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# Conformations of dendrimers in dilute solution

## I Introduction

Dendrimers represent a class of well defined hyper–branched macromolecules  which can be synthesised via a sequence of carefully controlled repetitive reactions producing regular structures . There are high aspirations  of chemists and physicists regarding applications of such novel polymers as advanced materials for medicinal  uses, superior catalysts , and drug delivery vehicles , to mention just a few. Importantly for such applications, dendrimers are quite flexible molecules, which have a well accessible interior part as well as a large exterior surface. Furthermore, dendrimers can controllably change their size and density distribution under the influence of external conditions. Some of the potential applications of dendrimers moreover require a hollow interior, which could be used for accommodating guest molecules . In addition, spacers, charges, and distinct types of monomer units should allow one to further fine tune particular behaviour of dendrimers.

Although the ideal model of dendrimers with the harmonic springs or random walks can be solved analytically , such results are of a limited value since the excluded volume interactions are of paramount importance for dendrimers . However, including these in order to describe the range of the coil–to–globule transition in sufficient detail is a considerable challenge even for the homo– dendrimer. This problem has attracted a number of researchers yielding a significant body of theoretical and computational work in recent years, with some experimental results  available to assist them.

De Gennes and Hervet  have performed a seminal calculation using a version of the Edwards’ self-consistent field method upon an assumption that an onion–like layered distribution of the dendrimer generations applies. They have predicted a density minimum at the core of the dendrimer and the scaling law for the radius of gyration, $`_gN^{1/5}`$, where $`N`$ is the total number of monomers, both of which henceforth have been debated. Later on Boris and Rubinstein  have proposed a more complicated self–consistent mean–field and related Flory–type theories. They have found that the density is monotonically decreasing with a maximum at the core. However, such a theory does not contain spatial correlations and thus may have considerable limitations in predicting the internal structure of dendrimers.

A version of the Gaussian variational theory , which relies on a somewhat problematic  virial representation of the excluded volume interactions , has been used by Ganazzoli et al for describing the size, shape and intrinsic viscosity of dendrimers in a good solvent . Based on this approach the dynamic properties such as the relaxation times spectrum, dynamic structure factor and the viscoelastic moduli, , as well as the inter–chain theta–temperature  have been also investigated. Unfortunately, constraints of the numerical procedure employed limited such studies to dendrimers with $`D=1,2`$ spacers only.

A number of simulation studies using either Molecular Dynamics (MD) or Monte Carlo (MC), both on and off- lattice, whether atomistically detailed or coarse–grained, have been also performed. Naylor et al  have discussed the MD simulation of PAMAM (poly(amido-amine)) dendrimers. This study, albeit generally interesting, could cover a timescale of hundreds of picoseconds only. Later Lescanec and Muthukumar  have proposed a kinetic growth model in a 3-d off-lattice MC. They have reported the highest density at the core and have also found that the terminal monomers can traverse the dendrimer. Their approach, however, was in essence a non–equilibrium one as sufficient equilibration was not been allowed. This may explain a rather small reported value of the swelling exponent $`\nu 0.22`$ in the proposed scaling law $`_gN^\nu D^{1/2}`$ for the good solvent. Next, Mansfield and Klushin  have performed a MC simulation on a diamond lattice with $`D=7`$ spacers modelled as self–avoiding walks. Their paper has managed to overcome some of the previous limitations and it contained some important insights. Nevertheless, the $`D`$ dependence has not been investigated there. Furthermore, a possibility of lattice artefacts for the restricted branch points may raise some doubt in the more refined features of their predictions. Chen and Cui  have performed off–lattice MC simulations for a good solvent in a model with freely rotating bonds. They have also attempted to fit the radius of gyration as $`R_gD^\nu \mathrm{\hspace{0.17em}2}^{(2\nu 1)G}G^{1\nu }`$, i.e. in terms of both $`D`$ and the number of generations $`G`$. While the value of $`\nu `$ has been related to the inverse fractal dimension of the open/ring chain, just as in Ref.  containing the renormalisation group calculation by Biswas and Cherayil, the meaning of the $`G`$-dependent part of the scaling law lacked such clarity.

Further MD simulation by Murat and Grest  has relied on a coarse–grained model with the Lennard–Jones non–bonded and the FENE bonded interactions employing a white noise for the solvent and temperature effects. This simulation involved sufficient equilibration times and has yielded a number of interesting results. For instance, the dendrimer size at a fixed number of spacers $`D`$ in a good solvent was found to scale as $`R_gN^\nu `$ with the value of the exponent $`\nu `$ surprisingly close to $`1/3`$. Interestingly, the indication about a hollow domain inside the dendrimer, which has been first noted in Ref. , has been reiterated and further elaborated by performing the partial densities analysis over generations. These authors have also looked at the dendrimer contraction on changing the solvent quality from good to poor. They have concluded that the law $`_gN^{1/3}`$ (at fixed $`D`$) applies for the more compact globular dendrimer, which seemed reasonable from the point of view of the space filling argument.

Despite this considerable progress, understanding of the homo- dendrimers is not as yet fully satisfactory. First, a reasonably large span of spacer and generation numbers under variable solvent conditions has until now been hard to study. Second, it was difficult to achieve both a reliable equilibration and a good averaging statistics afterwards at the level of affordable computational times. Clearly though, these requirements must be met at the same time in order to be able to extract reliable scaling predictions and to make firm conclusions on the intricacies of the internal structure of dendrimers. Moreover, not only the good, but the theta- and poor solvents, as well as the thermodynamics of the coil–to–globule, are of interest. Perhaps, particular deficiencies of the techniques employed, an insufficient accuracy, and a limited range of systems may explain some of the discrepancies which remained between the results of different approaches. Therefore, we believe that it would be important to revisit the problem.

Here we shall try to re–examine the fundamentals of dendrimers in a broader context of their overall conformational behaviour as a function of the solvent quality. On the one hand, this may help to resolve some of the remaining controversy in the concrete predictions. On the other hand, it may shed some new light on the problem thanks to studying the observables which hitherto have not been investigated and to performing a type of analysis which is more novel. Last but not least, one may hope to improve the statistics and to study a broader range of dendrimers by using a well optimised MC code  on faster modern computers .

Our recent progress  on extending the Gaussian self–consistent (GSC) method may offer some advantages and permit comparisons to be made with the simulation data. The improved technique avoids the use of a virial expansion, but instead operates directly with a given Hamiltonian involving any pair–wise bonded and non–bonded interactions, just as in direct simulations. Ref.  deals with all the technical details and it contains a comprehensive comparison with the MC data performed for open, ring and star homopolymers with variable flexibility in a good and poor solvents. The method appears to be relatively accurate for a number of observables and its limitations are well understood. Because the new GSC technique is computationally very fast and since it directly yields the equilibrium averages for the observables of interest, it will allow us to consider a larger range of system sizes and a broader region of solvent conditions than with the equivalent MC simulation.

## II Model and notations

The current coarse–grained homo– dendrimer model is based on the following Hamiltonian (energy functional)  in terms of the monomer coordinates, $`𝐗_i`$:

$`{\displaystyle \frac{H}{k_BT}}`$ $`=`$ $`{\displaystyle \frac{1}{2\mathrm{}^2}}{\displaystyle \underset{ij}{}}\kappa _{ij}(𝐗_i𝐗_j)^2+{\displaystyle \frac{1}{2}}{\displaystyle \underset{ij,ij}{}}U^{(lj)}(|𝐗_i𝐗_j|).`$ (1)
Here the first term represents the connectivity of the dendrimer with harmonic springs of strength $`\kappa _{ij}`$ introduced between any pair of connected monomers (which is denoted by $`ij`$). The second term represents pair–wise non–bonded, specifically van der Waals interactions between monomers. We shall adopt the Lennard–Jones form of the potential,

$$U^{(lj)}(r)=\{\begin{array}{cc}+\mathrm{},\hfill & r<d^{(0)}\hfill \\ U^{(0)}\left(\left(\frac{d^{(0)}}{r}\right)^{12}\left(\frac{d^{(0)}}{r}\right)^6\right),\hfill & r>d^{(0)}\hfill \end{array},$$
(2)
with hard core part and the monomer diameter $`d^{(0)}`$, where $`U^{(0)}`$ is the dimensionless strength of the interaction.

It is important to introduce convenient notations. Let us consider a dendrimer of $`G`$ generations, each of which consists of $`D`$ spacers, with $`F_0`$ functional core (corresponding to the generation $`g=1`$) and $`F`$ functional other branch points (see Fig. 1). Thus, if $`D=a`$ and $`G=b`$ we shall briefly denote such a dendrimer as DaGb as in Refs. . Then the total number of monomers will be,

$$N=1+F_0D\frac{(F1)^{G+1}1}{F2}.$$
(3)
Note that below we shall consider results for a particular example of tri–functional branching $`F=F_0=3`$. It is convenient to represent monomer indices via triads $`i=(g,d,\phi _g)`$, where $`g=0,1,\mathrm{}G`$ is the generation index, $`d=0,1,\mathrm{}D1`$ is the spacer index, and $`\phi _g=0,1,\mathrm{}F_0(F1)^g1`$ is the angular in–generation index. It is also useful to define the shell radial index via $`\rho =Dg+d+1`$, and hence instead of the triad, one can use the ‘polar coordinates’ index notation $`i=(\rho ,\phi _g)`$. Both of these will be used interchangeably henceforth.

## III Techniques

### A Monte Carlo technique

We use the Monte Carlo (MC) technique with the standard Metropolis algorithm  and local monomer moves, based upon the implementation described by us in Refs. . The position of a randomly picked monomer in the spherical coordinates is displaced by $`\mathrm{\Delta }r=\delta r_1`$, $`\mathrm{\Delta }\theta =\pi \theta _1,`$ $`\mathrm{\Delta }\varphi =2\pi \varphi _1`$ where $`(r_1,\theta _1,\varphi _1)`$ is a triple of independent standard uniform deviates and $`\delta `$ is an additional parameter of the MC scheme characterising the timescale involved in the Monte Carlo sweep (MCS), the latter being defined as $`N`$ attempted MC steps. The Metropolis check, $`\mathrm{\Delta }Ek_BT\mathrm{ln}𝗋_1`$, where $`𝗋_1`$ is yet another standard uniform deviate, is then used as a criterion for accepting trial new conformations. As a result, the ensemble of independent initial conformations would converge to the Gibbs equilibrium distribution with increasing number of sweeps. Initial conformations of dendrimers were taken as planar and rather overstretched ones (akin to the schematic representation in Fig. 1), but then they were subjected to extensive equilibration for a required time before any simulation was commenced.

To ensure good equilibration, the behaviour of global observables such as the energy and radius of gyration was monitored. Upon reaching equilibrium these cease to have a global drift and start exhibiting characteristic fluctuating behaviour around well defined mean values. Then, depending on the dendrimer size, about $`Q=210^4`$ of statistical measurements have been performed, typically separated by about $`40N^2`$ of attempted Monte Carlo steps to ensure statistical independence of sampling. The mean value and error of sampling of an observable $`A`$ are then given by the mean $`A=(1/Q)_\gamma ^QA_\gamma `$ and by $`\pm \sqrt{(\mathrm{\Delta }A)^2/Q}`$ respectively.

### B The Gaussian Self–Consistent method

The main objects in the GSC method are the mean–squared distances between monomers,

$$𝒟_{ij}(t)\frac{1}{3}(𝐗_i(t)𝐗_j(t))^2.$$
(4)
The GSC method is based on replacing the stochastic ensemble for $`𝑿_i`$ with the exact Hamiltonian in the Langevin equation of motion onto the trial ensemble $`𝑿_i^{(0)}(t)`$ with a trial Hamiltonian $`H^{(0)}(t)`$, which is a generic quadratic form with matrix coefficients called the time–dependent effective potentials,

$$H^{(0)}[𝐗(t)]=\frac{1}{2}\underset{ij}{}V_{ij}(t)𝐗_i(t)𝐗_j(t).$$
(5)
Then one requires that the inter–monomer correlations satisfy the condition,

$$𝑿_i(t)𝑿_j(t)_0=𝑿_i^{(0)}(t)𝑿_j^{(0)}(t)_0,$$
(6)
which means that the trial ensemble well approximates the exact one. This yields the self–consistent equations , which in the absence of the hydrodynamic interactions are,

$$\frac{\zeta _b}{2}\frac{d}{dt}𝒟_{ij}(t)=\frac{2}{3}\underset{k}{}(𝒟_{ik}(t)𝒟_{jk}(t))\left(\frac{𝒜[𝒟(t)]}{𝒟_{ik}(t)}\frac{𝒜[𝒟(t)]}{𝒟_{jk}(t)}\right).$$
(7)
Here $`\zeta _b`$ is the friction coefficient of a monomer and the instantaneous free energy has the same functional expression via the instantaneous $`𝒟_{ij}(t)`$ as it has at equilibrium.

The expression for the free energy, $`𝒜^{(tot)}T𝒮`$ has been given in Ref. . We would not like to reproduce that expression here as it is somewhat cumbersome. However, it should be mentioned that the total mean energy includes the energy of the bonded and non–bonded interactions $``$ as well as the hard–core contribution as follows, $`^{(tot)}=+𝒜^{(hs)}`$. The second term is given by the generalised Carnahan–Starling term ,

$`{\displaystyle \frac{𝒜^{(hs)}}{k_BT}}`$ $`=`$ $`{\displaystyle \underset{i}{}}{\displaystyle \frac{\eta _i(43\eta _i)}{(1\eta _i)^2}},\eta _i={\displaystyle \underset{ji}{}}F^{(\eta )}\left[{\displaystyle \frac{\sqrt{𝒟_{ij}}}{d^{(0)}}}\right],`$ (8)
$`F^{(\eta )}[y]`$ $`=`$ $`{\displaystyle \frac{y\mathrm{erf}\left(\frac{1}{y\sqrt{2}}\right)\sqrt{2/\pi }\mathrm{exp}\left(\frac{1}{2y^2}\right)}{8y}},`$ (9)
where $`\eta _i`$ is known as the packing coefficient of the monomer $`i`$, which would have an important role below.

The stationary limit of the GSC Eqs. (7) produces the equations for the minimum of the free energy, which are the same as those derived from the Gibbs–Bogoliubov variational principle. Although here we shall only be concerned with the equilibrium, the numerical solution of Eq. (7), applied until the stationary limit is reached, presents one of the most efficient techniques for finding the global free energy minimum. This, based on the fifth order adaptive step Runge–Kutta integrator , is used for obtaining the results from the GSC technique.

It is also important to map out all equivalent pairs of the matrix $`𝒟_{ij}`$, which is discussed in Appendix A based on the concept of the topological tree, so that only $`C_{ind}^{(2)}=(G+1)(D/2)(D(G^2/3+(13/6)G+2)+2+G/2)`$ independent elements out of total $`C_{tot}=N(N1)/2`$ remain in it due to the kinematic symmetries of the dendrimer. It is interesting to remark, more generally, that exactly the same symmetries will exist for a hetero– dendrimer as long as the monomers at each shell index $`\rho `$ are identical to each other.

The kinematic symmetries for the matrix $`𝒟_{ij}`$ also yield analogous symmetries for the matrix $`V_{ij}`$. Thus, the computational expenses per step in our calculations are of order $`t_cNC_{ind}^{(2)}`$, where $`C_{ind}^{(2)}D^2G^3/6`$ is the total number of independent elements in the $`𝒟_{ij}`$ matrix (see Eq. (A1)). These symmetries significantly reduce the computational times compared to the equivalent system in the MC method, where such symmetries only appear in the observables after averaging over the statistical ensemble. For comparison, the computational expenses per step in MC are of order $`t_cN\mathrm{\Delta }tS`$, where $`\mathrm{\Delta }tN^2`$ is the number of MC steps needed to ensure good statistical independence between measurements, and $`S`$ is the number of measurements needed for sampling of observables. Typical values of $`S`$ should be of order of $`10^410^5`$ for good accuracy . For example, for D3G5 dendrimer (consisting of $`N=568`$ units) in the good solvent, $`U^{(0)}=1`$, the GSC method takes about $`22`$ minutes  to reach equilibrium and produce its data, whereas the MC manages to make only $`100`$ measurements of observables per hour after required equilibration. Thus, the GSC is about $`10^3`$ times faster than the MC for producing the same results here.

## IV Results

We shall restrict ourselves to springs of equal strength, $`\kappa _{ij}=1`$, and choose the hard sphere diameter equal to the statistical length, $`d^{(0)}=\mathrm{}`$, in Eq. (1) as in Ref. . Moreover, henceforth we shall use the mean energy $``$ expressed in units of $`k_BT`$ and the mean–squared distances $`𝒟_{ij}`$ and mean–squared radius of gyration, $`3_g^2`$, expressed in units of $`\mathrm{}^2`$.

In our figures below we shall present data from MC simulation via thick lines and empty circles, whereas data from GSC theory via thin lines and small filled circles. In this work we have analysed the following dendrimer sizes: $`G=17`$ for $`D=13`$ and $`G=16`$ for $`D=46`$.

### A Good solvent

We shall start by examining the dendrimer overall size and structure in the good athermal solvent, $`U^{(0)}=0`$.

The mean–squared radii of gyration $`3_g^2`$ of dendrimers with varying number of spacers $`D`$ vs the number of generations $`G`$ are depicted in Fig. 2. Clearly, $`3_g^2`$ increases with both $`D`$ and $`G`$, but in a rather different manner, which will be discussed in full detail below in Subsec. IV C. Corresponding MC and GSC curves follow each other quite closely, but the GSC theory increasingly overestimates the dendrimer size with increasing $`D`$ and $`G`$, in a manner similar to our discussion in Ref. .

As $`G`$ increases, dendrimers become more spherical, which is illustrated via the average normalised ‘axes of inertia’ $`\lambda ^{(a)}`$ defined by Eqs. (9,10) in Ref. . These converge towards a perfect sphere limit, $`\lambda ^{(a)}=1/3`$, as $`G`$ grows in Fig. 3. Interestingly, these quantities seem to be practically independent of the number of spacers $`D`$, which is illustrated by using circles ($`D=4`$) and lines ($`D=2`$) in the figure.

Typical snapshots of dendrimers D3G3 and D3G7 in Figs. 4 from MC simulation do confirm the observation that dendrimers become more spherical as $`G`$ increases. Generally, a fairly large dendrimer tends to fill in the available space quite effectively and relatively uniformly, although some local dilutions and accumulations remain. The size of the dendrimer is well defined with very few branches outstretching beyond it.

The shape of the static structure factor (SSF) in the Kratky representation in Fig. 5 for small $`G`$ is reminiscent of that of a ring, or a star with few arms (see Figs. 9,10 in Ref. ), but tends more to that of a globule with increasing number of generations. Even though the tail of the plot still increases with $`\widehat{p}`$, it develops a characteristic oscillating behaviour. This is consistent with the trends in $`\lambda ^{(a)}`$ above, particularly so since the $`D`$-dependence is almost unnoticeable in $`\widehat{S}`$ as well.

The total and partial densities,

$$g_g^{(1)}(r)\underset{ig}{}\delta (𝐫_i𝐫_{cm}𝐫),4\pi _0^{\mathrm{}}r^2𝑑rg_g^{(1)}(r)=N_g=F_0D(F1)^g.$$
(10)
of the dendrimers in Figs. 6 allow one to understand the monomer distributions in more detail. In a relatively small-$`G`$ dendrimer (Fig. a) the total density monotonically decreases with the separation from the centre–of–mass $`𝐫_{cm}`$. The highest density at the origin also occurs for the partial density of inner generations, and it follows a similar pattern. Remarkably, the terminal generation density is rather delocalised spreading evenly from the outer boundary towards the very centre of the dendrimer. This can only be rationalised by allowing a possibility of the ends re-entering the dendrimer and reaching far inside, although the density of the terminal generation exceeds that of the others somewhat near the very edge of the dendrimer.

These features are further complicated for dendrimers of a greater number of generations, typically for $`G>5`$, at least in the considered cases of $`D=2,4`$. While the behaviour of the terminal generation density remains very similar in Fig 6b, the density of non–terminal generations, and hence the total density, develop a well noticeable dip at certain separation. This indicates that larger-$`G`$ dendrimers have the lowest density domain fairly close to the centre, but not at the centre itself, which always has the highest density of all. We may note here also that while the core monomer coordinate does differ from that of the centre–of–mass somewhat, they are quite close to each other in a large-$`G`$ dendrimer. Thus, this most hollow domain is not located where the core monomer is and its separation from the core steadily increases with $`G`$. Clearly, from Fig 6b one can see that the increase of the total density at the origin comes entirely from the density of the innermost generations. However, the core domain is at its most dense in a small-$`G`$ dendrimer and it becomes less dense for larger dendrimers (in terms of both $`G`$ and $`D`$ actually) as can be seen by comparing the values of $`g^{(1)}(r=0)`$ in Figs. 6a and b. This ‘entropic pull’ effect is due to an increased entropy thanks to extra branches attached to a larger dendrimer, leading to a higher stretching of the springs near the core with larger $`G`$.

Indeed, in Figs. 7,8,9 we depict the mean–squared distances between nearest neighbours along a branch vs the shell index $`\rho `$. This is perhaps the best way to characterise such stretching. While the main bodies of Figs. 7,8 present the data from MC simulation, the insets exhibit the same results obtained from the GSC theory. Clearly, the concrete numbers for $`𝒟_{(\rho 1,0)(\rho ,0)}`$ are somewhat overestimated by the GSC theory compared to the MC data , especially for small $`\rho `$ in relatively large-$`G`$ dendrimers. Nevertheless, the particular patterns and overall shapes of the MC and GSC plots are rather similar.

As can be seen from Fig. 7, for small dendrimers D2G1-3, the spring from the core to the first monomer is stretched most, from the first to the second one is less, and so on, with the function $`𝒟_{(\rho 1,0)(\rho ,0)}`$ decreasing monotonically. However, for dendrimers with $`G>3`$ the function develops a characteristic descending step–like behaviour: the spring stretching within the same generation is about the same, but it has a dramatic drop when passing the branch point to the next generation. In all cases though, the bonds coming from the core are stretched most, with this feature becoming stronger for larger $`G`$, whereas the terminal bonds are the least stretched of all, with their length being nearly $`G`$-independent. The step–like behaviour can be easily interpreted by remarking that the number of springs doubles at any branch point. Hence the total unfavourable energy change due to a given magnitude of bonds stretching would be more significant near the edges than closer to the core. Note also that the step–like dependence vanishes for the terminal generation.

Plots in Fig. 8 for $`D=4`$ spacers show that the stretching near the core increases significantly with $`G`$ here as well. One can also see that the intra–generational steps develop a non–monotonic behaviour. Bonds within a non–terminal generation first become shorter with increasing index $`d`$ until about $`D/2`$, then grow longer again when approaching the next branch point. This U-pattern occurs because there is more steric congestion near the branch points than in the middle of generations. The terminal generation is the least stretched here as for $`D=2`$ and it has a similar monotonically diving behaviour ending up at a $`G`$ independent stretching value. Similar plots for dendrimers with $`D=6`$ spacers in Fig. 9 obtained from the GSC theory show the U-pattern becomes more pronounced as $`D`$ increases.

Finally, to address the issue of steric congestion we shall analyse the behaviour of the monomer packing coefficient $`\eta _i`$ defined by Eqs. (8,9). This quantity shows the volume fraction occupied by all other monomers around a given monomer number $`i`$, with the limit $`\eta _i1`$ corresponding to the fully packed situation according to Eq. (8).

In Figs. 10,11 the packing coefficients vs the shell index $`\rho `$ along a branch are shown for different dendrimers with $`G=6`$ and $`D=3`$ respectively. For the former case it is convenient to normalise the horizontal axis as $`\rho /D`$ so that branch points occur at integer values $`0,\mathrm{},G`$ with $`G+1`$ corresponding to the terminus. In Fig. 10 different curves correspond to different numbers of spacers $`D`$. The curve for $`D=1`$ gives a general outline of $`\eta _\rho `$ behaviour. The packing coefficient, and hence congestion, first increases, reaches a maximum and then rapidly decreases towards the termini, which are less crowded than the core domain. A larger number of spacers $`D`$ leads to an U-pattern behaviour for $`g<G`$ and a rapid dive for the terminal generation, similar to our discussion of Fig. 9. Again, the middle of generations, where $`\eta _\rho `$ has smooth minima, has a lower steric congestion since the monomers have only two nearest neighbours along the chain there compared to three for branch points, where $`\eta _\rho `$ has sharp maxima. As for the terminus, it has a single nearest chain neighbour only, resulting in a pronounced minimum of $`\eta _\rho `$.

In Fig. 11 we likewise present the packing coefficients for dendrimers with increasing number of generations $`G`$ and the fixed number of spacers $`D=3`$. The general behaviour of $`\eta _\rho `$ is similar here. For small $`G<5`$ the function $`\eta _\rho `$ oscillates around a constant, dropping down dramatically on the terminal generation. However, in larger dendrimers, $`G5`$, the function $`\eta _\rho `$ starts from much lower values for small $`\rho `$ and then increases overall up to penultimate generations, dropping down for the terminal $`g`$. Such behaviour is consistent with a lower density domain near the core seen via the spatial density distribution in Fig. 6b. For the D3G7 dendrimer, the lowest packing coefficient value occurs at around the middle of the $`g=0`$ generation (monomers 1,2,3 in diagram Fig. 1, which are buried deep inside the dendrimer as in Fig. 4b). Note also that here we have $`\eta _{D(G+1)}>\eta _0`$, indicating the onset of overcrowding in the terminal generation, which would become very severe for larger $`G`$. Overall, the packing coefficient typically changes nearly twice in its value for relatively large $`D`$ and $`G=6`$, whereas the range of change in $`\eta _\rho `$ increases further with increasing $`G`$.

Limited simulations with a smaller monomer diameter $`d^{(0)}=0.3\mathrm{}`$ have been also performed and similar results have been obtained. Dendrimers with such reduced repulsions are more compact and, clearly, as $`d^{(0)}`$ is decreased further they change in a cross–over manner towards the behaviour of the ideal dendrimers.

### B Coil–to–globule transition and poor solvent

Now we shall bring our attention to the coil–to–globule transition. Upon increasing Lennard–Jones attraction $`U^{(0)}`$ the dendrimer contracts and the mean–squared radius of gyration decreases as shown in Fig. 12a. The magnitude of this change is quite significant, being over $`20`$ times for D6G5 dendrimer. As our plot is drawn in a single logarithmic scale one can see that the region of maximal relative change in value of $`3_g^2`$ occurs at around $`U^{(0)}2.5`$, with the change being more pronounced in larger dendrimers. Clearly, from this plot and from Fig. 12b, which depicts the derivative of the specific mean energy, one can conclude that the transition is continuous (second–order like).

The quantity $`d(/N)/dU^{(0)}`$ changes from one asymptotic behaviour at small $`U^{(0)}`$ to another at large arguments, reaching eventually a constant value corresponding to the maximal packing. The maximal change in this quantity occurs at $`U_{^{}}^{(0)}2.5`$, which may be viewed as a reasonable practical definition of the transition point . As the transition is continuous it has a finite width and hence any such definition is somewhat arbitrary. However, as $`N`$ increases the transition narrows and becomes sharper. It would be easy to consider the point of vanishing of the non–bonded part of the second virial coefficient (binary integral), $`u_{LJ}^{(2)}(1/2)𝑑𝐫(1\mathrm{exp}(U^{(lj)}(|𝐫|)))`$, which occurs at about $`U_{LJ}^{(0)}1.386`$. Unfortunately, such a definition of the theta–point is unacceptable as it produces a result which does not depend on the polymer connectivity or size. Instead, one has to consider the total $`u^{(2)}`$ with the full account of the bonded and non–bonded interactions. This, however, is technically quite complicated as the Mayer–Ursell expansion is not easy to apply to dendrimers with both types of interactions involved. Thus, we shall use $`U_{^{}}^{(0)}`$ as a convenient numerical definition of a point which becomes close to the exact theta–point for sufficiently large $`N`$.

In Tab. I we report the values of $`U_{^{}}^{(0)}`$ for dendrimers with varied $`D`$ and $`G`$. Clearly, either increased number of generations or spacers, and hence increased $`N`$, would lead to a lower value of $`U_{^{}}^{(0)}`$ (larger temperature $`T_{^{}}`$) of the transition. Indeed, the point $`U_{^{}}^{(0)}`$ corresponds to the compensation of the positive conformational entropy $`𝒮^{(gau)}`$ with the negative two–body $`^{(lj)}`$ energy growing as $`N^2`$ and much faster than $`𝒮^{(gau)}`$ in $`N`$, so that smaller $`U_{^{}}^{(0)}`$ would suffice for the compensation. More non–trivially though, if we compare, for example, D3G6 and D6G5 dendrimers, both having about the same $`N`$, the larger $`D`$ system would have a lower $`U_{^{}}^{(0)}`$ (larger temperature $`T_{^{}}`$).

For linear or ring polymers one can alternatively define the theta–point of the current model by finding a value of $`U^{(0)}`$ at which the radius of gyration of the system matches that of the corresponding ideal system ($`d^{(0)}=0`$). In Tab. I such values $`U_{}^{(0)}`$ are presented in parentheses. Clearly though, this definition is inappropriate for dendrimers as $`U_{}^{(0)}`$ shifts deep into the globular area for dendrimers with sufficiently large $`G`$.

The region beyond $`U_{^{}}^{(0)}`$ corresponds to a globular conformation of the dendrimers, to discussion of which we shall now turn. In Fig. 13 we display the mean–squared radii of gyration for dendrimers with different number of spacers $`D`$ vs the number of generations $`G`$. The solid lines correspond to the globule with $`U^{(0)}=7`$, that is, well beyond the transition region, whereas the dashed lines correspond to similar ideal dendrimers ($`d^{(0)}=0`$ and $`U^{(0)}=0`$). These grow with $`D`$ at a fixed $`G`$, and vice versa in both cases. Interestingly, while the globule is more compact than the corresponding ideal dendrimer at relatively small $`G`$, for D1G$`>`$6 this trend reverses. This is due to a significant role of the repulsive part of the non–bonded potential in dendrimers with excluded volume interactions and it shows a limited relevance of the model of ideal dendrimers when applied to the coil–to–globule transition. In fact, the scaling behaviour at the transition point differs from that of the ideal dendrimer unlike in the simpler cases of open or ring polymers. Such issues will be examined by us further in Subsec. IV C.

Next, we shall compare the mean–squared distances between nearest neighbours along a branch vs the shell index $`\rho `$ for the globule in Fig. 14 to that in the good solvent in Fig. 9. The function $`𝒟_{(\rho 1,0)(\rho ,0)}`$ here has a similar U-pattern inside each generation, a dive at the terminal generation, and it increases as $`G`$ is increased, just as before. However, the descending stairway behaviour seen for the good solvent is no longer present now even for large $`G`$, and the function oscillates around a constant value. Thus, the bond stretching near the core is reduced, and apart from the intra–generational variation and the special role of the termini, the globular dendrimers are fairly evenly stretched as well as have uniform density (see inset in Fig. 6a). Note also that the maxima occur at pairs of subsequent chain indices $`\rho `$. This means that the mean–squared distances from the pre–branch monomer to the branch point are almost the same as from the branch point to the post–branch one, which indicates similarity in overall bond stretching with increasing $`\rho `$ and hence an approximate equivalence of all branch points in the globule. Therefore, the connectivity structure of the dendrimer is less significant and more locally manifested in the globular state.

Similar conclusions can be made also from the behaviour of the monomer packing coefficient for globular dendrimers in Fig. 15. Again, $`\eta _\rho `$ only depends periodically on the spacer index $`d`$, being nearly identical for all generations but the terminal one. The peaks occur at the branch points and the termini have the lowest packing coefficient of all just as for the good solvent in Fig. 11. Note, however, that the actual magnitudes of $`\eta _\rho `$ are much larger for the globule than for the good solvent and approach $`1/2`$. Moreover, the mean value of $`\eta _\rho `$ in the globule steadily increases with $`N`$ and there is no hollow domain in the globular conformation even for $`G>5`$. Indeed, the total density $`g^{(1)}(r)`$ of a globule dendrimer shown in the insets of Figs. 6a,b is practically uniform and rather localised within the size of the globule, thus having higher values than for the good solvent. Remarkably, the terminal generations still can traverse the dendrimer even in such a dense state.

### C Scaling relations

First, one can fit the mean–squared radii of gyration at a fixed number of generations $`G`$ in terms of $`N`$ expressed via $`D`$ by Eq. (3) as,

$`\text{Good solvent:}\sqrt{3_g^2}`$ $`=`$ $`a_GN^{\nu _G},`$ (11)
$`\text{Theta–solvent:}\sqrt{3_g^2}`$ $`=`$ $`𝖺_GN^{𝗏_G},`$ (12)
$`\text{Poor solvent:}\sqrt{3_g^2}`$ $`=`$ $`A_GN^{\upsilon _G}.`$ (13)
The values of the exponent $`\nu _G`$ obtained from fitting of the data are presented in Tab. II,

$`\text{MC:}\nu _G0.58\pm 0.02,`$ (14)
$`\text{GSC:}\nu _G0.62\pm 0.01.`$ (15)
Note that $`\nu _G`$ here practically coincides with the inverse fractal dimension of an open repulsive chain. Thus, we can interpret $`\nu _G`$ as the Flory swelling exponent, the value of which for large $`N`$ is more accurately known from the renormalisation group calculation, namely $`\nu _F=0.588\pm 0.001`$. As discussed in Ref.  the GSC theory overestimates the Flory swelling exponent by about $`0.04`$ as compared to the MC data for this range of finite polymer sizes. This is consistent with the amount by which the GSC values for $`\nu _G`$ exceed those of the MC simulation.

At the same time, the prefactor $`a_G`$ does not obey a power law in $`G`$, but it can be fitted well via the following expression,

$$\text{GSC: }a_G=(0.74\pm 0.01)\mathrm{\hspace{0.17em}2}^{\frac{G+1}{4.07\pm 0.1}},\text{MC: }a_G=(0.9\pm 0.03)\mathrm{\hspace{0.17em}2}^{\frac{G+1}{3.9\pm 0.2}}.$$
(16)
Or by using Eq. (3) again, we can express this for the good solvent via,

$`\sqrt{3_g^2}`$ $``$ $`\left({\displaystyle \frac{3D}{N}}\right)^{1/4}N^{\nu _F}D^{1/4}N^{\nu _F1/4},`$ (17)
$`\sqrt{3_g^2}`$ $``$ $`D^{\nu _G}(F1)^{\nu _D(G+1)},\nu _D\nu _G{\displaystyle \frac{1}{4}}.`$ (18)
Indeed, as can be seen from Tab. III, the resulting exponent $`\nu _D0.37\pm 0.01`$ in the GSC method, whereas from MC the resulting exponent value is $`\nu _D0.335\pm 0.0081/3`$. These notations for the exponents $`\nu _G`$, $`\nu _D`$ at fixed values of either $`G`$ or $`D`$ are akin to those traditionally used in thermodynamics.

For the poor solvent a similar procedure gives the following values for $`N>200`$,

GSC: $`A_G=0.560\pm 0.007,`$ $`\upsilon _G=0.331\pm 0.002\text{for }U^{(0)}=7,`$ (19)
GSC: $`A_G=0.516\pm 0.004,`$ $`\upsilon _G=0.333\pm 0.001\text{for }U^{(0)}=10,`$ (20)
MC: $`A_G=0.60\pm 0.004,`$ $`\upsilon _G=0.31\pm 0.02\text{for }U^{(0)}=6,`$ (21)
or, roughly speaking, $`\upsilon _G\upsilon =\frac{1}{3}`$, with coefficient $`A_G`$ decreasing slowly with increasing $`U^{(0)}`$ and being almost independent of other parameters such as $`G`$. Hence, we have for a poor solvent,

$$\sqrt{3_g^2}N^\upsilon D^{\upsilon _G}(F1)^{\upsilon _D(G+1)},\upsilon _D=\upsilon _G\upsilon =\frac{1}{3}.$$
(22)
It is interesting to note that for the ideal chain (absence of the excluded volume interactions, $`d^{(0)}=0`$) we obtain the following accurate asymptotic expression  for large $`D`$ and $`G`$,

$$\sqrt{3_g^2}\mathrm{}\sqrt{3}D^{1/2}G^{1/2}.$$
(23)
Therefore, generally, the dependence of the radius of gyration on the spacer exponent is always the same as for an open/ring chain, but the ideal system lacks the complicated dependence on the number of generations $`G`$. It is worthwhile to comment also that such ideal system should not be confused with the system in the theta–solvent near the transition point $`U_{^{}}^{(0)}`$. For the latter we shall have a scaling akin to Eqs. (18,22),

$$\sqrt{3_g^2}D^{𝗏_G}(F1)^{𝗏_D(G+1)},𝗏_G=\frac{1}{2},\upsilon _D𝗏_D\nu _D.$$
(24)
The values for $`𝗏_G`$, $`𝗏_D`$ obtained from the GSC theory are reported in Tabs. II,III. We can conclude that indeed $`𝗏_G=1/2`$ with a high accuracy, whereas $`𝗏_D0.35`$. We expect the latter to be somewhat lower in the MC simulation than in the GSC theory again.

## V Discussion and Conclusion

In this paper we have studied a range of homo– dendrimers with $`D=16`$ spacers and $`G=17`$ generations in the good and poor solvents, as well as across the coil–to–globule transition. These studies have been performed by two different techniques yielding a satisfactory agreement between their results. The first technique is based on the Gaussian self–consistent (GSC) method, while the second one is that of Monte Carlo (MC) simulation in continuous space. Both rely on the same coarse–grained model involving harmonic springs for connected monomers and the Lennard–Jones pair–wise potential with a hard core part. The overall accord between these two rather distinct approaches is quite important due to the limitations of both techniques. The MC technique, while in principle exactly modelling a given system, in practice is always limited by the statistical accuracy and quality of equilibration for very large dendrimers computationally affordable. The GSC method, on the other hand, is about $`10^3`$ faster for the studied range of dendrimer sizes and it directly produces the ensemble averaged equilibrium observables. However, it is only an approximate technique, which has some intrinsic inaccuracies, for instance somewhat overestimating the size of polymers in the good solvent.

We have proposed a new scaling law for the radius of gyration of dendrimers which involves the two exponents $`\nu _G`$ (at fixed $`G`$) and $`\nu _D`$ (at fixed $`D`$),

$$_gD^{\nu _G}(F1)^{\nu _D(G+1)}D^{\nu _G\nu _D}N^{\nu _D},$$
(25)
where $`\nu _G=\nu `$, with $`\nu 3/5`$, $`1/2`$, and $`1/3`$ being the inverse fractal dimension of an open/ring chain in the good, ideal and poor solvents respectively. While this agrees with the conclusions of Refs.  for $`\nu _G`$, we have obtained a rather different dependence on the number of generations. Namely, we have concluded that $`\nu _D\nu 1/40.338`$ for the good solvent, and $`\nu _D\nu =1/3`$ for the globule. This is consistent with Ref. , but our estimate of $`\nu _D`$ for the good solvent is more accurate enabling us to claim that $`\nu _D`$ is certainly above, although quite close to the poor solvent value $`1/3`$.

It is important to emphasise also that the law in Eq. (25) is valid for the model with the harmonic bonds employed here. Dendrimers with bonds possessing a finite stretchability and angular potentials would in all likelihood have more complicated and non–universal features in their behaviour. However, the harmonic model is an important and well tractable reference point for further studies at the level of full atomistic detail for concrete dendrimers, which could have bonds stretchable in different ranges.

We have concluded that the coil–to–globule transition for dendrimers is continuous and that for the theta–solvent the scaling law for $`_g`$ differs from that of the ideal dendrimer, in which $`_g(DG)^{1/2}`$, having instead the $`G`$-dependence of the form given by Eq. (25) with $`1/3\nu _D3/51/4`$.

Details of the conformational structure of dendrimers have been analysed for the good and poor solvents also. In some respects, our results support certain observations of Ref.  made for the good solvent. Namely, we find a strong evidence of the re–entry of the terminal generation into the dendrimer up to its very centre, producing a rather delocalised partial density for those monomers. This results in the highest total density near the core for relatively small dendrimers, which decreases in larger dendrimers due to the ‘entropic pull’ effect of extra branches. However, as the number of generations exceeds $`G=5`$ there also develops a lower density domain inside the dendrimer. Moreover, we have analysed the bond stretching along a continuous branch. This is highest near the core, especially for dendrimers with a large number of generations. The stretching decreases with increasing generation index and oscillates in the magnitude with the spacer index. This observation is interpreted consistently with the connectivity contribution to the mean energy.

Furthermore, we have attempted to elucidate the degree of the steric congestion in a dendrimer by considering the shell index dependence of the monomer packing coefficient $`\eta _\rho `$. The latter is the volume ratio of the space occupied by all other monomers around a given one. In a relatively small dendrimer $`\eta _\rho `$ oscillates in the spacer index with only a weak generation index dependence, except for the terminal generation which is less congested. A dendrimer with a large number of generations, however, has a less congested hollow domain inside it and the highest congestion in the penultimate generations in accord with the density distributions.

The degree of asphericity of dendrimers appears to decrease with the increasing number of generations, depending rather weakly on the number of spacers. This is also confirmed by the behaviour of the static structure factor, which develops an oscillating globule–like character for larger $`G`$.

Interestingly, while incorrect in concrete detail, the onion model predictions of Ref.  do have a rather limited meaning in a sense that there exists a hollow domain inside a dendrimer of large enough number of generations, but not at the core itself. However, the partial densities of generations fall off only beyond the appropriate cut–off radii. These densities are totally delocalised until the cut–offs (see Fig 6b), being fairly large at the core , and certainly are not concentrated within thin layers as surmised.

A similar analysis has been carried out for the poor solvent as well. The globular conformation of a dendrimer is much more compact, and it is rather uniform without any hollow domains. The packing coefficient for the globule is much larger in value than for the good solvent and depends on the spacer index only for the monomers in the inner generations. There is also much less stretching of bonds involved near the core than for the good solvent, even in a dendrimer with a large $`G`$. Generally, the bond stretching in the globule is stronger for the branch points than for the middle of spacers or terminal monomers. Thus, the connectivity of a dendrimer in the globular state manifests itself in a much more localised manner, and with a significantly smaller effect than for the good solvent.

We believe that our results allow one to reconcile some of the disparate predictions from previous theoretical and simulation studies by finding some simple limiting regimes and by discovering non–monotonic dependencies of various observables and the local structure of dendrimers on the number of generations. These unusual features of dendrimers indeed make them extremely appealing for numerous future applications ranging from catalysis, rheology modifiers, to drug delivery and biotechnology more generally.

###### Acknowledgements.

The authors acknowledge interesting discussions with Professor G. Allegra, Dr G. Raos, and particularly with Professor F. Ganazzoli who attracted our attention to the field of dendrimers. We are also grateful to Gillian Flanagan and Marese O’Brien for their help and insight during their undergraduate research projects. Support from the IRCSET basic research grant SC/02/226 is also acknowledged.

## A The topological tree

The concept of the kinematic symmetries can be best explained by using the topological tree presented in Fig. 16, which is equivalent to the dendrimer diagram of Fig. 1. Hence, the horizontal line would represent any selected consecutive branch of the dendrimer, which we shall name the primary branch $``$, with the core monomer being on the left. The length of $``$ is then $`n_{}=D(G+1)`$, excluding the core monomer itself. Any two branches become topologically non–equivalent to each other as long as they diverge from the common parent sub-branch at some value of the generation index $`g`$. We shall call any two such branches non–equivalent of order $`g`$. The leftmost vertical line on the left of Fig. 16 represents any branch non–equivalent to $``$ of order $`g=0`$, which we shall denote as $`_0`$ with the length $`n__0n_0`$. Similarly then, we shall have branches $`_g`$ non–equivalent to $``$ of order $`g`$ with the length $`n_g=D(Gg+1)`$ for all values of $`g=0,1,\mathrm{}G`$ in our topological tree. Any two pairs of monomers then would have $`𝒟_{ij}=𝒟_{i^{}j^{}}`$ as long as the pair $`(i^{},j^{})`$ lies in the same places in the topological tree as the pair $`(i,j)`$, thereby defining the equivalence classes of monomer pairs.

Moreover, we can easily count the number of independent degrees of freedom in the matrix $`𝒟_{ij}`$. For that we have to count the number of possible pairs $`(\rho ,\rho ^{})`$ in Fig. 16 such that e.g. $`\rho ^{}\rho `$, where $`i=(\rho ,\phi )`$ and $`i^{}=(\rho ^{},\phi ^{})`$. Accidentally, we note that the topological tree disregards the angular coordinates $`\phi `$ of any equivalent monomers. There are two possibilities of pairing $`\rho `$ and $`\rho ^{}`$: a) $`\rho ,\rho ^{}`$ and b) $`\rho `$ and $`\rho ^{}_g`$ for some $`g`$. In the former case we get the number of pairs $`C_{}=_{i=1}^n_{}i=n_{}(n_{}+1)/2`$, whereas in the latter case we obtain $`C_g=_{i=n_g}^1i=n_g(n_g+1)/2`$. Thus, we have derived the total number of independent degrees of freedom,

$$C_{ind}^{(2)}=C_{}+\underset{g=G}{\overset{0}{}}C_g=(G+1)\frac{D}{2}\left(D\left(\frac{G^2}{3}+\frac{13}{6}G+2\right)+2+\frac{G}{2}\right),$$
(A1)
which is identical to Eq. (A-1) in Ref. .

Similarly, the total number of independent 1-point observables (e.g. the packing coefficient $`\eta _i`$), which depend on $`\rho `$ only, is simply the length of the primary branch $`_0`$,

$$C_{ind}^{(1)}=D(G+1)+1.$$
(A2)
## Figure Captions

## Tables


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# Remarks on a conjecture of Gromov and Lawson

## 1. Introduction

In their influential paper \[GL2\] Gromov and Lawson proposed the following conjecture.

###### 1.1.

Gromov-Lawson Conjecture \[GL2\]. Let $`M`$ be a smooth, compact manifold without boundary of dimension $`n5`$ with fundamental group $`\pi `$. Then $`M`$ admits a positive scalar curvature metric if and only if $`pD([M,u])=0KO_n(B\pi )`$.

Here $`u:MB\pi `$ is the map classifying the universal covering of $`M`$, and $`[M,u]\mathrm{\Omega }_n^{spin}(B\pi )`$ is the element in the spin bordism group represented by the pair $`(M,u)`$. The maps $`D`$ and $`p`$ are natural transformations between generalized homology theories:

$$\mathrm{\Omega }_n^{spin}(X)\stackrel{𝐷}{}ko_n(X)\stackrel{𝑝}{}KO_n(X),$$

referred to as ‘spin bordism’, ‘connective $`KO`$-homology’ and ‘periodic $`KO`$-homology’, respectively. As the name suggests, $`KO_n()`$ is periodic in the sense that $`KO_n(X)KO_{n+8}(X)`$; moreover,

$$KO_n(\mathrm{point})\{\begin{array}{cc}\hfill & \text{if }n0mod4\hfill \\ /2\hfill & \text{if }n1,2mod8\hfill \\ 0\hfill & \text{otherwise}\hfill \end{array}.$$

The homology theory $`ko_n()`$ is connective; i.e., $`ko_n(\mathrm{point})=0`$ for $`n<0`$. Moreover, the natural transformation $`p`$ induces an isomorphism $`ko_n(\mathrm{point})KO_n(\mathrm{point})`$ for $`n0`$ (this does not hold with $`\mathrm{point}`$ replaced by a general space $`X`$).

We remark that the assumption $`n5`$ (which wasn’t present in \[GL2\]) should be added since Seiberg-Witten invariants show that the conjecture is false for $`n=4`$ even if the group $`\pi `$ is trivial. In their paper \[GL2\] Gromov and Lawson prove the ‘only if’ part of Conjecture 1.1 for some groups $`\pi `$, but later Rosenberg \[Ro1\] noticed that the ‘only if’ statement does not hold e.g. for finite cyclic groups, since any lens space $`M`$ admits a metric with positive scalar curvature, but $`pD([M,u])`$ is non-trivial. He proposed the following variant of Conjecture 1.1.

###### 1.2.

The Gromov-Lawson-Rosenberg Conjecture \[Ro3\]. Let $`M`$ be a smooth, compact manifold without boundary of dimension $`n5`$ with fundamental group $`\pi `$. Then $`M`$ admits a positive scalar curvature metric if and only if $`\alpha ([M,u])=0KO_n(C_r^{}\pi )`$.

Here $`\alpha `$ is the following composition

(1.3)
$$\mathrm{\Omega }_n^{spin}(B\pi )\stackrel{𝐷}{}ko_n(B\pi )\stackrel{𝑝}{}KO_n(B\pi )\stackrel{𝐴}{}KO_n(C_r^{}\pi ),$$

where $`A`$ is the assembly map, whose target is the $`KO`$-theory of the (reduced) real group $`C^{}`$-algebra $`C_r^{}\pi `$ (this is a norm completion of the real group ring $`\pi `$ and is equal to the latter for finite $`\pi `$).

Rosenberg proved the ‘only if’ part of this Conjecture in \[Ro2\] by interpreting the image of $`[M,u]\mathrm{\Omega }_n^{spin}(B\pi )`$ under $`\alpha `$ as a ‘fancy’ type of index of the Dirac operator on $`M`$ and showing that this index vanishes if $`M`$ admits a metric of positive scalar curvature. We note that if $`A`$ is injective for a group $`\pi `$ (which can be shown for many groups $`\pi `$ and is expected to hold for all torsion free groups according to the Novikov-Conjecture), both conjectures are equivalent.

All partial results concerning Conjectures 1.1 and 1.2 discussed so far have to do with the ‘only if’ part or equivalently, with finding obstructions (like the index obstruction $`\alpha `$) against the existence of positive scalar curvature metrics. For a few groups $`\pi `$ constructions have been found of sufficiently many positive scalar curvature metrics to prove the ‘if’ part as well and hence to prove the Gromov-Lawson-Rosenberg Conjecture 1.2. This includes the trivial group \[St1\], cyclic groups and more generally all finite groups $`\pi `$ with periodic cohomology \[BGS\]. However, a counter example has been found for $`\pi =/3\times ^4`$, $`n=5`$ \[Sch\]. So far, no counter example to the Gromov-Lawson-Rosenberg Conjecture has been found for finite groups $`\pi `$ (which actually is the class of groups the conjecture was originally formulated for; cf. \[Ro3\], Conjecture 0.1 and §3).

In this paper we address the question of whether the Gromov-Lawson Conjecture and/or Gromov-Lawson-Rosenberg Conjecture might be true for torsion free groups. Alas, the answer is ‘no’ in both cases; more precisely:

###### Theorem 1.4.

There are finitely generated torsion free groups $`\pi `$ for which the ‘if’ part of the Gromov-Lawson Conjecture 1.1 (and hence also the ‘if’ part of the Gromov-Lawson-Rosenberg Conjecture 1.2) is false. In other words, there is a closed spin manifold $`M`$ of dimension $`n5`$ with fundamental group $`\pi `$ and $`pD([M,u])=0`$ which does not admit a positive scalar curvature metric.

Still, one might hope to save these conjectures at least for groups $`\pi `$ satisfying some additional geometric conditions, say of the kind that guarantee that the assembly map $`A`$ is an isomorphism (we remark that according to the Baum-Connes Conjecture the assembly map is an isomorphism for all torsion free groups $`\pi `$). For these groups in particular the ‘only if’ part of the conjectures is true.

###### 1.5.

Examples of groups $`\pi `$ for which the assembly map is an isomorphism

1. Any countable group $`\pi `$ in the class $`𝒞=_n𝒞_n`$, where the class $`𝒞_0`$ consists just of the trivial group, and $`𝒞_n`$ is defined inductively as the class of groups which act on trees with all isotropy subgroups belonging to $`𝒞_{n1}`$ \[Oy\].
2. The fundamental group of a closed manifold which is CAT(0)-cubical complex, i.e. a piecewise Euclidean cubical complex which is non-positively curved in the sense of Alexandrov (cf. (5.1))
3. Any word hyperbolic group in the sense of Gromov, in particular fundamental groups of strictly negatively curved manifolds (in the Riemannian sense or in the sense of Alexandrov).

In the second case the claim that the assembly map is an isomorphism follows from combining work of Niblo and Reeves \[NR\] and Higson and Kasparov \[HK\]. Niblo and Reeves \[NR\], compare \[Ju, p. 158\] show that any group acting properly on a CAT(0)-cubical complex has the Haagerup property (in other words, is a-T-menable). Higson and Kasparov prove that for such groups the Baum-Connes Conjecture holds.

The third case is proved by Mineyev and Yu \[MY\] (reducing to some deep results of Lafforgue \[L1, L2\]). Note that the fundamental group of a negatively curved manifold is known to be word hyperbolic.

We note that the papers cited above deal with the complex version of the Baum-Connes Conjecture, whereas we are interested in the real version. However, it is a “folk theorem” that the complex isomorphism implies the real isomorphism, compare e.g. \[Ka\].

Unfortunately, making these kinds of assumptions about the group $`\pi `$ does not save Conjectures 1.1 or 1.2:

###### 1.6.

Addendum to Theorem 1.4. The group $`\pi `$ in Theorem 1.4 may be chosen to be in the class $`𝒞`$ and to be the fundamental group of a closed manifold which is a CAT(0)-cubical complex. Alternatively, we may choose $`\pi `$ to be the fundamental group of a closed manifold which is negatively curved in the Alexandrov sense.

With this ‘negative’ result showing that Conjectures 1.1 and 1.2 are false even for very “reasonable” groups $`\pi `$, the challenge is to find a necessary and sufficient condition for $`M`$ to admit a positive scalar curvature metric. To the authors knowledge there is that this point in time not even a candidate for this condition.

## 2. Outline of the proof

As a first step we rephrase Conjectures 1.1 and 1.2. The key for this is the following result of Gromov-Lawson \[GL1\] (see also \[RS\]):

###### Theorem 2.1.

Let $`M`$ be a spin manifold of dimension $`n5`$, and let $`u:MB\pi `$ be the classifying map of its universal covering. Then $`M`$ admits a positive scalar curvature metric if and only if $`[M,u]\mathrm{\Omega }_n^{spin,+}(B\pi )`$.

Here for any space $`X`$, the group $`\mathrm{\Omega }_n^{spin,+}(X)`$ is by definition the following subgroup of $`\mathrm{\Omega }_n^{spin}(X)`$:

$$\mathrm{\Omega }_n^{spin,+}(X)=\left\{[N,f]|\begin{array}{c}N\text{ is an }n\text{-dimensional spin manifold}\\ \text{with positive scalar curvature metric,}\\ f:NX\end{array}\right\}$$

It should be emphasized that while the ‘only if’ portion of the above theorem is of course tautological, the ‘if’ part is not; it can be rephrased by saying that if $`M`$ is bordant (over $`B\pi `$) to some spin manifold $`N`$ with a positive scalar curvature metric, then $`M`$ itself admits a positive scalar curvature metric.

We claim that for a finitely presented group $`\pi `$ the Gromov-Lawson Conjecture 1.1 (resp. Gromov-Lawson-Rosenberg Conjecture 1.2) is equivalent to the first (resp. second) of the following equalities for $`n5`$

(2.2) $`\mathrm{\Omega }_n^{spin,+}(B\pi )`$ $`=\mathrm{ker}pD`$
(2.3) $`\mathrm{\Omega }_n^{spin,+}(B\pi )`$ $`=\mathrm{ker}\alpha `$
By the Bordism Theorem 2.1 it is clear that these equations imply Conjectures 1.1 resp. 1.2. Conversely, if $`\pi `$ is a finitely presented group, then a surgery argument shows that every bordism class in $`\mathrm{\Omega }_n^{spin}(B\pi )`$, $`n5`$ can be represented by a pair $`(M,u)`$, where $`M`$ is a manifold with fundamental group $`\pi `$, and $`u:MB\pi `$ is the classifying map of the universal covering of $`M`$. This shows that the Gromov-Lawson Conjecture 1.1 implies equation (2.2) and that the Gromov-Lawson-Rosenberg Conjecture 1.2 implies equation (2.3).

Using this translation, our main result Theorem 1.4 is a consequence of the following slightly more precise result.

###### Theorem 2.4.

For $`5n8`$, there are finitely presented torsion free groups $`\pi `$ such that $`\mathrm{\Omega }_n^{spin,+}(B\pi )\mathrm{ker}pD`$.

To prove this statement, we need to produce a bordism class $`x\mathrm{\Omega }_n^{spin}(B\pi )`$ in the kernel of $`pD`$ and show that it cannot be represented by a manifold of positive scalar curvature. At present, three methods are known to show that a manifold $`M`$ does not admit a positive scalar curvature metric: the index-theory of the Dirac operator on $`M`$, the Seiberg-Witten invariants, and the stable minimal hypersurface method pioneered by Schoen and Yau \[SY\]. For the case at hand, the first two methods are useless: the index of any manifold $`M`$ representing $`x`$ vanishes due to our assumption $`pD(x)=0`$ and the Seiberg-Witten invariants of $`M`$ are only defined for $`4`$-dimensional manifolds. As explained in \[Sch, Proof of Cor. 1.5\], a corollary of the stable minimal hypersurface method is the following result.

###### Theorem 2.5 (\[Sch\], Cor. 1.5).

Let $`X`$ be a space, and let $`H_n^+(X;)`$ be the subgroup of $`H_n(X;)`$ consisting of those elements which are of the form $`f_{}[N]`$, where $`N`$ is an oriented closed manifold of dimension $`n`$ which admits a positive scalar curvature metric, and $`f`$ is a map $`f:NX`$. Let

$$\alpha :H_n(X;)H_{n1}(X;)$$

be the homomorphism given by the cap product with a class $`\alpha H^1(X;)`$. Then for $`3n8`$ the homomorphism $`\alpha `$ maps $`H_n^+(X;)`$ to $`H_{n1}^+(X;)`$.

We remark that a better regularity result for hypersurfaces with minimal volume representing a given homology class proved by Smale \[Sm\] makes it possible to include the case $`n=8`$ in the above result (see \[JS, §4\] for a detailed explanation).

###### Corollary 2.6.

Let $`X`$ be the classifying space of a discrete group $`\pi `$. Assume that $`x\mathrm{\Omega }_n^{spin}(X)`$ is a bordism class for $`5n8`$, satisfying the condition

(2.7)
$$\alpha _1\mathrm{}\alpha _{n2}H(x)0H_2(X;)$$

for some cohomology classes $`\alpha _1,\mathrm{},\alpha _{n2}H^1(X;)`$ (here $`H:\mathrm{\Omega }_n^{spin}(X)H_n(X;)`$ is the Hurewicz map given by sending a bordism class $`[M,f]`$ to $`f_{}[M]`$, where $`[M]H_n(M;)`$ is the fundamental class of $`M`$). Then $`x`$ is not in the subgroup $`\mathrm{\Omega }_n^{spin,+}(X)`$.

###### Proof.

Assume $`x\mathrm{\Omega }_n^{spin,+}(X)`$. Then $`H(x)H_n^+(X;)`$ (by definition of $`H_n^+(X;)`$); applying Theorem 2.5 first to the cohomology class $`\alpha _1`$, then $`\alpha _2`$, e.t.c., we conclude $`\alpha _1\mathrm{}\alpha _{n2}H(x)H_2^+(X;)`$. This is the desired contradiction, since the element $`\alpha _1\mathrm{}\alpha _{n2}H(x)`$ is assumed non-zero, while the group $`H_2^+(X;)`$ is trivial: by the Gauss-Bonnet Theorem, the only closed oriented $`2`$-manifold $`N`$ with positive scalar curvature are disjoint unions of $`2`$-spheres; however any map $`f`$ from such a union to the classifying space of a discrete group is homotopic to the constant map, which implies $`f_{}[N]=0`$. ∎

We note that Corollary 2.6 implies Theorem 2.4, provided we can find a bordism class $`x`$ in the kernel of $`pD`$ satisfying condition 2.7. Whether there is such a bordism class is in general a pretty hard question; fortunately the following homological condition is much easier to check, and, as Theorem 2.9 below shows, it implies the existence of a spin bordism class $`x`$ in the kernel of $`pD`$ with property (2.7).

###### 2.8.

Homological condition. There are (co)homology classes $`\alpha _1,\mathrm{},\alpha _{n2}H^1(X;)`$ and $`zH_{n+5}(X;)`$ such that

$$\alpha _1\mathrm{}\alpha _{n2}\delta P^1\rho (z)0H_2(X;)$$

Here

* $`\rho :H^{}(X;)H^{}(X;/3)`$ is mod $`3`$ reduction,
* $`P^1:H_{}(X;/3)H_4(X;/3)`$ is the homology operation dual to the degree $`4`$ element $`P^1`$ of the mod $`3`$ Steenrod algebra (see \[SE, Chapter VI, section 1\]), and
* $`\delta :H_{}(X;/3)H_1(X;)`$ is the Bockstein homomorphism associated to the short exact coefficient sequence $`\stackrel{\times 3}{}/3`$ (i.e., the boundary homomorphism of the corresponding long exact homology sequence).

In section 3 we will use the Atiyah-Hirzebruch spectral sequences converging to $`\mathrm{\Omega }_{}^{Spin}(X)`$ resp. $`KO_{}(X)`$ to prove the following result.

###### Theorem 2.9.

Let $`X`$ be a space which satisfies the homological condition 2.8 for $`5n8`$. Then there is a bordism class $`x\mathrm{\Omega }_n^{spin}(X)`$ in the kernel of $`pD`$ satisfying condition 2.7 above.

Putting these results together, we obtain the following corollary.

###### Corollary 2.10.

Let $`X`$ be a space satisfying the cohomological condition 2.8 for $`5n8`$. If $`X`$ is the classifying space of some discrete group $`\pi `$, then $`\mathrm{\Omega }_n^{spin,+}(B\pi )\mathrm{ker}pD`$.

For a given space $`X`$ it is not hard to check the homological condition 2.8, provided we know enough about the (co)homology of $`X`$. For example, in section 4 we will prove the following result by a straightforward calculation.

###### Proposition 2.11.

For $`n2`$, let $`\mathrm{\Gamma }_n`$ be the cartesian product of $`2`$ copies of $`/3`$ and $`n2`$ copies of $``$. Then the classifying space $`B\mathrm{\Gamma }_n`$ satisfies the homological condition 2.8.

In particular, Corollary 2.10 then shows that the Gromov-Lawson Conjecture 1.1 does not hold for the group $`\mathrm{\Gamma }_n`$ for $`5n8`$. This is very similar to the result of one of the coauthors \[Sch\] who constructed a $`5`$-dimensional spin manifold with fundamental group $`\pi =/3\times ^4`$ whose index obstruction $`\alpha ([M,u])KO_5(C^{}\pi )`$ is trivial, but which does not admit a metric of positive scalar curvature. However, the example in \[Sch\] does not provide a counter example to the Gromov-Lawson Conjecture 1.1, since it can be shown that $`pD([M,u])KO_5(B\pi )`$ is non-trivial.

As explained in the introduction, it is more interesting to find torsion free groups $`\pi `$ for which the conjecture goes wrong. It seems conceivable that experts might know explicit examples of torsion free groups and enough about their (co)homology to conclude that the homological condition 2.8 is satisfied (or the cohomological condition 4.2, which is stronger, but easier to check).

Lacking this expertise, we argue more indirectly to prove Theorem 2.4. We use a construction of Baumslag, Dyer and Heller \[BDH\], who associate a discrete group $`\pi `$ to any connected CW complex $`X`$ and show that there is a map $`B\pi X`$ which is an isomorphism in homology. Moreover, if $`X`$ is a finite CW complex, then $`B\pi `$ has the homotopy type of a finite CW complex. In particular, the group $`\pi `$ is finitely presented. We would like to mention that originally Kan and Thursten described a similar construction \[KT\]. However, their groups are usually not finitely presented and hence not suitable for our purposes.

To prove Theorem 2.4 we let $`X`$ be any finite CW complex satisfying the condition 2.8, e.g., the $`n+5`$-skeleton of $`B\mathrm{\Gamma }_n`$ and let $`\pi `$ be the discrete group obtained from $`X`$ via the Baumslag-Dyer-Heller procedure. Then $`\pi `$ is a discrete group which is finitely presented and torsion free since its classifying space $`B\pi `$ is homotopy equivalent to a finite CW complex. Moreover, $`B\pi `$ satisfies the homological condition 2.8 and hence Corollary 2.10 implies Theorem 2.4.

Applying more sophisticated ‘asphericalization procedures’ due to Davis-Januskiewicz \[DJ\] respectively Charney-Davis \[CD\], we can produce groups $`\pi `$ satisfying the geometric conditions mentioned in Addendum 1.6. This is explained in section 5.

## 3. A spectral sequence argument

The goal of this section is the proof of Theorem 2.9. We consider the Atiyah-Hirzebruch spectral sequence (AHSS for short)

(3.1)
$$E_{p,q}^2(X)=H_p(X;\mathrm{\Omega }_q^{spin})\mathrm{\Omega }_{p+q}^{spin}(X).$$

We recall that the Hurewicz map $`H:\mathrm{\Omega }_n^{spin}(X)H_n(X;)`$ is the edge homomorphism of this spectral sequence; i.e., $`H`$ is equal to the composition

$$\mathrm{\Omega }_n^{spin}(X)E_{n,0}^{\mathrm{}}(X)E_{n,0}^2(X)=H_n(X;).$$

This shows that in order to produce a bordism class $`x\mathrm{\Omega }_n^{spin}(X)`$ satisfying condition (2.7) it suffices to produce a homology class $`yH_n(X;)`$ such that

(3.2)
$$yH_n(X;)=E_{n,0}^2\text{is an infinite cycle for the AHSS }\text{3.1}$$

(3.3)
$$\alpha _1\mathrm{}\alpha _{n2}y0$$

To guarantee that the element $`x`$ produced this way is in the kernel of the natural transformation $`pD:\mathrm{\Omega }_n^{Spin}(X)KO_n(X)`$, we note that $`pD`$ induces a map of spectral sequences

$$E_{p,q}^r(X;\mathrm{\Omega }^{Spin})E_{p,q}^r(X;KO).$$

To simplify the analysis of these spectral sequences, from now on we localize all homology theories at the prime $`3`$, which has the effect of replacing all homology groups as well as the groups in the AHSS converging to them by the corresponding localized groups; i.e., their tensor product with $`_{(3)}=\{\frac{a}{b}b\text{ is prime to }3\}`$. Note that we continue to write e.g. $`H_{}(X;)`$, but mean the localized group.

In particular, the coefficient ring $`KO_{}`$ is now the ring of polynomials $`_{(3)}[b]`$ with generator $`bKO_4`$. This implies that in the AHSS converging to $`KO_{}(X)`$ only the rows $`E_{p,q}^r`$ for $`q0mod4`$ are possibly non-trivial. In particular, the first differential that can be non-trivial is $`d_5`$. To finish the proof of Theorem 2.9 we will need the following result, which identifies $`d_5`$ with a homology operation. This is certainly well known among experts; since we failed to find an explicit reference in the literature, for completeness we include a proof of this result below.

###### Lemma 3.4.

In the AHSS converging to $`KO_{}(X)`$ localized at $`3`$, the differential

$$d_5:E_{p,q}^5=E_{p,q}^2=H_p(X;)E_{p5,q+4}^5=E_{p5,q+4}^2=H_{p5}(X;)$$

for $`q0mod4`$ is the composition

(3.5)
$$H_p(X;)\stackrel{𝜌}{}H_p(X;/3)\stackrel{P^1}{}H_{p4}(X;/3)\stackrel{𝛿}{}H_{p5}(X;).$$

For the notation, compare 2.8.

###### Proof of Theorem 2.9.

Assume that the space $`X`$ satisfies the homological condition 2.8; i.e., there are (co)homology classes $`\alpha _1\mathrm{},\alpha _{n2}H^1(X;)`$ and $`zH_{n+5}(X;)`$ with

$$\alpha _1\mathrm{}\alpha _{n_2}y0\text{for}y\stackrel{\text{def}}{=}\delta P^1\rho (z).$$

We observe that $`y`$ has property 3.3 by our assumption on $`z`$; moreover, it also has property 3.2 (i.e., it survives to the $`E^{\mathrm{}}`$-term of the AHSS converging to $`\mathrm{\Omega }_{}^{spin}(X)`$) by the following argument. The map of spectral sequences

$$E_{p,q}^r(X;\mathrm{\Omega }^{Spin})E_{p,q}^r(X;KO)$$

is an isomorphism on the rows $`q=0,4`$ for $`r=2`$ and hence for $`r=3,4,5`$ (all the other rows in the range $`4<q<8`$ are trivial since we work localized at the prime $`3`$). Lemma 3.4 shows that the differential

$$d_5:E_{n+5,4}^5(X;KO)E_{n,0}^5(X;KO)$$

sends $`zH_{n+5}(X;)=E_{n+5,4}^2(X;KO)=E_{n+5,4}^5(X;KO)`$ to $`yE_{n,0}^5(X;KO)`$. In particular, $`y`$ is in the kernel of $`d_5`$ in the spectral sequence converging to $`KO_{}(X)`$, and hence also in the kernel of $`d_5`$ in the spectral sequence converging to $`\mathrm{\Omega }_{}^{Spin}(X)`$. The next possibly non-trivial differential

$$d_9:E_{n,0}^9(X;\mathrm{\Omega }^{Spin})E_{n9,8}^9(X;\mathrm{\Omega }^{Spin})$$

is trivial due to our assumption $`n8`$.

This shows that there is a bordism class $`x\mathrm{\Omega }_n^{Spin}(X)`$ with $`H(x)=y`$. Next we want to show that with a careful choice of $`x`$ we can also arrange for $`pD(x)=0`$. We note that the relation $`d_5(z)=y`$ in the spectral sequence converging to $`KO_{}(X)`$ implies that $`pD(x)`$ is zero in

$$E_{n,0}^{\mathrm{}}(X;KO)=F_nKO_n(X)/F_{n1}KO_n(X).$$

This does not imply that $`pD(x)`$ is zero, only that $`pD(x)`$ lies in the filtration $`n1`$ subgroup $`F_{n1}KO_n(X)KO_n(X)`$.

We want to show that replacing $`x`$ by $`x^{}=xx^{\prime \prime }`$ for a suitable $`x^{\prime \prime }F_{n1}\mathrm{\Omega }_n^{Spin}(X)`$ produces an element with the desired properties $`H(x^{})=H(x)`$ and $`pD(x^{})=0`$. We note that the first condition is satisfied because $`H`$ sends elements of

$$F_{n1}\mathrm{\Omega }_n^{spin}(X)=\mathrm{im}\left(\mathrm{\Omega }_n^{spin}(X^{(n1)})\mathrm{\Omega }_n^{spin}(X)\right)$$

to zero, since $`H_n(X^{(n1)};)=0`$. To obtain $`pD(x^{})=0`$, we need to be able choose $`x^{\prime \prime }`$ such that $`pD(x^{\prime \prime })=pD(x)`$; in other words, we need to show that the map

$$pD:F_{n1}\mathrm{\Omega }_n^{spin}(X)F_{n1}KO_n(X)$$

is surjective for $`n8`$. The argument is the following. The map $`\mathrm{\Omega }_q^{spin}KO_q`$ is an isomorphism for $`0q<8`$ and surjective for $`q=8`$. It follows that the map of spectral sequences

$$E_{p,q}^r(X;\mathrm{\Omega }^{Spin})E_{p,q}^r(X;KO)$$

is a surjection for $`r=2`$, $`0q8`$. Since all the differentials of the domain spectral sequence in the range $`0<q8`$, $`n=p+q8`$ are trivial, the above map is also surjective for $`r=3,\mathrm{},\mathrm{}`$ in that range. The groups $`E_{p,q}^{\mathrm{}}`$, $`n=p+q8`$, $`q>0`$, are the associated graded groups for the filtered groups $`F_{n1}\mathrm{\Omega }_n^{spin}(X)`$ (resp. $`F_{n1}KO_n(X)`$). This shows that the map $`F_{n1}\mathrm{\Omega }_n^{spin}(X)F_{n1}KO_n(X)`$ is surjective for $`n8`$ and finishes the proof of Theorem 2.9. ∎

###### Proof of Lemma 3.4.

Multiplication by the periodicity element $`bKO_4`$ produces a homotopy equivalence of spectra $`\mathrm{\Sigma }^4KOKO`$, which in turn induces an isomorphism of spectral sequences $`E_{p,q}^r(X;KO)E_{p,q+4}^r(X;KO)`$. Hence it suffices to prove the corresponding statement for the differential $`d_5:E_{p,0}^5(X;KO)E_{p5,4}^5(X;KO)`$.

Given an integer $`k`$, let $`KOkKO`$ be the $`(k1)`$-connected cover of $`KO`$. Up to homotopy equivalence, $`KOk`$ is characterized by the properties that $`\pi _n(KOk)=0`$ for $`n<k`$ and that the induced map

$$\pi _n(KOk)\pi _n(KO)$$

is an isomorphism for $`nk`$. The spectrum $`KO0`$ is also known as the connective real $`K`$-theory spectrum and is usually denoted $`ko`$. Given a second integer $`lk`$, let $`KOk,l`$ be the part of the Postnikov tower for $`KO`$, whose homotopy groups $`\pi _n(KOk,l)`$ are trivial for $`n<k`$ or $`n>l`$ and are isomorphic to $`\pi _n(KO)`$ for $`knl`$ (this isomorphism is induced by a map $`KOkKOk,l`$). In particular, $`KOk,k`$ has only one possibly non-trivial homotopy group and hence can be identified with the Eilenberg-MacLane spectrum $`\mathrm{\Sigma }^kH\pi _k(KO)`$ (here $`HA`$ for an abelian group $`A`$ is the Eilenberg-MacLane spectrum characterized by $`\pi _0(HA)=A`$ and $`\pi _n(HA)=0`$ for $`n0`$).

We note that the maps $`KO0KO`$ and $`KO0KO0,4`$ induce isomorphisms of AHSS’s in the range $`0q4`$ for $`r=2,3,4,5`$ (since we work localized at $`3`$, all rows for $`q0mod4`$ are trivial, and hence the first possibly non-trivial differential is $`d_5`$). The AHSS $`E_{p,q}^r(X;KO0,4)`$ has only two non-trivial rows and hence degenerates to a long exact sequence

$$\begin{array}{c}\mathrm{}KO0,4_n(X)E_{n,0}^5=H_n(X;)\stackrel{d_5}{}\hfill \\ \hfill E_{n5,4}^5=H_{n5}(X;)KO0,4_{n1}(X)\mathrm{}.\end{array}$$

This can be identified with the long exact homotopy sequence induced by the Puppe sequence

$$\begin{array}{c}KO4,4XKO0,4XKO0,0X=HX\hfill \\ \hfill \stackrel{f1}{}\mathrm{\Sigma }KO4,4X=\mathrm{\Sigma }^5HX\end{array}$$

The homotopy class of $`f:H\mathrm{\Sigma }^5H`$ can be interpreted as a cohomology class in $`H^5(H;)/3`$ (we’ve localized at $`3`$). The generator of $`H^5(H;)`$ is given by applying $`\delta P^1\rho `$ to the generator of $`H^0(H;)_{(3)}`$. This shows that $`d_5`$ is a multiple of the homology operation 3.5.

To shows that it is a non-trivial multiple, it suffices to show that the differential is non-trivial for some space or spectrum $`X`$. We choose $`X=H/3`$, and consider the AHSS

$$E_{p,q}^r(H/3;ko)ko_{p+q}(H/3)=\pi _{p+q}(koH/3)=H_{p+q}(ko;/3).$$

It is well known that $`H^{}(ko;/3)A/\left(AQ_1+A\beta \right)`$. For this, see \[AP, Prop. 2.3\]; that proposition applies to the spectrum $`X=KO4`$, which localized at $`3`$ by Bott-periodicity may be identified with $`\mathrm{\Sigma }^4ko`$). Here $`A`$ is the mod $`3`$ Steenrod algebra, $`\beta A_1`$ is the Bockstein ($`A_nA`$ consists of the elements of degree $`n`$), and $`Q_1A_5`$ is the commutator of $`P^1A_4`$ and $`\beta `$. In particular, since $`\beta P^1`$ and $`P^1\beta `$ form a basis of $`A_5`$, the cohomology group $`H^5(ko;/3)`$ and hence the group $`H_5(ko;/3)=ko_5(H/3)`$ is trivial. It follows that the non-trivial elements in

$$E_{5,0}^2(H/3;ko)=H_5(H/3;)/3$$

do not survive to the $`E^{\mathrm{}}`$-term. For dimensional reasons the only possibly non-trivial differential is $`d_5`$. This finishes the proof of Lemma 3.4. ∎

## 4. Construction of spaces satisfying the homological condition 2.8

The goal of this section is the construction of spaces satisfying the homological condition 2.8; in particular, we will prove Proposition 2.11, which claims that the classifying space $`B\mathrm{\Gamma }_n`$ satisfies this condition, where $`\mathrm{\Gamma }_n`$ is the product of two copies of $`/3`$ and $`n2`$ copies of $``$. For this calculation it is convenient to pass to cohomology. The following lemma will give a cohomological condition which implies the homological condition 2.8.

To state the lemma, we first need some notation. Let $`\rho :H^{}(X;)H^{}(X;/3)`$ be mod $`3`$ reduction and let $`\beta :H^{}(X;/3)H^{+1}(X;/3)`$ the mod $`3`$ Bockstein homomorphism, the boundary map of the long exact cohomology sequence induced by the short exact coefficient sequence $`/3\stackrel{\times 3}{}/3^2/3`$. We recall that $`\beta `$ is the composition $`\rho \delta `$, where $`\delta :H^{}(X;/3)H^{+1}(X;)`$ is the integral Bockstein. Let $`Q_1`$ be the degree $`5`$ element of the mod $`3`$ Steenrod algebra which is the commutator $`Q_1=[P^1,\beta ]`$.

###### Lemma 4.1.

Let $`X`$ be a space and assume there are cohomology classes $`\alpha _1,\mathrm{},\alpha _{n2}H^1(X;)`$ and $`\zeta H^2(X;/3)`$ such that

(4.2)
$$\rho (\alpha _1)\mathrm{}\rho (\alpha _{n2})\beta Q_1\zeta 0H^{n+6}(X;/3).$$

Then $`X`$ satisfies the homological condition 2.8.

###### Proof.

The assumption of the lemma implies that there is a homology class $`yH_{n+6}(X;/3)`$ such that the Kronecker product

$$\rho (\alpha _1)\mathrm{}\rho (\alpha _{n2})\beta Q_1\zeta ,y$$

is non-zero. We calculate, using that $`Q_1`$ and $`\beta `$ are graded derivations and that the cohomological $`\beta `$ and $`Q_1`$ are dual to the homological versions,

$`0`$ $`\rho (\alpha _1)\mathrm{}\rho (\alpha _{n2})\beta Q_1\zeta ,y`$
$`=\rho (\alpha _1)\mathrm{}\rho (\alpha _{n2})Q_1\zeta ,\beta y\text{(since }\beta \rho =0\text{)}`$
$`=\rho (\alpha _1)\mathrm{}\rho (\alpha _{n2})\zeta ,Q_1(\beta y)\text{(since }Q_1(H^1(X))=0\text{)}`$
$`=\rho (\alpha _1)\mathrm{}\rho (\alpha _{n2})\zeta ,\beta P^1\rho (\delta y)\text{(since }\beta \beta =0\text{)}`$
$`=\zeta ,\rho \left(\alpha _1\mathrm{}\alpha _{n2}\delta P^1\rho (\delta y)\right)\text{(since }\beta =\rho \delta \text{)}`$
This shows that the non-triviality of $`\rho (\alpha _1)\mathrm{}\rho (\alpha _{n2})\beta Q_1\zeta `$ implies that $`\alpha _1\mathrm{}\alpha _{n2}\delta P^1\rho (z)`$ for $`z=\delta y`$ is non-trivial. ∎

Recall the statement of Proposition 2.11:

###### Proposition 2.11 1.

For $`n2`$, let $`\mathrm{\Gamma }_n`$ be the Cartesian product of $`2`$ copies of $`/3`$ and $`n2`$ copies of $``$. Then the classifying space $`B\mathrm{\Gamma }_n`$ satisfies the homological condition 2.8.

###### Proof of Proposition 2.11.

We recall that the cohomology ring of

$$B\mathrm{\Gamma }_n=\underset{n2}{\underset{}{S^1\times \mathrm{}\times S^1}}\times B/3\times B/3$$

is given by

$$H^{}(B\mathrm{\Gamma }_n;/3)=\mathrm{\Lambda }(\rho (\alpha _1),\mathrm{},\rho (\alpha _{n_2}),x_1,x_2)/3[\beta x_1,\beta x_2],$$

where $`\alpha _iH^1(B\mathrm{\Gamma }_n;)`$ is the pull back of the generator of $`H^1(S^1;)`$ via the projection to the $`i`$-th copy of $`S^1`$, and $`x_1`$ (resp. $`x_2`$) is the pull back of the generator of $`H^1(B/3;/3)`$ via the projection to the first (resp. second) $`B/3`$-factor of $`B\mathrm{\Gamma }_n`$.

We calculate for $`j=1,2`$

$$Q_1(x_j)=[P^1,\beta ]x_j=P^1\beta x_j\beta P^1x_j=(\beta x_j)^3.$$

Since $`\beta `$ and $`Q_1`$ are graded derivations, it follows that

$$\beta Q_1(x_1x_2)=\beta \left((\beta x_1)^3x_2x_1(\beta x_2)^3\right)=(\beta x_1)^3\beta x_2\beta x_1(\beta x_2)^30.$$

It follows that $`\zeta =x_1x_2`$ satisfies the cohomological condition (4.2). ∎

## 5. Asphericalization procedures

In this section we prove Addendum 1.6 to our main theorem claiming that the groups $`\pi `$ for which we can construct counter examples to the Gromov-Lawson Conjecture 1.1 may be chosen to have classifying spaces which are manifolds which are non-positively (resp. negatively) curved in the Alexandrov sense. This means the following.

###### Definition 5.1.

A *length space* is a metric space where any two points can be joined by a geodesic. A length space $`X`$ is called a (locally) *CAT($`r`$)-space* for $`r`$, if given a triangle $`T`$ in a sufficiently small open set of $`X`$ and a vertex $`x`$ of $`T`$, the distance from $`x`$ to the opposite edge is not more than the corresponding distance in a comparison triangle in a simply connected manifold with constant curvature equal to $`r`$. A *comparison triangle* is a triangle with the same side lengths as the given one.

We say that $`X`$ is *negatively curved in the Alexandrov sense* (resp. *non-positively curved*), if $`X`$ is a CAT($`r`$)-space with $`r<0`$ (resp. $`r=0`$).

This is a generalization of the classical notion: every complete Riemannian manifold of negative curvature is negatively curved in the Alexandrov sense, and correspondingly for non-positive curvature.

To produce discrete groups $`\pi `$ whose classifying space is a manifold which is non-positively curved (resp. negatively curved) in the Alexandrov sense, we use asphericalization procedures due to Davis-Januskiewicz \[DJ\] and Charney-Davis \[CD\]. An asphericalization procedure assigns to every space $`X`$ in a certain class of spaces an aspherical space $`BLX`$ together with a map $`BLXX`$ with certain homological properties. Here the notation $`BLX`$ is chosen to reflect the fact that $`BLX`$ serves as a classifying space for its fundamental group, for which the notation $`LX`$ is used.

Typically, the spaces $`X`$ considered are simplicial (or cubical) cell complexes and $`BLX`$ is constructed by replacing each $`n`$-cell of $`X`$ by some ‘model space’ and by gluing together these model spaces to form $`BLX`$ according to the same combinatorial patters as the cells of $`X`$ are glued to form $`X`$.

If this is done carefully, as in the procedures described below, one can construct metrics on the result which satisfy appropriate curvature conditions. However, even if the resulting space is a smooth manifold, it is not clear at all whether the metric can be chosen to be a smooth Riemannian metric.

### Baumslag-Dyer-Heller asphericalization

The construction of Baumslag, Dyer and Heller uses as basic building block an acyclic group, i.e. a non-trivial group with trivial integral homology. For suitable choices of this building block, their construction gives explicit descriptions of $`LX`$ as elements of $`𝒞`$. This description uses the combinatorics of the simplicial complex $`X`$ (compare also the description of a very similar asphericalization procedure in \[Bl\]). The map $`BLXX`$ they produce induces an isomorphism in homology.

### Davis-Januskiewicz asphericalization

The goal of constructing $`BLX`$ which is non-positively curved can be achieved using an asphericalization procedure of Davis and Januskiewicz \[DJ\]. If $`X`$ is a closed $`n`$-manifold, their construction produces a new $`n`$-manifold $`BLX`$ which is non-positively curved in the Alexandrov sense, and whose fundamental group $`LX`$ belongs to the class $`𝒞`$. The price to be paid is that the map $`BLXX`$ unlike in the case of the Baumslag-Dyer-Heller procedure in general does not induces an isomorphism in homology (necessarily so: e.g. for $`X=S^2`$ there is no non-positively curved $`2`$-manifold with the same homology as $`S^2`$). However, the map $`H_{}(BLX;)H_{}(X;)`$ is still surjective.

This is good enough to prove part (1) of Addendum 1.6 as follows. Let $`Y`$ be the manifold with boundary obtained as a ‘thickening’ of the $`n+5`$-skeleton of $`B\mathrm{\Gamma }_n`$ (cf. Prop. 2.11) in $`^N`$ with $`N`$ large. Let $`X`$ be the boundary of $`Y`$ We note that the homology of $`X`$ is isomorphic to the homology of $`B\mathrm{\Gamma }_n`$ in degrees $`n+5`$ for $`N`$ sufficiently large. In particular, since $`B\mathrm{\Gamma }_n`$ satisfies the homology condition 2.8, so does the manifold $`X`$. Then the surjectivity of the map $`H_{}(BLX;)H_{}(X;)`$ implies that also $`BLX`$ satisfies the condition, and hence Corollary 2.10 implies that the Gromov-Lawson Conjecture does not hold for $`\pi =LX`$.

### Charney-Davis asphericalization

This procedure is essentially a strengthening of the Davis-Januskiewicz procedure: from a closed $`n`$-manifold $`X`$ it produces an $`n`$-manifold $`BLX`$ which is negatively curved in the Alexandrov sense and a map $`BLXX`$ which induces a surjection on homology. However, $`LX`$ might not belong to the class $`𝒞`$.

With the same argument as above, we can then produce a group $`\pi `$ for which the Gromov-Lawson Conjecture doesn’t hold, which is the fundamental group of a negatively curved manifold. This proves the second part of Addendum 1.6.