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# A Search for Fine Structure of the Knee in EAS Size Spectra

## 1 Introduction

The existence of the ’knee’ in the spectra of extensive air showers (EASs) has been known by now for more than 40 years . First seen in the number of electrons (the shower ’size’) observed near sea level it was later also observed in the muon number , hadron properties  and muon densities . In fact it seems to show up in all shower observables if investigated in sufficient detail. Nevertheless its origin is still obscure. Of the explanations proposed two seem to have found more general acceptance.

The first of these relates the knee to the influence of interstellar magnetic fields during propagation of the cosmic ray particles in or leakage from the Galaxy or in the course of acceleration for which magnetic fields probably play a major role. Since the radius of curvature of an extremely relativistic particle in a magnetic field is proportionate to its energy $`E`$ and inversely proportionate to its nuclear charge $`Z`$ one would expect the knee then to show up at different energies for different nuclear species among the primary particles. In fact one would expect the energy spectra of each element to show a knee at an energy displaced by a factor of $`Z`$ with respect to that of protons. This was probably first realized by Peters  who discussed the implications on various shower observables in great detail111I thank P. Grieder (Bern) for drawing my attention to this important old reference.. The effect of this on the total energy distribution of cosmic ray particles is illustrated in fig. 1 which shows the result of a simple model calculation based on data compiled by Wiebel-Sooth et al. . These authors give, for each element up to nickel ($`Z=28`$), the differential flux at 1 TeV and the exponent of the power law spectrum. These partial spectra were extrapolated up to a knee which was assumed to lie at $`lg(E_{K,Z}[TeV])=3.4+lgZ`$. This corresponds to a knee energy of c. 2.5 PeV for protons. It was then assumed that the exponent increased abruptly at the knee by 0.35 for all elements. All statistical errors (which are of course substantial owing to the extrapolation by some orders of magnitude) were neglected. The full line in fig. 1 represents the sum of all contributions from hydrogen to nickel. The two dotted lines are the extrapolations of the all particle spectrum from below the proton and above the iron knee. As fig. 1 shows the change of slope is, unsurprisingly, not confined to one position or small range along the line. At least three bends are obvious corresponding to hydrogen, helium and the iron group. Hence in this case one would clearly expect a more complicated structure of the spectrum than a simple bend for all shower observables depending on primary energy.

The second proposal, less popular than the first one though recently reasserted by Nikolsky and Romachin , attributes the origin of the knee to the properties of high energy interactions in the atmosphere. A change of the spectrum of observables on ground level might of course occur if strong interaction changes by some kind of threshold phenomenon. The knee energy is estimated to be near a few PeV which is approximately a factor of 2 above the highest centre of mass energy available in the laboratory today. Therefore such an effect cannot at present be excluded. Since an EAS induced by a nucleus of mass number $`A`$ and energy $`E`$ may, to a reasonable first approximation, be considered as a superposition of $`A`$ showers induced by nucleons of energy $`E/A`$ (superposition principle) one would expect, under this assumption, a similar shift of the knee position as described above but by a factor of $`A`$ instead of $`Z`$. Again a more complex structure of the knee would appear natural and a picture very similar to the one shown in fig. 1 would be obtained.

It should be mentioned that the KASCADE collaboration has recently presented evidence that the knee is to be attributed to light nuclei and that the spectrum of heavier nuclei does not exhibit a change of slope in the vicinity of the ’main’ knee. This claim is based on a comparison of electron and muon numbers of EASs with Monte Carlo simulations  but also on a phenomenological classification of EAS by their electron to muon ratios .

Erlykin and Wolfendale have recently, in a series of papers , claimed observational evidence for a more complicated structure of the knee region. This structure which according to the authors does not show up clearly in single measurements but becomes visible when averaging several ones, is attributed to the influence of a recent nearby supernova. It is probably not unfair to say that not many have been convinced by the empirical evidence claimed by the authors. But the underlying idea appears very intriguing and reasonable. The solar system has, during the 4.5 billion years of its existence, probably been passed by several if not many shock fronts from supernovae exploding in its vicinity. One of these clearly must be the most recent one and it appears well conceivable that the cosmic ray spectrum which we observe today is influenced by this individual event (and hence not typical for the whole Galaxy). The possibility of a single source having a large impact on the energy and mass distributions of cosmic rays at the earth was already realized by Peters .

For all these reasons it appears interesting to study the shape of the knee region in more detail and to look as to whether it can be really described by a simple bend between two power laws or whether any of the effects mentioned above can be identified. Except for the work by Erlykin and Wolfendale the author is not aware of any other attempt in this direction. A definite negative result would not only worry some authors but also present difficulties for the usual models of the origin of the knee whose existence, on the other hand, is beyond any doubt.

In this paper I attempt to compare 28 different measured spectra of the electron number $`N`$ in the knee region. (I drop the usual subscript $`e`$ because there can be no confusion in this paper.) The data originate from 7 experiments and cover a range of atmospheric depths between 730 and 1250 \[$`g/cm^2`$\]. The electron number (or shower ’size’) is probably the shower observable for which the largest amount of measurements exist. The basic procedure adopted is the following: Each spectrum is first fitted separately by an adequate function adjusting either 4 or 5 parameters. In a next step the residual spectra are shifted to the same knee position and averaged. It may be expected that this averaging reduces not only the statistical fluctuations of the measurements but also (at least part of) the systematic ones and hence should make any deviations from the pre-chosen fit function more conspicuous.

The data used and their analysis are described in the following section. In section 3 we compare the results of the analysis with a simple model and present our conclusions in section 4.

## 2 Data and analysis

### 2.1 The data base

A list of the spectra analysed in this paper and their sources can be found in table 1. The EAS-TOP experiment is the only one which has published  the $`N`$ spectra in numerical form222It should be mentioned that the scale factor quoted in the caption of the relevant table 1 of ref.  should read $`10^7`$ instead of $`10^8`$ .. The CASA data were read from table 6.2 of reference  (which is equivalent to fig. of ref. ). Such a procedure is of course of limited accuracy and does not exhaust the statistical precision of the data (especially at low shower sizes). All other data sets were made available in numerical form by the authors333I thank A. Chilingarian (Yerevan), R. Glasstetter (Karlsruhe), G. Heinzelmann (Hamburg), N. N. Kalmykov (Moscow) and M. Nagano (Tokyo) for their invaluable support.. Table 1 gives some details of the data together with the quality of the two kinds of fits described in the next subsections. Several experiments registered events in different ranges of zenith distance which then of course correspond to different atmospheric depths. The total data set comprised 784 points which is to be compared with a total of 112 or 140 derived parameters for the four or five parameter fits, respectively.

### 2.2 Four parameter fits

All fits performed were least squares fits with $`lgN`$ and $`lg(N^{2.5}I)`$ as the variables and employing the usual weights derived from the quoted errors. Here $`I`$ is the differential flux. In a first step, the fit function chosen consisted of two power laws connecting continuously at the knee position:

$$I(N)=I_K\left(\frac{N_K}{N}\right)^\gamma $$
(1)
Here $`I_K`$ is the differential flux at the knee position and $`\gamma =\gamma _1`$ for $`N<N_K`$ and $`\gamma =\gamma _2`$ for $`N>N_K`$.

The quantities $`I_K,N_K,\gamma _1`$ and $`\gamma _2`$ were adjusted to describe the data. After the fit, the differences between observed and fit values were calculated for each of the 28 spectra. These spectra of residuals were then shifted along the $`lgN`$ axis to the same knee position. This amounts to choosing $`lg(N/N_K)`$ as the new independent variable where $`N_K`$ is the knee position found for the respective spectrum. The scatter of the data points after these procedures is illustrated in fig. 2 which clearly exhibits the statistical nature of the residuals (and the increase of the errors with increasing $`N`$). No errors bars have been drawn because this would completely confuse the picture but most of them are compatible with 0.

As the next step, all data points within horizontal intervals of width 0.1 were averaged neglecting the horizontal uncertainties resulting from the errors of $`N_K`$. The latter were smaller than the chosen bin width for almost all spectra. The number of data points within a given interval was above 30 in the vicinity of the knee and dropped to near 1 at the extreme ends of the total range because the $`N`$ ranges of the various measurements did not coincide. It should be mentioned that most of the original data were also binned in intervals of 0.1 width so this choice was very natural.

The averaging procedure described actually amounts to taking the geometric means of $`I_{obs}/I_{fit}`$ (with adequate weights). This eliminates all sensitivity to the absolute normalization of the data. There is reason to suspect that the quantity which different experiments call shower size $`N`$ is not the same. This is most obvious when the influence of muons on the experimental results is considered. The electron detectors, in all experiments scintillation counters, are also sensitive to muons. Some experiments, such as KASCADE , put a lot of effort into correcting for this effect. This is impossible, on the other hand, if muons are not measured independently as is the case in some of the experiments included in this analysis. Also different detector thresholds or saturation effects may lead to systematic differences. The advantage of choosing $`lg(N/N_K)`$ as a new variable is that constant scale factors cancel. Although not all of the effects mentioned above will lead to modifications of $`N`$ by a constant factor at least some instrumental effects will be reduced or even removed.

The weighted averages thus obtained are displayed in fig. 3 with their statistical errors (which have been multiplied, as usual, by the root of $`\chi ^2/F`$ if the latter was larger than 1). A number of points at the upper end of the spectrum have been omitted here because of their huge errors. These were all compatible with 0 within their statistical errors. In spite of the considerable errors the mean residuals can hardly be said to scatter statistically. The most significant deviations, at the two points neighbouring the knee position, amount to $`7.6\sigma `$ and $`4.6\sigma `$ and are therefore highly significant.

A large discrepancy in the immediate vicinity of the knee position is in no way surprising because several experiments have shown that the slope of the spectrum does not change abruptly at the knee but rather smoothly over a finite range of $`lgN`$. The sign of the deviation is precisely as would be expected in such a situation. So the most prominent deviation just reflects a well known and expected feature. On the other hand, this result also shows that the procedure adopted in this paper is suitable to reveal more clearly a structure where it is present. But obviously a more suitable fit function has to be employed.

It is worthwhile mentioning that the knee positions resulting from the fits show the well known dependence on atmospheric depth. Five of the seven experiments with 18 spectra are in good agreement with a simple linear dependence. The other two can be made to agree when the shower sizes are scaled down by 30% and 70%. The latter would not affect the present analysis in any way, of course. The scatter of the other parameters is clearly larger than the quoted statistical errors would indicate. This is subject of further analysis. Since in this study we are focussing on deviations from a smooth size dependence in a limited size range I would not expect such (apparently systematic) differences between experiments to influence my conclusions.

### 2.3 Five parameter fits

Several different methods have been used to describe a smooth knee all of which seem to work reasonably well. A very popular procedure is to select a finite interval in the vicinity of the knee and then first fit power laws to the regions above and below this interval. In a second step these functions are then connected smoothly, e.g. by a polynomial. A disadvantage of this method is, in my opinion, that at least two but usually more additional parameters are introduced (which does not seem to be always realized).

Ter-Antonyan and Haroyan  have used a function which avoids this disadvantage. Their expression

$$I(N)=I_K\left(\frac{N}{N_\mathrm{K}}\right)^{\gamma _1}\left(1+\left(\frac{N}{N_\mathrm{K}}\right)^\epsilon \right)^{(\gamma _1\gamma _2)/\epsilon }$$

can be shown to approach pure power laws far from the knee and to tend to eq. (1) for $`ϵ0`$. The additional parameter $`ϵ`$ does not lend itself to a direct physical interpretation, though. Also the two regions above and below the knee are not described in a formally equivalent way.

I have adopted a different approach. It consists of folding eq. (1) with a normalized distribution of finite variance. This implies a model in which a hypothetical underlying spectrum with a sharp knee is observed with finite resolution. The exact shape of the ’resolution function’ is not really important but if a log-normal distribution is chosen the following closed expression is obtained:

$$I(N)=I_K\left(e^{\sigma ^2\gamma _1^2/2}\mathrm{\Phi }(u_1)\left(\frac{N_K}{N}\right)^{\gamma _1}+e^{\sigma ^2\gamma _2^2/2}[1\mathrm{\Phi }(u_2)]\left(\frac{N_K}{N}\right)^{\gamma _2}\right)$$
(2)
$$u_i=\sigma \gamma _i\frac{ln(N/N_K)}{\sigma }$$

Here $`\sigma `$ is the standard deviation of the log-normal distribution and $`\mathrm{\Phi }(u)`$ is the error integral:

$$\mathrm{\Phi }(u)=\frac{1}{\sqrt{2\pi }}\underset{\mathrm{}}{\overset{u}{}}e^{x^2/2}𝑑x$$

It is again straightforward to show that eq. (2) approaches power laws at sufficient distances from the knee and tends to eq. (1) for $`\sigma 0`$. As far as the physical interpretation is concerned one should realize that $`\sigma `$ does not primarily represent instrumental effects. It is well known from simulations of EAS development in the atmosphere that the shower size $`N`$ fluctuates considerably for events of fixed primary energy, mass and direction of incidence. The effects of these fluctuations are also incorporated in the parameter $`\sigma `$.

I should like to point out that it is, in my opinion, very much a matter of taste which of the described approaches is chosen. Since all describe the experimental spectra well within observational uncertainties they will all lead to the same conclusions.

The fitting and averaging was then performed as described in the preceding subsection. Fig 4 displays the result. The residuals are now below 0.005 (which corresponds to a difference between fit and measurement of less than $`1\%`$) for the whole lower part of the spectrum, up to $`lg(N/N_K)0.6`$.

The remaining deviations in the upper part amount to $`10\%`$ on the positive side and $`5\%`$ on the negative side. Their regular pattern with increasing size can hardly be called statistical in spite of the fact that only two of the last 15 data points differ from 0 by more than 2 standard deviations. A possible explanation is discussed in the next section where the origin of the dotted curve in fig. 4 will also be explained.

One might argue that several data points in the lower size range clearly differ from 0 by a similar amount statistically or even recognise an oscillatory structure. But this deviation is on the 1 % level and hence a factor of 5 to 10 smaller than the one in the upper size range. I would tend to argue, to the contrary, that an agreement between various experiments on this level is rather impressive and would hesitate to draw far reaching conclusions from these observations.

## 3 Discussion

The results displayed in fig. 4 show clearly that the lower part of the observed size spectrum is well describeded by two power laws and a simple knee. I find it difficult to believe, on the other hand, that the discrepancy visible in the upper part of the size range is purely statistical, in spite of the large errors of the individual points (but this is of course left to the reader’s own judgement). It is much more difficult to assess possible systematic errors. I will come back to the latter question later in this section and first turn to a possible explanation of the observed deviations assuming they are real.

Let us suppose that the real size spectrum exhibits two knees displaced by one or two orders of magnitude with respect to each other. This is not unreasonable in view of the considerations extended in the introduction and illustrated in fig. 1. Then a situation might occur which is sketched in fig. 5. Here the full line represents a hypothetical spectrum with two knees. If one tries to fit this spectrum with an expression allowing only one knee this will be adjusted to the lower one because it is more pronounced. Also statistical errors of the data points increase with increasing shower size and hence the lower points carry larger weights. But the deviation of the data from a pure power law in the higher size range will influence the fit and might lead to a situation illustrated by the dotted line in fig. 5. This would then result in differences between data and fit which agree qualitatively with those observed in fig. 4. I admit that the separation of the full and dotted lines in fig. 5 does not look dramatic but one should be aware of the difference in the vertical scales between figs. 4 and 5.

It is possible to extend this conjecture a step further. For this let us try to estimate the size spectrum resulting from an energy spectrum as displayed in fig. 1. Essentially all simulations of EASs lead to a power law relation between shower size and energy for primary protons, at least in the range of energy and atmospheric depth relevant for this analysis:

$$N_p=aE_p^\delta $$

The corresponding relation for a heavier primary may then be estimated by help of the superposition principle invoked already in the introduction:

$$N_A=Aa\left(\frac{E_A}{A}\right)^\delta $$

Here $`E_A`$ denotes the energy of a nucleus of mass number $`A`$. Assuming again, as in the introduction, that the knee position in energy is shifted by a factor of $`Z`$, $`E_{K,A}=ZE_{K,p}`$, one obtains for the shift of the knee in shower size

$$N_{K,A}=Aa\left(\frac{E_{K,A}}{A}\right)^\delta =aZ^\delta A^{1\delta }E_{K,p}^\delta $$

$$lgN_{K,A}=lgN_{K,p}+\delta lgZ(\delta 1)lgA$$

So in this simple model the shift depends only on mass and charge of the nuclei. The second column of table 2 shows these shifts for some abundant elements. The value of $`\delta 1.30`$ which is the only additional information needed, was calculated from simulation results reported in tables 20 and 26 of  (for the QGS-JET model; the other 4 models given in the same tables differ from this by at most 0.04). The separation between hydrogen and helium is reduced as compared to the corresponding shift in the energy spectrum due to the difference in mass to charge ratio. So the knees of these elements would merge if the smoothness is taken into account. Hence in this case the knee observed in the size spectrum has probably to be attributed to the combined effect of protons and helium. It is obvious that the shift of the knee for iron is of the right order of magnitude to explain a deviation as seen in fig. 4.

If the other (less popular) proposal for the origin of the knee is adopted, $`E_{K,A}=AE_{K,p}`$, one obtains in a similar way

$$lgN_{K,A}=lgN_{K,p}+lgA$$

The corresponding values have also been entered into table 2. Intriguingly, the position of the iron knee obtained under the assumption of $`E_{K,A}A`$ is in better quantitative agreement with the deviations observed in fig. 4. On the other hand, the knees originating from protons and helium should then appear well separated of which there is not much evidence in the figure.

In order to check this possibility further I have calculated the following ’toy’ model. I have assumed that the size spectrum can be described by the sum of two functions of the type given in eq. (2) with different intensities, the same slopes and the two knees separated by $`\mathrm{\Delta }lgN_K=1.7`$. This model spectrum then has two free parameters to adjust, the ratio of intensities and the change of the power law exponents. For the latter $`\mathrm{\Delta }\gamma =0.5`$ was assumed. The parameters $`\sigma `$ were chosen to reproduce the variance of the simulation results in the quoted tables of ref.  and were 0.44 for protons and 0.08 for iron. This choice neglects all instrumental effects on the size resolution and should therefore represent a lower limit. This calculated spectrum was then fitted by a single function of the same type with the knee at the same position as the lower of the other two. Intensity and slope below the knee were taken to be the same as those of the model spectrum, and the slope above the knee adjusted. The difference of the model and fit spectra are shown in fig. 4 as the dotted line. It should be emphasized that the width of the knees were not varied but kept fixed at the values quoted above. The three new parameters (relative intensity, change of the exponent of the model function and slope above the knee of the fit function) were adjusted to some extent but no serious attempt was made to obtain a perfect fit. For this all elements expected to be present in primary cosmic rays should have to be taken into account. Also there is no compelling reason to believe that all partial spectra have the same exponents. This would then leave more parameters to adjust than data points in fig. 4. Although the dotted line does not reproduce the data perfectly the model gives a reasonable description in view of its crudeness. Hence the data can be said to be in agreement with a second component in the overall spectrum exhibiting a knee at higher shower size. It remains surprising, though, that the displacement is clearly in better agreement with a proportionality of the knee position to mass rather than to charge of the primary nuclei (if the second component is attributed to iron which appears to be the most reasonable choice).

This is probably the right moment to stop speculating and to turn to the thornier question of systematic errors. It should be mentioned that the number of experimental points averaged drops from 29 at $`lgN=0.6`$ to 7 at 2.1. So the region where the deviation is observed covers the highest data points of several experiments and these might be under suspicion to suffer from saturation effects. Saturation will lead to an overestimate of the differential flux increasing towards the end of the range of measurement. Therefore it is, in my opinion, not possible to exclude at this moment systematic effects as a possible origin of the observed deviations without more detailed investigations. These require a better knowledge of experimental details and have to be performed for each experiment separately. This is beyond the scope of the present paper.

## 4 Summary

I have presented an analysis of 28 size spectra from 7 different experiments. Their results can be well represented by two power laws with a smooth knee in between up to a shower size a factor of $`4`$ above the bend. At larger sizes a deviation occurs which appears statistically sound though not overwhelming. The maximum of this deviation roughly coincides with the position where one would expect a knee originating from primary iron nuclei if the knee in energy is assumed to be shifted in proportion to primary mass. I realize of course that, to the best of my knowledge, no such feature has ever been seen before in size spectra although a second knee was seen in the derived energy spectrum by the AKENO group . (The deviations claimed by Erlykin and Wolfendale  are closer to the main knee position and cannot therefore be identified with the ones observed here.) But on the other hand no analysis so far has taken advantage of the statistics of 28 spectra from 7 experiments. The effect shows up in a region where detectors might start to saturate which may lead to distortions of the spectrum. Hence systematic errors cannot, in my opinion, presently be ruled out as the origin of the observed fine structure.

I would consider it worthwhile to study the data from experiments with high statistics and high detector quality in more detail, especially as far as saturation effects are concerned, in order to verify or not the existence of this fine structure. One way of checking the influence of saturation is to compare spectra taken by the same experiment in different bins of zenith distance. The measured size of a primary of given energy and mass decreases with increasing zenith angle. This results in a shift of the knee position to lower sizes with increasing zenith distance. This shift has been observed by many experiments and is also clearly visible in the data of the 5 experiments which have contributed more than one spectrum to this investigation. Hence vertical showers should saturate at lower values of $`lg(N/N_K)`$. If the same structure is observed at all zenith distances the influence of saturation can be ruled out. The range of shower sizes of such a study should of course extend up to at least two orders of magnitude above the ’main’ knee. This implies a reduction of particle flux by about 4 orders of magnitude and hence requires very good statistics as well as detectors of a considerable dynamic range.

It should be mentioned that the analysis described in section 2 of course also yields numerical values for the 4 or 5 parameters and their statistical errors and it appears interesting to compare the results from the various experiments and study their dependence on atmospheric depth. This will be the subject of a forthcoming paper.

Acknowledgements
Writing this paper would have been impossible without the generous support of quite a number of colleagues. I thank especially A. Chilingarian (Yerevan), R. Glasstetter (Karlsruhe), G. Heinzelmann (Hamburg), N. N. Kalmykov (Moscow) and M. Nagano (Tokyo) for making the results of their respective experiments available in numerical form. I am also grateful to P. Grieder (Bern) and L. Jones (Ann Arbor) for their help in retrieving literature and D. Heck and M. Roth (both at Karlsruhe) for their advice concerning LATEX and PAW (and their patience). Last not least I thank the Forschungszentrum Karlsruhe, especially H. Blümer, for permission to use its facilities even after retirement.


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# References

## List of figures

1. Results of the model for the pseudorapidity distribution of charged particles for central (5 %) PbPb collisions at 17.3 GeV per nucleon in the center of mass (dashed-dotted line), and central (6 %) AuAu collisions at 56 (dotted line), 130 (dashed line) and 200 (solid line) GeV per nucleon in the center of mass, compared with experimental data at SPS from NA49  (black square) and WA98  (black, upward pointing triangle), and at RHIC from PHOBOS  (black, downward pointing triangle for 56 GeV, open circle for 130 GeV and black circle for 200 GeV), BRAHMS  (open square) and PHENIX  (open triangle).

2. Pseudorapidity density of charged particles at $`\eta =0`$ divided by one half the number of participant nucleons, versus the number of participant nucleons, in PbPb collisions at 17.3 GeV per nucleon in the center of mass (multiplied by 1/2, lower curves and symbols) and in AuAu collisions at 130 GeV per nucleon in the center of mass (upper curves and symbols); also the experimental number for $`\overline{\mathrm{p}}`$p collisions at 130 GeV per nucleon is given , filled square. Experimental data are from PHENIX  (filled triangles), PHOBOS  (open triangle), WA98  (filled circles) and NA49  (open circle). Curves are results of the model for the 75 % more central events, without fusion or rescattering (dotted lines), with fusion (dashed lines) and with fusion and rescattering (solid lines).

3. The same as in Fig. 2, but for PbPb collisions at 5.5 TeV per nucleon in the center of mass.

4. Transverse momentum spectrum ($`1/(2\pi p_T)dN/(d\eta dp_T)|_{\eta =0}`$ versus $`p_T`$) of charged particles at $`\eta =0`$ in AuAu collisions at 130 GeV per nucleon in the center of mass, for central collisions (5 %, solid and dashed lines and filled circles) and for minimum bias collisions (92 %, multiplied by 0.01, dotted and dashed-dotted lines and open circles). Data are from PHENIX ; solid and dotted lines are results of the model with string fusion, dashed and dashed-dotted lines with string fusion and rescattering.

## List of tables

1. Different particle ratios in central (10 %) AuAu collisions at 130 GeV per nucleon in the center of mass in the model without string fusion or rescattering (NF), with string fusion (F) and with string fusion and rescattering (FR) for particles with $`p_T>0.2`$ GeV/c, compared with experimental data . For the centrality criteria and kinematical cuts in the different experiments and ratios, see the experimental references and comments in the text.

Figures:

Tables:


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# Quantum and Thermal Phase Transitions of Halogen-Bridged Binuclear Transition-Metal Complexes

## Abstract

Aiming to settle the controversial observations for halogen-bridged binuclear transition-metal (MMX) complexes, finite-temperature Hartree-Fock calculations are performed for a relevant two-band Peierls-Hubbard model. Thermal, as well as quantum, phase transitions are investigated with particular emphasis on the competition between electron itinerancy, electron-phonon interaction and electron-electron correlation. Recently observed distinct thermal behaviors of two typical MMX compounds Pt2(CH3CS2)4I and (NH4)4\[Pt2(P2O5H2)4I\]$``$2H2O are supported and further tuning of their electronic states is predicted.

PACS numbers: 71.10.Hf, 71.45Lr, 75.30.Fv, 65.50.$`+`$m

There is a class of quasi-one-dimensional materials containing chains of transition-metal (M) complexes bridged by halogens (X). Their representatives such as Wolffram’s red ($`\text{M}=\text{Pt},\text{X}=\text{Cl}`$) and Reihlen’s green ($`\text{M}=\text{Pt},\text{X}=\text{Br}`$) salts  are composed of mononuclear metal complexes and are thus referred to as MX chain compounds. These PtX chains generally exhibit a mixed-valence ground state with strong dimerization of the X sublattice. When Pt is replaced by Ni , a mono-valence regular-chain structure is instead stabilized, which is nothing but a tuning from the Peierls to Mott insulator. The electronic state of the MX chain system can such widely be tuned that the optical energy gap changes from $`0.8`$ to $`3.3`$ eV by varying the transition metals, the surrounding ligands, the bridging halogens and the counter ions . In recent years, further efforts have been devoted to bridging polynuclear metal complexes by halogens and physical as well as chemical interest in this system has been renewed. A new group, MMX, consists of two families, R4\[Pt2(pop)4X\]$``$$`n`$H2O ($`\text{X}=\text{Cl},\text{Br},\text{I}`$; $`\text{R}=\text{Li},\text{K},\text{Cs},\text{NH}_4`$; $`\text{pop}=\text{diphosphonate}=\text{H}_2\text{P}_2\text{O}_5^{\mathrm{\hspace{0.17em}2}}`$)  and M2(dta)4I ($`\text{M}=\text{Pt},\text{Ni}`$; $`\text{dta}=\text{dithioacetate}=\text{CH}_3\text{CS}_2^{}`$) , which are generically called the pop and dta complexes, respectively. The MMX chain system potentially provides not a few topics of qualitatively new aspect. The formal oxidation state of the metal ions is $`3+`$ in MX chains, whereas $`2.5+`$ in MMX chains. Therefore, MMX chains possess an unpaired electron per metal dimer even in their trapped-valence states, which is in contrast with the valence-trapped state consisting of M2+ and M4+ in MX chains. The M($`d_{z^2}`$)-M($`d_{z^2}`$) direct overlap in MMX chains effectively reduces the on-site Coulomb repulsion due to its $`d_\sigma ^{}`$ character and may therefore enhance the electrical conductivity. In the dta complexes with no counter ion, the chains weakly interact with each other through van der Waals contacts but are free from relatively strong hydrogen bonds, raising an increased possibility of the metal sublattice, as well as the halogen sublattice, being distorted. Nowadays, the chemical explorations along this line have reached a novel MMMMX chain compound HH-\[Pt(2.5+)4(NH3)8($`\mu `$-C4H6NO)4Cl\](ClO4)3Cl2 .

In response to recent stimulative observations for MMX chain compounds, we here study quantum and thermal phase competitions in one-dimensional unit-assembled spin-charge-lattice coupling systems. We employ the $`\frac{5}{6}`$-filled one-dimensional two-band three-orbital extended Peierls-Hubbard Hamiltonian:

$``$ $`=`$ $`{\displaystyle \underset{m,s}{}}{\displaystyle \underset{j=1,2}{}}\left(\epsilon _\mathrm{M}\beta l_{j:n}\right)n_{j:m,s}+{\displaystyle \underset{m,s}{}}\epsilon _\mathrm{X}n_{3:m,s}`$ (1)
$``$ $`{\displaystyle \underset{m,s}{}}{\displaystyle \underset{j=1,2}{}}\left(t_{\mathrm{MX}}\alpha l_{j:n}\right)\left(a_{j:n,s}^{}a_{3:n,s}+a_{3:n,s}^{}a_{j:n,s}\right)`$ (2)
$``$ $`{\displaystyle \underset{m,s}{}}t_{\mathrm{MM}}\left(a_{1:n,s}^{}a_{2:n1,s}+a_{2:n1,s}^{}a_{1:n,s}\right)`$ (3)
$`+`$ $`{\displaystyle \underset{m}{}}{\displaystyle \underset{j=1,2}{}}U_\mathrm{M}n_{j:m,+}n_{1:m,}+{\displaystyle \underset{m}{}}U_\mathrm{X}n_{3:n,+}n_{3:n,}`$ (4)
$`+`$ $`{\displaystyle \underset{m,s,s^{}}{}}{\displaystyle \underset{j=1,2}{}}V_{\mathrm{MX}}n_{j:m,s}n_{3:m,s^{}}`$ (5)
$`+`$ $`{\displaystyle \underset{m,s,s^{}}{}}V_{\mathrm{MM}}n_{1:m,s}n_{2:m1,s^{}}+{\displaystyle \underset{m}{}}{\displaystyle \underset{j=1,2}{}}{\displaystyle \frac{K}{2}}l_{j:m}^2,`$ (6)
where $`n_{j:m,s}=a_{j:m,s}^{}a_{j:m,s}`$ with $`a_{j:m,s}^{}`$ being the creation operator of an electron with spin $`s=\pm `$ (up and down) for the M $`d_{z^2}`$ ($`j=1,2`$) or X $`p_z`$ ($`j=3`$) orbital in the $`m`$th MXM unit, and $`l_{j:m}=(1)^j(u_{j:m}u_{3:m})`$ with $`u_{j:m}`$ being the chain-direction displacement of the metal ($`j=1,2`$) or halogen ($`j=3`$) in the $`m`$th MXM unit from its equilibrium position. $`\alpha `$ and $`\beta `$ are, respectively, the intersite and intrasite electron-lattice coupling constants, while $`K`$ is the metal-halogen spring constant. We assume, based on the thus-far reported experimental observations, that every M2 moiety is not deformed, namely, $`u_{1:n}=u_{2:n1}`$. $`\epsilon _\mathrm{M}`$ and $`\epsilon _\mathrm{X}`$ are the on-site energies of isolated metal and halogen atoms, respectively. The electron hoppings between these levels are modeled by $`t_{\mathrm{MM}}`$ and $`t_{\mathrm{MX}}`$, whereas the electron-electron Coulomb interactions by $`U_\mathrm{M}`$, $`U_\mathrm{X}`$, $`V_{\mathrm{MM}}`$ and $`V_{\mathrm{MX}}`$. Though different-site Coulomb interactions may in principle be coupled with lattice displacements in a two-band description, any alternation of them is usually neglected renormalizing $`\beta `$ under the mean-field treatment of $`_sn_{3:n,s}`$. We always set $`t_{\mathrm{MX}}`$ and $`K`$ both equal to unity.

Current empirical arguments on the electronic structures of MMX compounds are aiming to distinguish between four types of one-dimensional charge ordering mode , which are illustrated as (a) to (d) in Fig. 1, assuming that the X $`p_z`$ orbitals are stably filled and irrelevant. Quite recently, potential magnetic phases have also been pointed out ((e) to (h) in Fig. 1) and a systematic study of broken-symmetry solutions in the two-band scheme has been presented . The two-band description of all the phases is also given in Fig. 1. We learn that (c) and (g) should be characterized by charge and spin modulation on the X sublattice, respectively, rather than by any density wave on the M2 sublattice. The relevance of the X $`p_z`$ orbitals in these states has indeed been visualized numerically .

Most of the ground states of the pop-family MMX compounds have now been assigned to (d) , though early structural analyses  were rather controversial. However, due to the relatively small Peierls gaps in comparison with those of MX compounds, they can be tuned from the strongly valence-trapped state toward the paramagnetic or antiferromagnetic valence-delocalized state by replacing halogen and/or counter ions . Since the halogen character increases in the $`d_\sigma `$ Pt-Pt wave functions in the order $`\text{Cl}<\text{Br}<\text{I}`$, even further charge fluctuation toward (c)  may be observed in the iodo complexes. Such a reverse Peierls instability can be reinforced under external pressure . In general, the complete valence localization breaks down with increasing temperature . (NH4)4\[Pt2(pop)4I\]$``$$`2`$H2O clearly exhibits a thermal phase transition from (d) to (a) .

There has also been a controversy over the electronic structures of the dta-family compounds. Early investigations  reported similar semiconducting behaviors for both Pt and Ni complexes. However, later magnetic-susceptibility  and proton-spin relaxation-time  measurements claimed to distinguish Ni2(dta)4I from Pt2(dta)4I elucidating the distinct antiferromagnetic spin structure with strong exchange coupling for the former. Furthermore, recent extensive physical measurements  on Pt2(dta)4I have revealed its metallic conduction above room temperature as well as a totally different scenario for its valence structure: With decreasing temperature, there occurs a metal-semiconductor transition at room temperature, which can be regarded as the transition from the valence-delocalized state (a) to the trapped-valence state (b), and further transition to the Peierls-insulating charge-ordering mode (c) follows around $`80\text{K}`$.

We calculate the free energy for the broken-symmetry solutions (a) to (h) of the Hamiltonian (6) within the Hartree-Fock approximation. The lattice distortion is adiabatically treated and can therefore be described as a function of the electron density matrices. The numerical convergence of each solution is ensured and accelerated by the irreducible decomposition of the mean-field Hamiltonian . Surrounded with plenty of parameters, we observe the phase competition especially from the point of view of electron itinerancy, electron-phonon interaction and electron-electron correlation.

Figure 2(a) is a good interpretation of the observed thermal phase transitions. With increasing temperature, X-CDW is transformed into PM via BOW, whereas M-CDW directly into PM, each of which coincides with the thermal behaviors of the dta and pop complexes, respectively. The thermal stabilization of PM and BOW is convincing when we consider their electronic structures. In comparison with X-CDW and M-CDW with cell doubling, PM and BOW maintain the original lattice symmetry and therefore possess effectively half-filled conduction bands, which is visualized in Fig. 3. Since an energy gap crossing over the Fermi level is disadvantageous in gaining entropy via thermal excitations, PM and BOW may compete with X-CDW and M-CDW at finite temperatures. Figure 3 suggests that the conduction band for BOW is less dispersive than that for PM, which can justify BOW preceding PM in thermal stabilization. The quantum fluctuation between X-CDW and M-CDW is also convincing from the point of view of electron transfer. The orbital hybridization within every M2 moiety is essential in the strongly valence-trapped M-CDW state, while it is the overlap of the $`d_\sigma ^{}`$ orbitals on neighboring M2 moieties that stabilizes the relatively valence-delocalized X-CDW state. Therefore, M-CDW is more stabilized with increasing $`t_{\mathrm{MM}}`$. Based on semiempirical quantum-chemical band calculations, Borshch et al.  pointed out a possibility of twisting of the dta ligand reducing the electronic communication by $`\pi `$ delocalization between adjacent metal sites and ending in X-CDW with charge disproportionation in the M2 moiety. The transition from PM to BOW can also be understood as charge disproportionation within every M2 moiety with decreasing $`t_{\mathrm{MM}}`$. However, the contrast between the pop and dta complexes may not be attributable mainly to their transfer integrals. Early x-ray structural investigations  reported the Pt-Pt distance in the dimer to be $`2.813`$ Å and $`2.677`$ Å for K4\[Pt2(pop)4Cl\]$``$$`3`$H2O and Pt2(dta)4I, respectively. Even if we assume the general tendency $`t_{\text{Pt-Cl}}<t_{\text{Pt-Br}}<t_{\text{Pt-I}}`$, it is rather hard to conclude that $`t_{\mathrm{MM}}/t_{\mathrm{MX}}`$ for the dta complex is generally smaller than those for the pop complexes. The idea of larger M($`d_{z^2}`$)-M($`d_{z^2}`$) overlap of the dta complex can further be justified by its higher conductivity ($`13`$ $`\mathrm{\Omega }^1\text{cm}^1`$) compared with those of the pop-family iodo complexes ($`10^210^4`$ $`\mathrm{\Omega }^1\text{cm}^1`$).

Then, what is the leading factor of such a striking contrast between the pop and dta complexes? We seek it in their electron-lattice interactions. Figure 2(b) shows that M-CDW is stabilized with increasing $`\beta `$, whereas X-CDW with increasing $`\alpha `$. The orbital hybridization mainly stays within every M2 moiety for M-CDW, while it essentially extends over neighboring M2 moieties for X-CDW. Therefore, X-CDW is quite sensitive to $`\alpha `$ effectively describing the alternation of the MXM interdimer transfer. In comparison with $`\beta `$ which is a measure for the mobility of the X sublattice, $`\alpha `$ relatively describes the mobility of the M2 sublattice. The halogen ions are rather free in both pop and dta complexes and therefore $`\beta `$ may not characterize these materials well. On the other hand, $`\alpha `$ must distinguish Pt2(dta)4I from the pop-family compounds. The M2 moieties are tightly locked together in the pop complexes due to the hydrogen bonds between the ligands and the counter cations, whereas they are rather movable in the dta complex owing to its neutral chain structure. Thus, explicitly considering interdimer elastic constants as well, a significantly larger $`\alpha `$ is expected for Pt2(dta)4I. Now Fig. 2(b) allows us to attribute the distinct thermal behaviors of the pop and dta complexes mainly to their electron-phonon interactions. We never exclude out the effect of their transfer integrals as an underlying driving force. Phase transitions from this point of view may definitely be observed under external pressure . As the adjacent metals in the dimer are tightly locked to each other by the surrounding ligands, an applied pressure enhances $`t_{\mathrm{MX}}`$ rather than $`t_{\mathrm{MM}}`$.

In relation to replacing the metals and the halogens, it is also interesting to observe the phase competition as a function of the Coulomb interactions. Such a tuning of the electronic state is visualized in Figs. 2(c) and 2(d). Pt can be replaced by Ni in the dta complexes. Considering that the orbital energies of Ni and I are so close as to be possibly reversed ($`\epsilon _\mathrm{M}\epsilon _\mathrm{X}\mathrm{\Delta }\epsilon <0`$) in the crystal and the on-site $`d`$-$`d`$ Coulomb repulsion is considerably strong for Ni , Fig. 2(c) well supports the observations  for Ni2(dta)4I$``$no Peierls distortion and the Mott-insulating behavior exhibiting an antiferromagnetic spin susceptibility. On the other hand, as $`\mathrm{\Delta }\epsilon `$ increases, M-CDW begins to compete with X-CDW. This is quite convincing from the point of view of orbital hybridization. We have already learnt in Fig. 1 that X-CDW should be characterized by the charge density wave on the X sublattice. When we add up the charge densities on the adjacent metal sites in every M2 moiety, they shall no more modulate for X-CDW but still oscillate for M-CDW. Furthermore Fig. 3 shows that the largest gap opens between the two highest-lying bands primarily of $`d_\sigma ^{}`$ character for M-CDW, whereas between the two lowest-lying ones for X-CDW implying an essential hybridization of the M $`d_{z^2}`$ and X $`p_z`$ orbitals. We are thus convinced that M-CDW and X-CDW are stabilized and destabilized, respectively, with the increase of $`\mathrm{\Delta }\epsilon `$. Figure 2(c) is then an interpretation of the close Pt $`d_{z^2}`$ and I $`p_z`$ orbital energies. Finally we take a look at Fig. 2(d) raising a possibility of the novel antiferromagnetic state X-SDW appearing by the replacement of the halogens. $`U_\mathrm{X}`$ increases in close cooperation with the increase of $`\mathrm{\Delta }\epsilon `$ and therefore its stabilization is not so trivial in practice. A somewhat tricky situation $`V_{\mathrm{MM}}<V_{\mathrm{MX}}`$ advantageously acts on X-SDW . Otherwise we wonder whether a Pd chain chloride could be synthesized.

We hope that the present calculations will settle the controversial observations especially for Pt2(dta)4I  and contribute to a semiquantitative estimation of the essential parameters. In such circumstances that even the hopping amplitudes are not yet revealed, a close collaboration between experimental and theoretical investigations is really expected.

The author is grateful to Prof. K. Yonemitsu and Dr. K. Iwano for useful discussions. He thanks Prof. H. Okamoto and Prof. H. Kitagawa as well for helpful comments on MMX materials. This work was supported by the Japanese Ministry of Education, Science, and Culture. The numerical calculation was done using the facility of the Supercomputer Center, Institute for Solid State Physics, University of Tokyo.


text:
# BIOMOLECULES IN THE INTERSTELLAR MEDIUM AND IN COMETS

## INTRODUCTION

The birth sites of solar-mass stars and their planetary systems are dense interstellar clouds. Such clouds provide the building blocks, in the form of interstellar molecules and dust, for the formation of planets, comets, asteroids, and other macroscopic bodies in protostellar disks (Ehrenfreund & Charnley 2000; Irvine et al. 2000; Lunine et al. 2000). These clouds are the site of an extremely active and complex chemistry; to date over 100 molecules have been detected in them. Many of these molecules are also observed in protoplanetary disks and comets. A central question in the fields of astrochemistry and astrobiology is how much of the material present in primitive bodies, such as comets and asteroids, is pristine interstellar material? In other words, to what extent does the chemical inventory of these objects and the planets reflect chemical processing, firstly in the collapsing cloud, and subsequently in the protoplanetary disk (e.g. van Dishoeck & Blake 1998; Langer et al. 2000)?

Answering this question is of fundamental concern to two areas of research. Firstly, chemical abundances, together with isotopic and ortho-para ratios, are sensitive tracers of the molecule formation conditions and so differences between the chemical inventory of the interstellar medium (ISM) and the solar system can be used to constrain models of low-mass star formation, many aspects of which are not well understood. Secondly, the molecules in the early solar nebula provided the seed from which life eventually formed. It is thought that a great deal of organic material was deposited on the young Earth by cometary and asteroid impacts (Chyba et al. 1990). Many of the organic molecules detected in dense interstellar clouds have important functions in terrestrial biochemistry. The presence of extraterrestrial amino acids in meteorites (e.g. Cronin & Pizzarello 1983) shows that extremely complex molecules are able to form in space. In order to assess the implications for life elsewhere in the universe, we need to understand if such complexity is a general feature of interstellar and/or protoplanetary disk chemistry, or if these molecules arose due to specific conditions in our solar system. We can obtain clues to the above question by comparing observations of comets – thought to be the most pristine objects in our solar system – with those of protoplanetary disks, protostellar cores, and interstellar clouds (Ehrenfreund et al. 1997; Ehrenfreund 2000; Ehrenfreund & Charnley 2000; Bockelée-Morvan et al. 2000; Irvine et al. 2000).

## THE INTERSTELLAR-COMET CONNECTION

Table 1 compares the abundances of a number of molecules in a dark cloud, ices toward a protostar, a star-forming ‘hot molecular core’ where ices have recently evaporated, and a cometary coma. Whilst the analysis is complicated by factors such as the probable depletion of CO and CO2 in cometary ices (Yabushita 1995), and the fact that some of the molecules in hot cores and comets are likely to be daughter species formed via post-evaporation chemistry in the warm gas, it is clear that there are many fundamental similarities between the different regions. However, there are also a number of differences between cometary and interstellar abundances, which suggests that whilst solar system objects may consist of some purely interstellar material, other constituents have undergone significant processing. It is also apparent that there are substantial differences between molecular abundances in interstellar dark clouds and warm protostellar regions. This can be explained in terms of surface chemistry occurring as atoms and molecules freeze out onto dust grains in the cold cloud, followed by a complex gas-phase hot core chemistry which is initiated when the grain mantles are evaporated by the nearby protostar. A similar chemistry is thought to occur as material falls onto the disks surrounding low-mass stars, and the products will then refreeze and be incorporated into cometesimals and planetesimals (Lunine et al. 2000). Therefore, it is clear that in order to address the above question in a quantitative manner, we require a detailed understanding of the relevant chemical reactions and physical processing that interstellar material experiences as it suffers the violent passage from a cold dense cloud into a protoplanetary system.

## ORGANIC ASTROCHEMISTRY: OBSERVATIONS AND THEORY

### Interstellar Medium

Cold Dark Clouds

The two most intensively studied dark clouds are TMC-1 and L134N (see Table 1 of Ehrenfreund & Charnley 2000). Because of the low temperatures in these clouds, the chemistry is driven by exothermic ion-molecule reactions, initiated by cosmic ray ionization. In general, chemical models are able to give reasonable agreement with the observed abundances, although there remain problems with sulphuretted molecules and carbon-chain species (e.g. Millar et al. 1997). It is also possible that grain surface chemistry may contribute to the formation of molecules seen in dark clouds. Although these clouds are cold, a number of possible non-thermal desorption mechanisms have been proposed to return material from grains to the gas phase (e.g. Markwick et al. 2000); these proposals are motivated by the fact that in dense clouds one would expect heavy elements to be almost totally depleted from the gas on timescales much less than the estimated ages of the clouds (cf. Charnley et al. 2001a). The largest molecules observed in dark clouds are linear carbon chain molecules, such as C8H and HC11N (e.g. Bell et al. 1997, 1999). However, the decline in abundance with increasing chain length suggests that only a small fraction of interstellar carbon is locked up in longer chains. Nevertheless, it is likely that a significant fraction of the carbon is in the form of large aromatic molecules (see below). After atoms and molecules accrete onto grains to form ice mantles, it is likely that the resulting ices are subsequently processed by UV photons and/or energetic cosmic ray impacts. Laboratory experiments involving irradiation and radiolysis of interstellar ice analogs have demonstrated that relatively simple ices can be processed into much more complex molecules such as ethanol, formamide, carbonic acid, lactic acid, urea, and even larger molecules (Agarwal et al. 1985; Bernstein et al. 1995; Moore & Hudson 1998). Greenberg (1998) has proposed that over the lifetime of a molecular cloud a substantial fraction of the ice is converted into complex organic material, and that when planetary systems form this material is eventually incorporated into comets.

Hot Molecular Cores

The first hot molecular cores to be discovered were the Hot Core and Compact Ridge sources in Orion-KL, which are characterised by large abundances of small saturated molecules (e.g. NH3, H2O, CH3OH) in warm ($`T100`$ K), dense ($`n10^7`$ cm-3) gas, with anomalously high molecular D/H ratios for such high temperatures (e.g. Blake et al. 1987). Many other hot cores have since been identified and studied, and many molecules have been detected in them (see Table 1). The relation of many hot cores with ultracompact H ii regions confirms that they are associated with the earliest stages of high-mass star formation (Kurtz et al. 2000), and their composition is thought to result from the evaporation of interstellar ices by the newly-formed protostars (Brown et al. 1988).

In addition to water, ammonia and methanol, hot cores also contain lesser abundances of larger saturated species such as ethanol and ethyl cyanide, which are not detected in dark clouds. On the other hand, the long unsaturated chain species which are observed in dark clouds, such as the larger of the cyanopolyynes, are absent from hot cores. This is generally taken to be evidence for a limited surface chemistry occurring on interstellar grains. The prevalence of hydrogen in the ISM, and the much greater mobility of H atoms on the grain surface, ensures that hydrogenation is the principal reaction for surface molecules (Tielens & Hagen 1982); saturated alkanes and alcohols are the end result of H addition to the linear chain molecules observed in dark clouds (e.g. Charnley 1997a). After the evaporation of the initial ices, a rich gas phase chemistry can occur, and large abundances of new molecules can be formed (Charnley et al. 1992, 1995). Although broadly similar, the detailed chemical composition of the gas is seen to vary between different hot cores. For example, the Orion Hot Core appears to be enriched in N-bearing species, whereas the Compact Ridge has enhanced levels of O-bearing species (Blake et al. 1987); similar spatial differentiation is seen in a number of other sources (e.g. Nummelin et al. 2000). Charnley et al. (1992) showed that the N/O differentiation can be explained by differing ammonia/methanol ratios in the original ices, since many of the large O-bearing species are formed in the hot gas via reactions involving protonated methanol, and the presence of ammonia suppresses the CH3OH$`{}_{}{}^{+}{}_{2}{}^{}`$ abundance since NH3 acts as a sink for protons. Caselli et al. (1993) proposed a mechanism to account for the initial differentiation in the ices, but recent observations suggest that NH3 and CH3OH do in fact coexist in interstellar ices (Gibb et al. 2000). Rodgers & Charnley (2001a) showed that the N/O differentiation may actually be an age/temperature effect, since ‘cool’ ($`T100`$ K) cores will eventually lose their NH3 after $`10^5`$ yrs, whereas at higher temperatures endothermic reactions become rapid enough to ensure that the NH3 abundance never drops substantially, and hence large abundances of O-rich organics never evolve. Similar age/temperature effects may also be apparent in the sulphur chemistry, since the presumed parent molecule, H2S, is processed into HS, S, S2, SO, SO2, H2CS, and CS, the peak abundances of which depend on the core temperature (which controls the O i abundance) and age. Therefore, observed abundance differences in sulphuretted hot core molecules may be used to constrain the age of the cores, and place limits on the time-scale for this phase of the star formation process (Charnley 1997b)

Finally, an alternative explanation for the chemical variety amongst hot cores lies in the nature of the source which drives the mantle evaporation and the gas phase chemistry. All the models discussed above assume temporally constant temperatures and densities. This will be (roughly) appropriate for cores which are heated radiatively, but it is likely that many hot cores have experienced the passage of shock waves caused by the impact of protostellar outflows into the surrounding natal cloud material. In this case the postshock temperature can reach values higher than 1000 K (e.g. Draine & McKee 1993), this permits many reactions which are endothermic, or have activation energy barriers, to occur. For example, Charnley & Kaufman (2000) showed that the low abundances of CO2 observed in hot cores can be explained if these regions are heated by shocks. Shock waves can also erode the refractory grain cores and the release of silicon, observed to be highly depleted in cold clouds, is now understood to account for the presence of SiO in star-forming regions (Schilke et al. 1997). These considerations ensure that a thorough understanding of hot core chemistry requires detailed chemical modelling, since only when all possible gas phase production routes have been investigated and ruled out, is it possible to infer that a particular molecule is a parent in the original ice. Through this type of modelling, we can gradually build up a secure inventory of interstellar ices (cf. Ehrenfreund & Charnley 2000). Comparison of inferred ice composition with that observed by the ISO satellite will allow us to determine the processing that the ices undergo as they are irradiated and evaporated by nearby protostars.

### Comets

The modern view of comets began with the work of Whipple (1950), who proposed the ‘icy conglomerate’, or ‘dirty snowball’ model of comet nuclei. Over the years this model has been refined, particularly after the discovery in comet Halley of large, so-called ‘CHON’, organic particles (Kissel et al. 1986), and comets are now known to consist of roughly equal parts by mass of ice (mainly water, with $`10\%`$ CO and CO2), inorganic refractories (mainly silicates), and organic refractories (CHON particles and other carbonaceous material) (Greenberg 1998). The ices also contain trace amounts of other molecules at the $`1\%`$ level or less (Table 1) – although only a minor constituent of the comet as a whole, these species are very important, since they can be used to trace the conditions under which comets were formed. The recent detection of Argon in comet Hale-Bopp (Stern et al. 2000) is proof that this comet has undergone very little thermal processing since its formation, as Ar sublimates at $`T35`$ K.

Based on their orbital characteristics it is possible to divide comets into two distinct populations: long- and short-period comets. A more strict classification is based on the Tisserand invariant, T; comets with $`\mathrm{T}>2`$ (short-period comets) are thought to originate from the Kuiper belt (located at a heliocentric distance $`30<r_h<50`$ AU), whereas long-period comets come from the Oort cloud ($`r_h5\times 10^4`$ AU). The current consensus is that Kuiper belt comets most probably formed near their current location, whereas Oort cloud comets were formed somewhere in the giant planet region of the protosolar nebula ($`5<r_h<30`$ AU), before being ejected to their present position via gravitational interaction with these planets (Weissman 1999). If this picture is correct, one would expect to see chemical differences between the two populations. This indeed seems to be the case for carbon chains; A’Hearn et al. (1995) showed that short-period comets are much more likely to be depleted in C2 and C3 than long-period comets. More recently, Mumma et al. (2000) observed ethane in the short period comet Giacobini-Zinner, and showed that it too is depleted relative to the long-period comet Hale-Bopp.

Our detailed knowledge of the molecular inventory of comets has been revolutionised in the past few years by the apparitions of the bright comets Hyakutake and Hale-Bopp; many of the molecules listed in Table 1 were observed for the first time in Hale-Bopp (Bockelée-Morvan et al. 2000). The use of interferometers allowed the first detailed maps to be made of the distributions of molecules in the coma (e.g. Blake et al. 1999; Kuan et al. 2001a). Mapping of ions such as HCO+ also allowed the structure of the cometary ionosphere to be determined (e.g. Lovell et al. 1997), and showed that ion-molecule chemistry may be important in the coma since, for example, HCO+ is formed from proton transfer to CO. The results of this mapping showed that, in addition to a nuclear source, some molecules also appeared to have an extended source in the coma. Although this was previously known to be the case for formaldehyde in comet Halley (Meier et al. 1993), it is now known that CO, OCS, HCN, and HNC also had extended sources in Hale-Bopp. Various theories exist to explain these distributions; it may be that these molecules are formed via photodissociation of some unknown parent, or they may be sublimating directly from icy grains in the coma. Alternatively, as in hot cores, these species and many others could possibly have been produced via post-sublimation gas-phase chemistry occurring in the coma.

In order to quantitatively assess the potential for chemical reactions to alter the composition of the coma, we have developed a model of the chemistry and physics in the coma (Rodgers & Charnley 2001d). Despite the differences in the physical parameters and the molecular lifetimes, the chemistry taking place in the coma is analogous in many ways to that which occurs in hot cores. However, because the physical conditions change throughout the coma, it is necessary to calculate the hydrodynamics in tandem with the chemistry and this ensures that the development of realistic coma models is a far more demanding task. Briefly, the model simultaneously solves the conservation equations for abundances, mass, momentum and energy appropriate for a steady spherical outflow. Endoergic chemical reactions driven by suprathermal H atoms are included, along with all the important microphysical processes that determine the heating and cooling in the coma. As described below, we have used this model to investigate possible production routes for HNC and complex organics, as well as the potential of gas-phase chemistry to alter D/H ratios in the coma (Rodgers & Charnley 1998, 2001b,c,d).

## COMPLEX ORGANICS

### Interstellar Medium

It has become clear in recent years that the ISM contains a large population of polycyclic aromatic hydrocarbon (PAH) molecules (e.g. Léger & Puget 1984; Allamandola et al. 1985), with a typical size of $``$20–100 C atoms. PAHs are thought to account for $``$10% of the interstellar carbon budget, and are most likely formed in the outflows of evolved stars (Frenklach & Feigelson 1989). However, it has not yet proved possible to definitively identify specific PAH molecules. The largest positively-identified molecule thus far detected in the ISM is HC11N (Bell et al. 1997). Yet, despite containing 13 atoms, structurally this is a simple linear chain molecule. In terms of structure the most complex interstellar molecules are seen in hot cores, where molecules such as ethanol, dimethyl ether, ethylene oxide, methyl formate, acetic acid, and glycolaldehyde have been detected. The latter three molecules are isomers of each other, as are ethanol and dimethyl ether. It is clear that any comprehensive theory of interstellar chemistry should be able to explain the prevalence of some isomers over others. In the previous section we discussed how the molecular abundances in hot cores are determined by two different chemical processes; surface chemistry in the cold gas prior to the formation of the hot core, and hot post-evaporation gas phase chemistry. Here we briefly describe a unified scheme to explain the observed molecular complexity in these regions (cf. Charnley 1997a, 2001; Charnley et al. 2001b).

Unconstrained grain surface reactions can potentially produce many molecules (e.g. Caselli et al. 1993), however, such models cannot account for the specific abundances seen in hot cores. We therefore limit the surface chemistry to consist of atomic addition reactions (one atom at a time), with the further constraint of radical stability imposed on the intermediate organic radicals. This results in surface production of alcohols and amines, although the existence of energy barriers for H addition to double and triple bonds may mean not all molecules are fully reduced, resulting in some aldehydes, ketones, and nitriles. This scheme naturally accounts for the methanol, formaldehyde, ethanol, ketene, acetaldehyde, vinyl cyanide, and ethyl cyanide seen in hot cores (Charnley 1997a). It can also explain the existence of the ring molecule ethylene oxide (c-C2H4O) via O atom addition to the C2H3 radical, which is formed when H atoms react with acetylene. If instead of an O atom an N atom is added to $`\mathrm{C}_2\mathrm{H}_3`$, either methyl cyanide or vinylimine can result; however a ring structure is also possible and this results in the azirines 1-H azirine ( H($`c`$–C$`=`$N–C)H2 ) and 2-H azirine ( H($`c`$-C$`=`$C–NH)H ). Complete reduction via addition of two further H atoms will result in aziridine ( H2(C–NH–C)H2 ). We therefore searched for these molecules in several hot cores with the NRAO 12m telescope (Kuan et al. 2001b; Charnley et al. 2001b). Figures. 1 and 2 show tentative detections of the azaheterocycles 2-H azirine and aziridine in Orion-KL, Sgr B2(N) and W51.

Whilst surface chemistry can account for the molecules discussed above, there are other molecules observed in hot cores that cannot be explained by this mechanism, such as dimethyl ether and methyl formate. Such molecules must therefore be formed in the warm gas; a plausible mechanism is alkyl cation transfer reactions, whereby a protonated alcohol transfers an alkyl group to a neutral base i.e.

$$\mathrm{ROH}_2^++\mathrm{R}^{}\mathrm{X}\mathrm{R}^{}\mathrm{XR}+\mathrm{H}_2\mathrm{O}$$

Many of these reactions have been measured in the laboratory and found to be rapid (e.g. Mautner & Karpas 1986), and methanol and ethanol are known to be abundant in hot cores. Thus, dimethyl ether can be formed via self-methylation of methanol, and methyl formate may arise from reactions of CH3OH$`{}_{}{}^{+}{}_{2}{}^{}`$ with H2CO or HCOOH (Charnley et al. 1995, 2001b). Transfer of methyl groups to other common hot core species can produce many other large molecules, e.g. CH3NCO, (CH3)2CO, NH2COCH3, CH3OC2H5, isocyanides and large amides (Ehrenfreund & Charnley 2000; Charnley & Rodgers, in preparation). Another predicted product is diethyl ether, which was tentatively detected by Kuan et al. (1999).

Finally, it is possible that the type of reactions we have discussed may lead to glycine, the simplest amino acid. The surface chemistry scheme we described can lead to aminomethanol, via hydrogenation of HNCO. Alternatively, aminomethanol is thought to be formed when ices containing H2O, NH3, and H2CO are heated (Woon 1999). In either case, one would expect significant abundances of aminomethanol to be evaporated into hot cores, and subsequent protonation followed by reaction with HCOOH may form glycine (Charnley 1997a). Despite many searches over the years, glycine has yet to be detected in the ISM, but recent tentative identification of several lines suggest that it may soon be conclusively identified (Charnley et al. 2001b).

### Comets

The brightness of comet Hale-Bopp means that it is the only comet in which many large organic molecules have been positively detected. The largest molecule observed in Hale-Bopp is methyl formate (HCOOCH3) (Bockelée-Morvan et al. 2000), and Kuan et al. (2001a) reported a tentative detection of its structural isomer acetic acid (CH3COOH). As discussed above, these molecules are also seen in hot cores where they are thought to be daughter species. Thus, it is possible that the HCOOCH3 (and CH3COOH) seen in Hale-Bopp were actually created in the coma. In order to investigate this possibility, we used our comet model to follow the organic chemistry which occurs in the coma following the sublimation of methanol rich ices from the nucleus (Rodgers & Charnley 2001b). We find that chemical reactions cannot form sufficient quantities of HCOOCH3 and other organic molecules detected in Hale-Bopp: HCOOH, HC3N and CH3CN. Therefore, these species must be present in the nuclear ice. Hence it appears that cometary ices are more processed than their interstellar counterparts, which is consistent with primordial interstellar ices being evaporated, perhaps within the protosolar nebula, undergoing a hot core-like phase of chemical processing, then refreezing onto pre-cometary grains. However, we cannot be absolutely certain that these large organics are daughter molecules in hot cores, and they may also be present in interstellar ices. One way to determine the origin of these molecules may be to use D/H and 13C/12C ratios (Rodgers & Millar 1996; Rodgers & Charnley 2001e; Charnley et al. 2001c).

Photo-fragmentation of cometary CHON particles, first detected by the Giotto probe in the coma of comet Halley, has been proposed to account for the extended sources seen for many molecules and radicals in the coma, in particular CO, C2, H2CO, CN and NH2. Specifically, to account for the coma sources of CO and H2CO, and also the regular peaks in the mass spectra of CHON particles seen by Giotto, it has been proposed that a substantial fraction of the CHON material consists of the formaldehyde polymer, polyoxymethylene (POM, \[–CH2–O–\]n) (e.g. Huebner 1987). Other potential candidates include hexamethylenetetramine (HMT, C6H12N4; Bernstein et al. 1995), polyaminocynaomethylene (PACM, \[–(NH2)C(CN)–\]n; Rettig et al. 1992), and PAHs (specifically phenanthrene, C14H10; Moreels et al. 1994). It is likely that a mixture of many types of organic particles are actually present in comets, but we may be able to constrain the amounts of the different types if we can model the predicted production rates for daughter molecules, and compare them with the observations.

## THE HNC/HCN RATIO

### Interstellar Medium

The HNC/HCN ratio varies a great deal in the ISM, with an inverse temperature dependence: in cold dark clouds the ratio is typically $`>1`$, whereas in hot cores it is low. This was previously thought to be caused by three factors; i) low temperature ion-molecule reactions preferentially forming HNC via the H2NC+ ion, ii) proton transfer reactions cycling between the two isomers via the HCNH+ ion, and iii) high temperature isomerization reactions transforming HNC into HCN. However, recent quantum chemical calculations have showed that assumptions (i) and (iii) are incorrect (e.g. Talbi et al. 1996).

In hot cores, HCN and HNC are thought to be daughter species, since HCN is produced efficiently from reactions of NH3 and C+; at high temperatures ($`>250`$K) the reaction of CN with H2 ensures that the net destruction rate of HCN is extremely small (Rodgers & Charnley 2001a). Proton transfer to HCN to form HCNH+ followed by recombination or proton transfer to ammonia forms HNC, and models predict HNC/HCN ratios of $`0.007`$–0.05 for a 300 K core, depending on the age and the initial NH3 abundance. This is in reasonable agreement with the observed value in these regions, but we are still unable to explain the excess of HNC in cold clouds.

### Comets

HCN has been seen in many comets, but HNC was detected for the first time in comet Hyakutake, where it was present with an abundance relative to HCN of 6% (Irvine et al. 1996). HNC was subsequently detected in comets Hale-Bopp and Lee, and the HNC/HCN ratio in Hale-Bopp showed a strong increase as the comet approached perihelion, from $`<0.02`$ at 2.5 AU to $`0.16`$ at 1 AU (Irvine et al. 1998). The Hyakutake results were originally interpreted as proof that cometary ices contain unprocessed material from the ISM, but the observations of Hale-Bopp proved conclusively that HNC must be a daughter species, and that its production is related to the solar photon flux and/or coma temperature.

We have used our comet model to investigate possible chemical production routes to HNC in the coma (Rodgers & Charnley 1998, 2001c). We find that ion-molecule chemistry is unable to synthesise the observed quantities of HNC, but that endothermic isomerisation reactions of HCN, driven by suprathermal H atoms produced in the photodissociation of parent molecules, may be efficient in large, active comets such as Hale-Bopp. However, in comets Hyakutake and Lee we demonstrated that HNC must be produced via the photodestruction of some unknown parent. Possible molecular candidates are HNCO and CH2NH, but the former is thought to be photodissociated into NH $`+`$ CO and/or H $`+`$ OCN, whereas the latter is not observed in comets. Hence, we consider it most likely that HNC is coming from CHON particles in the coma, and conclude that the most likely candidate is PACM (cf. Rettig et al. 1992). This source of HNC may also account for the extended sources of HCN and CN in the coma.

## CARBON CHAINS

### Interstellar Medium

Carbon chain molecules appear to be almost equally abundant in both the diffuse ISM and dense clouds (Allamandola et al. 1999), and it has been proposed that C-chain anions may be responsible for some of the diffuse interstellar bands (Tulej et al. 1998). The overall abundance of long C-chains ($`>10`$ C atoms) in diffuse clouds is $`10^{10}`$ with respect to hydrogen, and they are thought to account for a few parts per million of the total cosmic carbon. In comparison, $`10\%`$ of the total cosmic carbon is in PAHs (see above). Carbon chains are thought to be formed via neutral-neutral C-insertion reactions involving CN and C2H radicals (Fukuzawa et al. 1998).

The overall abundances of chain molecules are derived from infrared observations of C$`=`$C vibrational transitions; in order to identify specific molecules one must look at rotational transitions at millimeter wavelengths. The largest molecule identified to date is HC11N which was seen in the dark cloud TMC-1 (Bell et al. 1997). The abundances decrease with increasing chain length, and this detection is at the limit of current telescope capabilities, making the detection of longer chains difficult in the near-term. However, in recent years the spectra of a large number of chain molecules have been accurately characterised in the laboratory (e.g. McCarthy et al. 2000), and so future observations may be able to distinguish the precise molecular nature of the smaller chains ($`10`$ C atoms).

### Comets

Although there is no direct evidence for carbon chains in comets, the presence of the C2 and C3 radicals suggests that they are fairly abundant. The longest chain molecule positively detected in a comet is HC3N, which is a parent species in Hale-Bopp (Rodgers & Charnley 2001b). This suggests that longer cyanopolyynes may also be present in the nucleus, albeit in lower abundances. It is interesting that C2 and C3 are observed to be depleted in some Kuiper belt comets (A’Hearn et al. 1995), implying that C-chain molecules are more abundant in Oort cloud comets. This can be explained if these chains were formed more efficiently in the warmer, giant planet region of the protosolar nebula than the Kuiper Belt region. Alternatively, chain molecules may form readily in both regions, but undergo further processing in the outer region, perhaps involving saturation or the formation of ring molecules and fullerenes. We previously discussed the probable contribution of polymeric material to the CHON particles in comets (e.g. Huebner 1987; Rettig et al. 1992). However, this material cannot be unequivocally identified via spectroscopy of the coma, and we must wait until the Stardust mission returns a sample of comet dust the the Earth for laboratory analysis before we can properly understand the nature of the CHON grains.

## DEUTERIUM FRACTIONATION

### Interstellar Medium

The overall D/H ratio in our galaxy is $`1.6\times 10^5`$, but the D/H ratios in some molecules can be up to 104 times larger, since at low temperatures small zero-point energy differences result in the fractionation of ions such as H2D+, C2HD+, and CH2D+. Ion-molecule chemistry spreads the D-enrichment to a variety of molecules, and the observed D/H ratios can be used to constrain the gas temperature, the electron fraction, and the depletion of heavy elements (e.g. Millar et al. 2000). In addition, spatial variations in D/H ratios may allow the propagation of Alfvén waves to be traced in molecular clouds (Charnley 1998). The D/H ratios observed in interstellar molecules can also be used to probe the chemical mechanisms which form those molecules. Rodgers & Millar (1996) showed that D/H ratios in hot cores trace the values in the precursor ice, and Charnley et al. (1997) used this fact to show that the hot core abundances of the two isotopomers of deuterated methanol – CH2DOH and CH3OD – should always have a ratio of 3:1 if methanol is formed on grains via hydrogenation of CO. Rodgers & Charnley (2001e) considered NH3 production in dense cores, and showed that although the total fractionation of ammonia may vary from source to source, for a specific chemical production mechanism the ratio of the multiply deuterated isotopomers should be constant, and may be used to distinguish between gas phase and surface production of ammonia.

### Comets

To date, the only deuterated molecules observed in comets are HDO and DCN. HDO was detected in Halley, Hyakutake, and Hale-Bopp, and the observed HDO/H2O ratios lie in the range 5.7–6.6$`\times 10^4`$ (e.g. Meier et al. 1998a). DCN was seen only in Hale-Bopp, where a DCN/HCN ratio of 0.002 was determined (Meier et al. 1998b), although Blake et al. (1998) showed that the DCN/HCN ratio was a factor of ten larger in the dust jets. We have used our comet model to follow the deuterium chemistry which occurs in the coma and find that, as in hot cores, post-evaporation chemistry does not significantly alter the initial D/H ratios (Rodgers & Charnley 2001d). Therefore, for parent species we can use the observed coma ratios to infer the nuclear D/H ratio, and for daughter species we can use these ratios to constrain the nature of the parent and the chemical mechanism by which the species are formed. In particular, if the DNC/HNC ratio can be determined in a comet, we may be able to ascertain the origin of cometary HNC, which is currently not well understood (see above).

Comparison of cometary D/H ratios with interstellar values may be used to determine the physical conditions in the protosolar nebula, since it is likely that the original interstellar values were altered by chemical processing and/or mixing in the nebula (Aikawa & Herbst 1999; Mousis et al. 2000). The observed D/H ratios in comets are similar to the values in hot cores, but since HCN could possibly be a daughter species in hot cores, this leaves only one molecule, HDO, for which comparisons are currently possible. Future observations of other deuterated cometary molecules are therefore vital. An exciting recent development is the first tentative detection of HDCO in a comet, Hale-Bopp (Kuan et al. 2001a). A determination of the HDCO/H2CO ratio, when combined with the known D/H ratios in water and hydrogen cyanide, will further constrain models of cometary origin. It is also useful to compare cometary D-enrichment with that seen in the Earth’s oceans – it appears that comets have twice as much deuterium as the Earth, which casts doubt on the assertion that comets brought the bulk of the volatiles to the Earth. On the other hand, Delsemme (2000) has argued that the Earth’s water was deposited mainly by deuterium-poor comets formed in the inner region of the protosolar nebula; such comets should account for $`4`$% of the Oort cloud’s population.

### CARBON AND NITROGEN FRACTIONATION

### Interstellar Medium

Heavy isotopes of carbon and nitrogen, 13C and 15N, are formed in low- to intermediate-mass stars, and so their abundances relative to 12C and 14N increase toward the galactic center (e.g. Boogert et al. 2000). Langer et al. (1984) modelled the fractionation in 13C occurring in interstellar molecules, and concluded that it is preferentially locked up in CO, and hence depleted in species such as C+, H2CO, CS, CH, and HCN. Terzieva & Herbst (2000) modelled the fractionation occurring in 15N, and concluded that in typical dark clouds the resulting fractionation is negligible. However, there is growing evidence for the presence of ‘depletion cores’ in some clouds, where most of the molecules have frozen out onto grains, but some N2 remains in the gas phase (e.g. Charnley 1997c; Caselli & Walmsley 1999; Bergin et al. 2001). In this case, only simple N-bearing molecules are present in the gas, and significant fractionation can occur (Charnley & Rodgers 2001).

### Comets

No significant fractionation is seen in cometary dust (Jessberger 1999), except for some grains which are strongly depleted in 13C, which are thought to be unprocessed presolar grains formed in the outflows of massive stars. In cometary volatiles, the 12C/13C ratios have been determined from observations of C2, CN, and HCN in a number of comets (Wyckoff et al. 2000), and are found to lie in the range 85–93, consistent with the terrestrial value of 90. The cometary 14N/15N ratio has been measured in CN and HCN (Crovisier & Bockelée-Morvan 1999), and is found to equal 323, slightly larger than the terrestrial value of 272. However, the 15N/14N ratio is seen to vary amongst different solar system objects, and the initial protosolar value is uncertain (e.g. Kallenbach et al. 1998). Large 15N enhancements are seen in some meteoritic and interplanetary dust particle material (Messenger & Walker 1997), and the measurement of a large $`{}_{}{}^{15}\mathrm{NH}_{3}^{}/^{14}\mathrm{NH}_3`$ ratio in a comet would provide positive evidence for the interstellar fractionation scenario proposed by Charnley & Rodgers (2001).

## SULPHURETTED MOLECULES

### Interstellar Medium

The sulphur chemistry in cold clouds is not fully understood. Gas phase sulphur appears to be depleted in dark clouds by a factor of 100-1000 relative to its cosmic abundance, whereas it is undepleted in the diffuse ISM (e.g. Ruffle et al. 1999). It is clear that somehow sulphur must become preferentially incorporated into refractory material as compared with C, N and O. The only solid phase sulphuretted molecule detected to date is carbonyl sulphide (OCS) which has an abundance relative to H2O of 0.04–0.1% (Palumbo et al. 1997). In hot cores, a wide variety of S-bearing molecules are observed. Charnley (1997b) modelled the sulphur chemistry occurring after the evaporation of H2S, and showed that all the observed sulphuretted species except OCS can be formed in the hot gas from this one parent molecule. The predicted abundances of different S-bearing daughter molecules depend on the core age and temperature, which means that observations of species such as SO and SO2 may be used as ‘chemical clocks’ to determine the ages of the cores (e.g. Hatchell et al. 1998).

### Comets

To date, eight S-bearing molecules have been detected in comets, four of them solely in Hale-Bopp (Crovisier & Bockelée-Morvan 1999). Many of these are also observed in hot cores, so it is possible that sulphuretted cometary molecules are formed in the coma from reactions of H2S. We have previously discussed the fact that the organic molecules seen in Hale-Bopp cannot have been formed via coma chemistry, which appears to suggest that the S-bearing molecules in Hale-Bopp must also have been present in the nucleus. However, hot core organic chemistry is driven by ion-molecule reactions, whereas the sulphur chemistry is initiated by the reaction of H2S and H to form SH, which has a barrier of $`860`$ K. The large abundances of suprathermal H atoms in the inner coma may therefore be instrumental in rapidly converting H2S into other molecules (cf. Rodgers & Charnley 1998).

## CONCLUSIONS

In this article we have presented a review of our current understanding of the organic chemistry that can occur in dense molecular clouds and in comets. By comparing the respective molecular inventories of interstellar and cometary environments we can begin to elucidate the degree of alteration of the interstellar material as it becomes incorporated into protostellar nebulae. In the next decade, astronomical observations of distant star-forming regions, combined with analyses of meteoritic and cometary samples, should allow the relative degree of pristinity of cometary material to be determined. Space-based telescopes of relevance to interstellar and cometary chemistry include SIRTF, FIRST-Herschel, NGST, and SOFIA. Although cometary H2O can be detected from the ground through radiatively pumped ‘hot-band’ lines (Dello Russo et al. 2000), space-based observatories are essential to overcome the telluric extinction affecting most water lines. SWAS has observed H2O in comets Lee and McNaught-Hartley (Neufeld et al. 2000), and FIRST-Herschel should allow the determination of HDO/H2O in a large sample of comets, including both short and long period comets. The Stardust mission, although still some years from its encounter with comet P/Wild 2, has already detected interstellar dust particles. Preliminary results indicate that these particles are very similar to the complex organics seen in comet P/Halley, providing further evidence for a link between interstellar and cometary materials; such particles are understood to be destroyed in cometary comae to provide the observed ‘extended sources’ of molecules (e.g. Huebner 1987; Meier et al. 1993). Finally, the Rosetta mission will be launched in 2003 and is due to rendezvous with comet P/Wirtanen in 2011. The Rosetta lander module will allow the first in situ examination of the nature of a cometary nucleus, including the determination of the elemental, molecular and isotopic composition of the surface and subsurface layers. Assimilation and interpretation of the data returned by each of these missions will represent a significant advance in the quest for a detailed understanding of the connection between interstellar and cometary organic material.

## ACKNOWLEDGMENTS

Theoretical astrochemistry at NASA Ames is supported by NASA’s Origins of Solar Systems and Exobiology Programs through NASA Ames Interchange NCC2-1162. SDR is supported by a National Research Council postdoctoral research associateship. The research of YJK was supported by grants NSC 88-2112-M-003-013 and NSC 89-2112-M-003-004. NRAO is operated by the Associated Universities, Inc., in cooperative agreement with the National Science Foundation.