbers of modes.

We first examine the case $`D=0`$. Then we have only one term in the sum for $`c_0`$, and $`c_0=K^{}P_\mathrm{𝟎}`$. The expression for $`c_1`$ becomes

$`c_1`$ $`=K^{}{\displaystyle \underset{k=1}{\overset{N}{}}}{\displaystyle \frac{p_k}{1p_k}}P_\mathrm{𝟎}\left|\mathrm{\Lambda }_{1k}\right|^2K^{}{\displaystyle \frac{p_{\mathrm{max}}}{1p_{\mathrm{max}}}}{\displaystyle \underset{k=1}{\overset{N}{}}}P_\mathrm{𝟎}\left|\mathrm{\Lambda }_{1k}\right|^2`$
$`=K^{}RP_\mathrm{𝟎}=c_0R.`$ (20)
Thus we have shown that $`c_1/c_0R`$, so $`c_1p_{\mathrm{max}}`$. Hence there can be no improvement in the photon statistics if zero photons are detected. We can also obtain a similar result for the case $`D=1`$, provided all the input $`p_i`$ are equal. In that case, we have

$$c_0=K^{}\underset{k}{}\frac{p_{\mathrm{max}}}{1p_{\mathrm{max}}}P_\mathrm{𝟎}\left|\mathrm{\Lambda }_{2k}\right|^2=K^{}RP_\mathrm{𝟎}.$$
(21)
The value of $`c_1`$ is given by

$`c_1`$ $`={\displaystyle \frac{1}{2}}K^{}{\displaystyle \underset{k}{}}{\displaystyle \underset{l;lk}{}}R^2P_\mathrm{𝟎}\left|\mathrm{\Lambda }_{1l}\mathrm{\Lambda }_{2k}+\mathrm{\Lambda }_{1k}\mathrm{\Lambda }_{2l}\right|^2`$
$`{\displaystyle \frac{1}{2}}K^{}R^2P_\mathrm{𝟎}{\displaystyle \underset{k,l}{}}\left|\mathrm{\Lambda }_{1l}\mathrm{\Lambda }_{2k}+\mathrm{\Lambda }_{1k}\mathrm{\Lambda }_{2l}\right|^2=K^{}R^2P_\mathrm{𝟎}.`$ (22)
In the last line we have used the fact that $`\mathrm{\Lambda }_{1k}`$ and $`\mathrm{\Lambda }_{2k}`$ are orthonormal. Thus we again find $`c_1/c_0R`$, so $`c_1p_{\mathrm{max}}`$.

These results clearly eliminate the possibility of improving the probability of finding one photon with a two-mode interferometer. We have shown that detecting zero photons does not give an improvement, and if one photon is detected, then we must have $`MD=1`$ or 0, so there again can be no improvement. Along the same lines we can also eliminate the three-mode interferometer.

We have shown that it is impossible to improve the efficiency of a single-photon source by channeling more than one low-efficiency single-photon state into a linear optic interferometer and detecting all but one of the photons. This eliminates the most straightforward scheme for obtaining an output state with no more than one photon. It is possible to obtain an improvement for more general detection results, but at the expense of non-zero probabilities for two or more photons. We have not proven that it is impossible to obtain an improvement in the probability of a single photon while restricting to zero probability for two or more photons; however, numerical searches indicate that it is unlikely.

This work was funded in parts by the UK Engineering and Physical Sciences Research Council. One of the authors (SS) enjoys a Feodor-Lynen fellowship of the Alexander von Humboldt foundation. BCS appreciates valuable discussions with R. Laflamme in the early stages of this work. This research has also been supported by an Australian Department of Education Science and Training Innovation Access Program Grant to support collaboration in the European Fifth Framework project QUPRODIS, and by Alberta’s informatics Circle of Research Excellence (iCORE).