text:
# Fundamental building blocks of eumelanins: electronic properties of indolequinone-dimers.

## 1 Introduction

Melanin is a photoactive biopolymer , a common biological pigment responsible for much of coloration observed in nature. Despite its ubiquity, documented photoprotective  character, reported photosensitizing activity  and otherwise hypothesized multifunctionality of the pigment in animals and humans , neither the size nor the structure of the fundamental molecular unit of the melanins has been well understood yet. Black eumelanins are composed of indolic units derived from the oxidation of tyrosine: among those 5,6-dihydroxyindole (DHI or HQ) together with their oxidized forms (indole-5,6-quinone (IQ)) and semiquinone (SQ) and 5,6-dihydroxyindole-2-carboxylic acid (DHICA) are usually accepted  as main components of natural eumelanins and their synthetic analogues.
Photoreactivity, ability to bind transition metal ions, redox properties and presence of persistent free radical centers in the pigment structure are usually mentioned as main features of eumelanins , although their biological significance is still unclear.
X-ray diffraction measurements of dried synthetic pigments have led to a model that pictures eumelanin  as a $`\pi `$ \- stack of crosslinked planar oligomeric structures with a spacing of $`3.4`$Å. Such a $`\pi `$-conjugated, randomly arranged heteropolymer system could be responsible for intrinsic semiconductivity of eumelanins .
The eumelanins’ monomers, as well as their dimers and polymers have been subject to theoretical studies in the framework of Hückel theory  that have supported the hypothesis of eumelanins as semiconductors. A further investigation along those lines has been performed for the charged monomers  where the stability of charged HQ, SQ and IQ was investigated. Following that study all monomers have been concluded to be strong electron acceptors (in the decreasing order from SQ to IQ to HQ). Elucidation of the spectral properties of synthetic eumelanins has been also addressed  pointing out consequences of the assumed random organisation of the polymer that explains well experimental absorption spectra of synthetic eumelanins.
The aim of the present study is to examine electronic properties: orbital- and charge- localization of stacked eumelanins’ monomers forming an "indolic sandwich" with a characteristic separation distance of about $`3`$Å. Two parallel, mostly planar monomers (Figure 1) laying one above the other are chosen as a main unit for modelling.

A few assemblies in which one of the monomers has been rotated or moved apart have been also examined checking for the effect of conformational variations on formation of a stable dimeric unit.
Natural eumelanins are built of both DHI and DHICA  monomers but it is possible to prepare synthetic material as pure DHI– or DHICA–melanin . In this respect, the article focuses on a distinct class of synthetic eumelanins discussing properties of simple DHIs aggregates only.

## 2 Methods

Since experimental data on the geometry of the monomers are not available, the model structures have been created in the InsightII/MSI module  and geometrically optimized by use of the consistent valence forcefield (CVFF)  until the demanded covergence in energy has been achieved (the maximum derivative less than 0.0001 kcal mol-1 Å-1). Coordinates of such monomers have been used as input data for semiempirical INDO calculations . Ground electronic states of the neutral charged molecules, as well as of the negatively charged molecules from wich one H+ ion was removed (the number of electrons remains the same), have been obtained as closed-shell molecular orbital wave functions in the Hartree-Fock (RHF) framework. For molecules with an extra electron or without one elctron Unrestricted Hartree-Fock (UHF) method has been used.
For molecules without hydrogen ion the first excited states were calculated by configuration interactions (CI) among configurations generated as single excitations from RHF ground state. The CI method included the highest 10(20) occupied and lowest 10(20) unoccupied molecular orbitals for the monomers(dimers). 111Our test calculations have revealed that expansion of the CI basis to more than 20 highest occupied nad 20 lowest unoccupied orbitals does not change significantly neither the values of estimated excitation energies nor the main contributions $`c_{ik}`$ to the molecular orbitals of the dimer. At the first step, the calculations have been performed for each monomer (HQ, IQ and SQ) and then for the aggregates built of two stacked monomers (HH, II, SS, SH, HI, IS). For simplicity, we adopt here a notation where HH, II, SH, etc. stand for dimers of HQ-HQ, IQ-IQ and SQ-HQ, respectively. The distance between molecules has been controlled within the range 2.86-4.12Å by a translation (a shift in the $`z`$-coordinate) of all atoms forming a displaced monomer in the pair. In order to test whether the mirror symmetry of dimer coordinates in HH, II and SS assemblies does not generate special results in the INDO runs, model HQ-HQ aggregates were built in which one monomer has been optimized with the CVFF and the second with a slightly different version of the consistent valence forcefiled  intended for application to polymers and organic materials (PCFF). Such a procedure breaks the symmetry of the aggregate producing nevertheless fully agreeable INDO results for both HQpcff-HQcfvv and HQcfvv-HQcfvv sets of data. To check for localization of the HOMO and LUMO orbitals a simple routine has been undertaken: In the LCAO framework each molecular orbital ($`\psi _i`$) is composed as a linear combination of atomic orbitals ($`\varphi _k`$) $`\psi _i=_kc_{ik}\varphi _k`$. The ratio of the sum of squared coefficients $`c_{ik}^2`$ over atomic orbitals of one of the monomers to the relevant sum for all atoms in a dimer has been assumed to be a measure of the localization of the $`ith`$ molecular orbital:

$$\text{orbital localization}=\frac{_{\text{one monomer}}c_{ik}^2}{_{\text{both monomers}}c_{ik}^2}.$$
(1)
Based on the density matrix, all charges and their distributions have been calculated according to the Mulliken population analysis.

## 3 Results

### 3.1 Neutral dimers

In the absence of any extra charge both monomers remain neutral for all distances reported in this study. The biggest value for charge separation has been observed for SQ-HQ set at the distance222Intermolecular distances have been defined as distances between the mean planes located on all atoms of the separated monomers. 2.86 Å (charge 0.26 and -0.26 respectively). The degree of orbital localization as defined above is displayed in Figuress 2 and 3.

The results of the analysis are displayed as HOMO (LUMO) localization for HQ monomer in the sets of HS, IH dimers and as HOMO (LUMO) localization for SQ monomer in the IS dimers, respectively. By inspection of Figure 2 one can deduce that in the case of symmetrical assemblies HOMO is delocalized even at relatively large separations of monomers. This tendency remains also unchanged for HQcvff-HQpcff sets, for which the spatial symmetry of coordinates is broken. At extremal intermolecular distances ($``$ 10 Å) the HOMO orbital becomes localized on one of the monomers that has been examined for both HQcvff-HQpcff and HQcvff-HQcvff dimers sets. However, the delocalization decreases faster with encreasing distance when the mixed sets of dimers (SH, HI, IS) are analyzed. Distances of about 3.28-3.7Å seem to be "transition distances": If the monomers are closer to each other, they behave as supermolecule, if they are farther apart, they become two separated molecules.
Additional examination provides further arguments that at large distances ($`4`$Å), the supermolecular structure of dimers breaks down and monomers behave as two weakly interacting molecules. By analyzing the five largest coefficients $`c_{ik}`$ and the energy of the relevant orbitals we have found that at the distance 4.12 Å HOMO-1/HOMO/LUMO/LUMO+1 aggregates’ orbitals are created of HOMO/LUMO relevant monomers’ orbitals. (see Tab. 1).

When the intermolecular distance decreases, HOMO of the aggregate becomes a mixture of the HOMOs of both monomers. At the same time the HOMO-LUMO gap does not change and remains within the range 0.20-0.22a.u. for HI and 0.19-0.20a.u. for SH dimers, respectively. However, in the case of the IS dimers a monotonic decrease in the energy of the HOMO-LUMO gap is registered (from 0.20a.u. at 4.12 Å to 0.16 at 2.86 Å). Figure 2 comprises also an extra data set for SH dimers: In one case the molecules have been shifted apart preserving the same intermolecular distance - a bigger ring of one molecule was above the smaller ring of the other. In the second case, one of the molecules has been rotated in plane by 90 or 180 (monomers remained parallel). The results indicate that such a variation in the configuration of a dimer changes significantly localization of orbitals, although none persistent tendencies have been observed. In contrast to HOMO, LUMO orbitals reveal lower tendency to delocalization. Only LUMO of the IS aggregate is more delocalized (at small intermolecular distances) than its HOMO.

### 3.2 Charged dimers

In case of molecules with unchanged number of atoms both, negatively and positively charged assemblies have been examined. Charge localization for symmetrical sets (HH, II, SS) are displayed in the Figure 4.

As can be inferred from the latter, an extra charge placed on a dimer is localized on one of the monomers, although as expected, the smaller the distance, the tendency of charge delocalization becomes more noticeable.
For negatively charged heterogeneous assemblies (SH, HI, IS), at all intermolecular distances the charge is localized on the more electron-liked monomer, i.e. (SH)- results in localization of charge on S monomer, (SH)- = S-H and similarily, (HI)- = H-I and (IS)- = IS-.
This finding changes however when a positive charge is taken into account. The molecules are poor electron-donors and our results show that the positive charge becomes localized on one of the monomers without any correlation with distance or monomer’s redox state.
For negatively charged systems the localization of the HOMO orbital has been also examined indicating that the orbitals are restrained exactly to the same monomer as the charge itself.
Similar behavior has been observed for dimers of molecules with a proton removed from the -OH group of one of the constituing monomers (cf. Figures 5, 6).

With the exception of the HS-dimer sets, all HOMOs for deprotonated assemblies are localized on different monomer than the relevant LUMOs (cf. Figures 5, 6). At the same time negative charge is localized on the same monomer as the relevant HOMO of the dimer (Figure 7).

The results of our computational analysis point out a persistent tendency for localization of charge/HOMO/LUMO within the studied dimeric assemblies of DHI monomers at the separation exceeding 3.4Å. Following the observation of HOMOs and LUMOs localization in the dimer, we have also examined the structure of first excited states of the assemblies. In most cases, the first excited state of a dimer is composed of its relevant HOMO$``$LUMO excitation, the apparent exceptions are however HI dimers at 3.00–3.14 Å separation and SH dimers at 3.28Å separation whose first excited states are mostly composed of the HOMO-1$``$LUMO transitions. Similarily, the first excited state of the SH dimer at 3.00–3.14Å separation and of the IS dimer at 3.42Å (and more) separation are predominantly formed of the HOMO-1$``$LUMO and HOMO$``$LUMO+1 transitions, respectively.

## 4 Discussion and Summary

The simplest sets of the stacked monomers, building blocks of eumelanin polymers have been examined. Analysis of localization of additional charges and HOMO/LUMO orbitals in an indolic dimer structure has been performed. Charged aggregates have been created either by adding/removing one electron from the neutral dimeric structure, or by deprotonating the -OH group in one of the monomers. Our investigations show that the structure of the frontier orbitals of any particular dimer depends on redox state of its components as well as on the way the molecule has gained the charge. Heterogeneous structures (SH, HI, IS) tend to behave as two separate molecules even if the distance between the molecules is small. Moreover, negatively charged dimers formed by adding an excessive electron to the neutral aggregate are characterized by the charge localization on a more electron-like monomer. In dimers where one of constituing monomers has been deprotonated, the proton-deficient monomer holds the negative charge independent of the electron-affinity of the neighbouring molecule in the set.
Homogeneous sets (HH, II, SS) of monomers show a stronger tendency to create dimers than the respective heterogeneous assemblies and at comparable distances they behave as one supermolecule with its HOMO and LUMO orbitals smeared over the whole structure. Additional charge in this structures becomes, however, located on one monomer only. Similar conclusion can be drawn from the preliminary studies on sets of planar pentameric polymers formed of indolic units, whose structure and absorption properties have been discussed elsewhere . Same analysis performed for neutral and charged assemblies of that type has revealed that also in the pentamers of randomly assemblied HQ,IQ and SQ molecules, the excessive charge becomes localized on one of constituing monomers. This result suggests that, in spite of the electron-acceptor properties, the indolic dimers (and most likely, indolequinone polymers, in general) do not stabilize the charge by delocalization over the entire structure, but rather tend to position the charge on one of the composing molecules.
The additional analysis performed on the SH dimer sets with one molecule rotated or translated with respect to another suggests that electronic properties of the complex may strongly depend on its conformations. Nevertheless, if we limit our considerations to characteristic distances (3.4Å) reported in experimental studies, the aformentioned general conculsions remain valid.

The above findings along with the conclusions recalled from References  suggest a highly dynamic picture of hypothetical eumelanins, whose chemical structure has been proven to be composed mainly of DHI molecules in different redox states. The redox state of the melanin units may change spontaneously under the influence of the environment (acidity, exposure to light and oxygen) and their relevant proportion and state of oxidation may vary in time. In agreement with the former theoretical studies , our results show high charge localization in basic clusters of eumelanin structure. Given the latter and an apparent localization of the HOMO and LUMO orbitals on one of the monomers in the stack, the electron-acceptor behavior of the melanin can be viewed as a process in which an electron injected (or photogenerated) in the polymer remains trapped or transfers via a hopping mechanism in between the indolic subunits. Moreover, any temporary charge distribution within the eumelanin complex can be altered e.g. in the process of spontaneous HQ$``$IQ reaction that effectively will also influence structure of frontier orbitals of the aggregate. Discussed from that perspective, eumelanins can be understood as amorphous polymers whose macroscopic electronic properties are essentially ensemble-average of various structures.

## 5 Acknowledgements

The authors acknowledge the Research Grant (1999-2002) from the Marian Smoluchowski Institute of Physics, Jagellonian University.


format: text

text:
# Untitled Document

 I. L. Chuang, M. A. Nielsen: Quantum computation and quantum information. Cambridge University Press, Cambridge, 2000.   G. H. Hardy, E. M. Wright: An Introduction to the Theory of Numbers. fourth edition, Oxford University Press, Oxford, 1960.    D. E. Knuth: The Art of Computer Programming. Vol. 2: Seminumerical algorithms. Addison-Wesley Publishing Co., Reading, MA, 1969.    D. E. Knuth, A. C. Yao: Analysis of the subtractive algorithm for greatest common divisors. Proc. Nat. Acad. Sci. U.S.A. 72 (1975), no. 12, 4720–4722.    S. Lindhurst: An analysis of Shanks’s algorithm for computing square roots in finite fields. Number theory (Ottawa, ON, 1996), 231–242, CRM Proc. Lecture Notes, 19, Amer. Math. Soc., Providence, RI, 1999.    A. Lubotzky: Discrete groups, expanding graphs and invariant measures. Birkhäuser Verlag, Basel, 1994.    A. Lubotzky, R. Phillips, P. Sarnak: Ramanujan graphs, Combinatorica 8 (1988) 261–277.    A. Tonelli: Sulla risoluzione della congruenza $`x^2c`$ (mod $`p^\lambda `$), Atti R. Accad. Lincei 1 (1892), 116–120.

Navigating the Cayley graph of $`\mathrm{SL}_2(F_p)`$

by

Michael Larsen**Partially supported by NSF Grant DMS 97-27553.

Department of Mathematics, Indiana University

Bloomington, IN 47405, USAAMS Classification 20F05

larsen@math.indiana.edu

ABSTRACT

We present a non-deterministic polynomial-time algorithm to find a path of length $`O(\mathrm{log}p\mathrm{log}\mathrm{log}p)`$ between any two vertices of the Cayley graph of $`\mathrm{SL}_\text{2}(\text{𝔽}_p)`$.

It is well known that $`\mathrm{SL}_2(F_p)`$ is generated by $`\left(\begin{array}{cc}1& 1\\ 0& 1\end{array}\right)`$ and $`\left(\begin{array}{cc}1& 0\\ 1& 1\end{array}\right)`$. It is a much deeper theorem  that the Cayley diameter of this group with respect to these generators is $`O(\mathrm{log}p)`$. There are two known proofs. One depends on uniformly bounding the eigenvalues of the Laplacian on $`L_0^2(X(p))`$ away from zero . The other uses the circle method to show that any element of $`\mathrm{SL}_2(F_p)`$ lifts to an element of $`\mathrm{SL}_2(Z)`$ which has a short word representation . Neither method is constructive. A. Lubotzky asked  for an efficient algorithm to find short word representations of general elements of $`\mathrm{SL}_2(F_p)`$. In this note we give such an algorithm, but for word representations of length $`O(\mathrm{log}p\mathrm{log}\mathrm{log}p)`$ rather than $`O(\mathrm{log}p)`$. More precisely, we prove

Theorem 1: There exist constants $`c_1`$ and $`c_2`$ such that for any $`c_3<1`$, there exists $`c_4`$ such that for any prime $`p`$ and any element of $`\mathrm{SL}_2(F_p)`$, the algorithm will find a word of length $`c_1\mathrm{log}p\mathrm{log}\mathrm{log}p`$ in time $`c_4\mathrm{log}^{c_2}p`$ with probability $`c_3`$.

Consider first the basic strategy of lifting $`\alpha \mathrm{SL}_2(F_p)`$ to $`\stackrel{~}{\alpha }\mathrm{SL}_2(Z)`$ and then using Euclid’s algorithm to represent $`\stackrel{~}{\alpha }`$. The trouble is that we must use the subtractive Euclidean algorithm. That is, we have to pay for each operation of subtracting one row from another, so the performance of the algorithm is worse than that of the usual Euclidean algorithm (and harder to analyze as well). In terms of continued fractions, cost is the sum of the partial quotients instead of their number. A heuristic argument suggests a median word length of $`O(\mathrm{log}N\mathrm{log}\mathrm{log}N)`$ for a matrix with entries in $`[N,N]`$. By contrast, by a result of D. Knuth and A. Yao , the mean word length is $`O(\mathrm{log}^2N)`$. The difference between median and mean is due to the fact that a few matrices require very long words. In particular, the word length is guaranteed to be large if the largest matrix entry is much larger in absolute value than the smallest. The obvious ways of lifting to $`\mathrm{SL}_2(Z)`$ nearly always produce such unbalanced matrices. For example, if we lift the entries of the first row to elements of $`[0,p1]`$ and then lift the remaining entries to integers of minimal absolute value, they will typically be of order $`O(p^2)`$.

To avoid this difficulty, we turn the problem around and ask for elements of $`\mathrm{SL}_2(Z)`$ which can be represented by short words in our generators. Let $`a`$ and $`d`$ denote integers between $`1`$ and $`p`$ with mutually inverse reductions (mod $`p`$). Set $`c=p`$, so $`b=(ad1)/p`$. For most choices of $`a`$, $`a/p`$ has a continued fraction expansion with partial quotient sum $`O(\mathrm{log}p\mathrm{log}\mathrm{log}p)`$. To show this, one must justify the heuristic estimate mentioned above for the sum of the partial quotients of a random fraction of fixed demominator $`p`$. We do this by an elementary argument suggested by the circle method.

In the above construction, $`b`$ and $`d`$ are determined by $`a`$. To eliminate the dependence on $`b`$, we use the identity

$$\left(\begin{array}{cc}a& b\\ 0& d\end{array}\right)\left(\begin{array}{cc}1& 1\\ 0& 1\end{array}\right)\left(\begin{array}{cc}a& b\\ 0& d\end{array}\right)^1=\left(\begin{array}{cc}1& a^2\\ 0& 1\end{array}\right).$$

This provides a large number of unitriangular matrices with word representations of length $`O(\mathrm{log}p\mathrm{log}\mathrm{log}p)`$, from which one can easily construct all elements of $`\mathrm{SL}_2(F_p)`$.

It may be worth noting that the analogous problem for $`\mathrm{SU}(2)`$ has recently been solved: given a fixed finite set of topological generators, to approximate a given $`\alpha \mathrm{SU}(2)`$ with error $`ϵ`$ by a word of polylog length in polylog time. A solution using iterated commutators was discovered independently by R. Solovay and A. Kitaev  App. 3.

I would like to acknowledge the hospitality of the Hebrew University where this work was done. Peter Sarnak first called my attention to the problem of efficiently constructing short word representations for $`\mathrm{SL}_2(F_p)`$. He also made a number of helpful comments on an earlier version of this paper. I enjoyed a number of stimulating conversations with Alex Lubotzky on this problem. It gives me great pleasure to thank them both.

We begin with a careful analysis of the performance of the subtractive Euclidean algorithm. For terminology, notation, and basic facts related to continued fraction expansions, we refer to  and .

Definition 2: An element $`\left(\begin{array}{cc}a& b\\ c& d\end{array}\right)`$ of $`\mathrm{SL}_2(Z)`$ is left-dominated if $`a,b,c,d0`$ and $`a+cb+d`$.

Lemma 3: If $`\left(\begin{array}{cc}a& b\\ c& d\end{array}\right)`$ is left-dominated, then $`ab`$. Moreover, unless it is the identity matrix, $`cd`$.

Proof: If $`a<b`$, then $`d<c`$, which is impossible, since the matrix entries are non-negative and the determinant is $`1`$. Similarly, if $`c<d`$, then $`b<a`$, so $`bcad1`$, with equality if and only if $`b=c=0`$. $``$$``$

Lemma 4: If $`\left(\begin{array}{cc}a& b\\ c& d\end{array}\right)`$ is a left-dominated matrix other than the identity, then if $`ac`$, the matrix $`\left(\begin{array}{cc}a& b\\ ca& db\end{array}\right)`$ is left-dominated; otherwise $`\left(\begin{array}{cc}ac& bd\\ c& d\end{array}\right)`$ is left-dominated.

Proof: All that remains to be shown is that the entries of the specified matrix are non-negative. If $`ac`$, unimodularity implies $`d>b`$. If $`a>c`$ and $`d>b`$, unimodularity implies that $`\left(\begin{array}{cc}a& b\\ c& d\end{array}\right)`$ is the identity. $``$$``$

This lemma shows that the elementary row operations needed to reduce a left-dominated matrix to the identity can be chosen without reference to the right column. It therefore motivates the definition of a function $`S:N\times NN`$ as follows:

$$S(a,c)=\{\begin{array}{cc}0\hfill & \text{if }c=0\text{,}\hfill \\ S(ac,c)+1\hfill & \text{if }a>c>0\text{,}\hfill \\ S(a,ca)+1\hfill & \text{if }ca>0\text{.}\hfill \end{array}$$

We have immediately from this definition the following lemma:

Lemma 5: Any left-dominated matrix $`\left(\begin{array}{cc}a& b\\ c& d\end{array}\right)`$ can be written as a word of length $`S(a,c)`$ in the letters $`\left(\begin{array}{cc}1& 1\\ 0& 1\end{array}\right)`$ and $`\left(\begin{array}{cc}1& 0\\ 1& 1\end{array}\right)`$.

Every positive rational number has exactly two continued fraction expansions:

$$\frac{a}{c}=[k_0,k_1,\mathrm{},k_n]=[k_0,k_1,\mathrm{},k_n1,1].$$

Therefore, we may define $`T(a/c)`$ to be the sum of the partial quotients appearing in a continued fraction expansion of $`a/c`$.

Lemma 6: If $`a`$ and $`c`$ are relatively prime positive integers, $`T(a/c)=S(a,c)`$. Proof: Immediate by induction. $``$$``$

Our object will be to show that for any fixed prime $`p`$ there exist many positive integers $`a<p`$ such that $`S(a,p)`$ is not much greater than $`\mathrm{log}p\mathrm{log}\mathrm{log}p`$. To do this, it will be convenient to break up $`T(a/p)`$ into pieces corresponding to individual partial quotients. We therefore define $`T_d(a/p)`$ to be equal to $`k_i`$ if the denominator of $`[k_0,k_1,\mathrm{},k_{i1}]`$ is $`d`$ for some $`in`$; to be $`1`$ if $`d`$ is the denominator of $`[k_0,k_1,\mathrm{},k_n1]`$; and otherwise to be $`0`$. Thus $`T_d(a/p)>0`$ if and only if some fraction with denominator $`d`$ is a convergent of $`a/p`$. Moreover,

$$\underset{d=1}{\overset{\mathrm{}}{}}T_d(a/p)=\underset{d=1}{\overset{p1}{}}T_d(a/p)=T(a/p)+1.$$

The key proposition is as follows:

Proposition 7: For all $`ϵ>0`$, there exists a constant $`C`$ such that for all primes $`p`$,

$$\frac{|\{a[1,p1]N:S(a,p)<C\mathrm{log}p\mathrm{log}\mathrm{log}p\}|}{p1}1ϵ.$$

Proof: Let $`X=[1,p1]N`$. For $`\delta (0,1)`$ and $`dN`$ we define the “major arc” $`Y_d(\delta )`$ (really a union of major arcs) to be the subset of $`X`$ consisting of $`a`$ such that

$$\underset{bZ}{inf}\left|\frac{a}{p}\frac{b}{d}\right|<\frac{\delta }{d^2}.$$

For $`dp`$, $`Y_d(\delta )`$ is empty. Every $`d<p`$ is relatively prime to $`p`$, so there is at most one way to represent a given integer as $`adbp`$, $`aX`$, $`bZ`$, (and no way to represent $`0`$). Thus,

$$|Y_d(\delta )|\frac{2p\delta }{d}.$$

We define

$$X(\delta )=X\underset{d=1}{\overset{\mathrm{}}{}}Y_d(\delta ),$$

so

$$|X(\delta )|p1p\left(2\delta \underset{d=1}{\overset{p1}{}}1/d\right)1+p(12\delta (\mathrm{log}p+1))1+p(16\delta \mathrm{log}p).$$

On the other hand, the “minor arc” contribution satisfies

$$\underset{aX(\delta )}{}T(a/p)<\underset{aX(\delta )}{}\underset{d=1}{\overset{p1}{}}T_d(a/p).$$

If $`p_i/q_i`$ denotes the $`i`$th convergent of $`a/p`$, then

$$\left|\frac{p_i}{q_i}\frac{a}{p}\right|<\frac{1}{k_{i+1}q_i^2}.$$

In particular, unless $`|bpad|<p/d`$, $`b/d`$ cannot be a convergent of $`a/p`$. Thus,

$$\underset{aX(\delta )}{}T_d(a/p)2\underset{e[p\delta /d,p/d]N}{}\frac{p}{de}\frac{2}{\delta }\frac{2p\mathrm{log}\delta }{d}.$$

Summing over $`d`$,

$$\underset{aX(\delta )}{}T(a/p)<\frac{(2p2)}{\delta }2\mathrm{log}\delta (\mathrm{log}p+1)p.$$

Setting $`\delta =\frac{ϵ}{12\mathrm{log}p}`$, we get $`|X(\delta )|(1ϵ/2)p1`$ and

$$\underset{aX(\delta )}{}T(a/p)2p\mathrm{log}p\mathrm{log}\mathrm{log}p+o(p\mathrm{log}p\mathrm{log}\mathrm{log}p).$$

Choosing $`C`$ sufficiently large, the number of elements $`a`$ in $`X(\delta )`$ with

$$T(a/p)>C\mathrm{log}p\mathrm{log}\mathrm{log}p$$

is less than $`ϵp/2`$. Thus, the number of elements in $`X`$ with $`T(a/p)>C\mathrm{log}p\mathrm{log}\mathrm{log}p`$ is at most $`ϵp`$. $``$$``$

We can now prove the main theorem:

Proof: Setting $`ϵ`$ to be any constant less than $`1/16`$, we define $`C`$ as above. As the number of points on a nonsingular affine conic over $`F_p`$ is at least $`p1`$ and at most $`p+1`$, for any $`yF_p`$, there are $`p/4+O(1)`$ representations of $`y`$ as a sum of quadratic residues $`x_1`$ and $`x_2`$. We write $`a_i`$ for the representative of $`\sqrt{x_i}`$ in $`[1,p/2]`$. The number of choices of $`x_1`$ for which

$$\underset{i}{sup}T(a_i/p)>C\mathrm{log}p\mathrm{log}\mathrm{log}p$$

is at most $`4ϵp`$, so that if an element $`x_1`$ of $`F_p`$ is chosen at random, the probability is at least $`1/42ϵ>0`$ that $`x_1`$ is a square, $`S(a_1,p)C\mathrm{log}p\mathrm{log}\mathrm{log}p`$, and the same things are true for $`x_2=yx_1`$ and the unique integer $`a_2[1,p/2]`$ such that $`a_2^2`$ reduces to $`x_2`$. Define $`d_i`$ to be the integer in $`[1,p1]`$ which reduces to the inverse of the reduction of $`a_i`$, and set $`b_i=(a_id_i1)/p`$. Thus,

$$\left(\begin{array}{cc}a_1& b_1\\ 0& d_1\end{array}\right)\left(\begin{array}{cc}1& 1\\ 0& 1\end{array}\right)\left(\begin{array}{cc}a_1& b_1\\ 0& d_1\end{array}\right)^1\left(\begin{array}{cc}a_2& b_2\\ 0& d_2\end{array}\right)\left(\begin{array}{cc}1& 1\\ 0& 1\end{array}\right)\left(\begin{array}{cc}a_2& b_2\\ 0& d_2\end{array}\right)^1$$

can be written as a word of length at most $`4C\mathrm{log}p\mathrm{log}\mathrm{log}p+2`$, and its (mod $`p`$) reduction is $`\left(\begin{array}{cc}1& y\\ 0& 1\end{array}\right)`$.

For square roots, we use Shanks’s algorithm (, ), which is probabilistic and polylogarithm. Note that one has a deterministic square root algorithm when $`p3\text{(mod }4\text{)}`$, but nevertheless, our algorithm remains nondeterministic since it depends on how many tries are needed before we find a good $`x_1`$.

Applying transpose, we can likewise find words of length $`O(\mathrm{log}p\mathrm{log}\mathrm{log}p)`$ for lower unitriangular matrices. Since every matrix which is not upper triangular can be written

$$\left(\begin{array}{cc}1& y_1\\ 0& 1\end{array}\right)\left(\begin{array}{cc}1& 0\\ y_2& 1\end{array}\right)\left(\begin{array}{cc}1& y_3\\ 0& 1\end{array}\right),$$

every matrix in $`\mathrm{SL}_2(F_p)`$ can be written as a product of at most four upper or lower unitriangular matrices. Therefore, for every constant $`c_4<(1/4)^4`$, we can find $`c_1`$, $`c_2`$, and $`c_3`$ satisfying the conditions of the theorem. To deal with $`c_44^4`$, we use repeated independent trials of the algorithm.

$``$$``$

References


text:
# Anisotropy of the Mobility of Pentacene from Frustration

## I Introduction

Charge transport in organic molecular conductors has gained prominent interest as it is expected that in ultra-clean materials band transport with high electronic mobilities can be obtained. Recent progress in synthetic procedures have minimized mobility reducing factors, such as disorder, Frenkel defects, and Schottky defects. Thus, mobilities up to $``$ 1 cm2/Vs have been obtained in thin film devices and in single crystals at room temperature.

Pentacene has gained prominent interest because of a number of favorable materials properties. Large single crystals can be easily grown by vapor transport, and the material can be handled in air. The reactivity of pentacene to impurity levels of oxygen and hydrogen is often underestimated, but can be minimized using appropriate synthetic conditions. Despite the presence of at least four different polymorphs, there are no structural phase transitions observed for the most stable polymorph, the single crystal polymorph. The layered crystal structure indicates a highly two-dimensional charge transport.

In this paper we use first-principles density functional theory (DFT) to calculate the bandstructure of pentacene. We find a very large anisotropy of the effective mass within the layers, resulting from a frustration of the electron transfer along the crystallographic b-axis. This frustration is rationalized using a tight-binding fit of the band structure, and is intimately related to the herringbone geometry of the crystal structure of pentacene. Our results imply that the mobility is strongly directionally dependent within the layers.

## II Structure

The crystal structure of bulk pentacene, depicted in Fig. 1, has been reported by several groups. It is a layered structure, triclinic, with spacegroup $`P\overline{1}`$. The molecular layers consist of pentacene molecules arranged in a herringbone pattern. We chose the unit vectors following Ref. , with a and b in the molecular plane and c inter-relating the molecular planes. The unit cell contains two inequivalent molecules. The molecules are not perpendicular to the molecular planes, but are at finite angles. This slant can be understood as a relative shift of the molecules. Starting from one molecule, moving along $`(𝐚+𝐛)/2`$ one arrives at an another (inequivalent) molecule, that is shifted along its longest molecular axis (LMA) by 2.13 Å, i.e. approximately the length of one ring in the pentacene molecule. Going along $`(𝐚𝐛)/2`$ the shift is a mere 0.12 Å, i.e. it is negligible. This “staircase” pattern is indicated in Fig 1(b), which shows a projection of a molecular layer along the LMA.

## III Technical details

The bandstructure has been calculated using density functional theory in the generalized gradient approximation (GGA). The ab initio total-energy and molecular-dynamics program VASP (Vienna Ab initio Simulation Program) was used. Electron-ion interactions were described using the projector augmented wave method. The kinetic energy cutoff on the wave function expansion was 500 eV.

The self-consistent calculations were carried out using the experimental positions and cell (determination at 90 K from Ref. ) with a 4$`\times `$4$`\times `$2 k-point mesh. Convergence was tested with a 6$`\times `$6$`\times `$4 mesh and found to be sufficient.

The bandstructure of the single molecular layer was calculated also from a 3D crystal, but with an extra vacuum region of 6 Å thickness inserted between the layers. Thus interactions between the layers were avoided. Moreover, the $`𝐜`$-axis was chosen perpendicular to the $`\mathrm{𝐚𝐛}`$ plane, i.e. the lattice was transformed to that of a monoclinic crystal.

## IV Results

Fig. 2 displays the calculated density of states (DOS) of pentacene. All bands below the Fermi level are completely filled. The unoccupied bands are separated from the valence bands by a band gap of 0.7 eV. This is consistent with experiment, as undoped pentacene is an insulator. The experimental band gap is 2.2 eV. However, an underestimation of the band gap is not unusual for GGA/DFT and, in general, doesn’t much affect the other features of the electronic structure. The DOS peak of the HOMO (just below 0 eV) and of the LUMO (at 1 eV) are both well separated from the other peaks. Each of them doesn’t mix with bands derived from other molecular states. The calculated HOMO and LUMO band widths are $``$ 600 and $``$ 700 meV respectively.

Another, recent theoretical calculation gives values of 608 and 588 meV respectively. This compares well with our results, although we find a bit wider LUMO band.

Both the DOS of the single layer and of the complete 3D crystal are plotted. On the scale of the plot, differences are only apparent above 3 eV. The electronic structure of the single layer should be a good first approximation to that of the complete crystal. Its bandstructure is only 2D, which greatly facilitates the interpretation.

### A Bandstructure of a Single Layer

The band structure near the Fermi level of a molecular layer is depicted in Fig. 3. Both the HOMO and the LUMO complex consist of two bands, as there are two molecules in the unit cell. For both, the maximum and minimum are at M \[($`\frac{1}{2}`$,$`\frac{1}{2}`$)\]. Therefore, upon doping (both with electrons and with holes) the charge carriers will be created in the vicinity of this point. Their effective mass is strongly directionally dependent. In particular, note the flatness of the bands near the extrema for the direction M-Y. These observations will be further elaborated upon below.

Since the band complexes are well separated from the other bands, we can attempt a tight-binding (TB) fit, for both the HOMO and the LUMO separately. The fit parameters are the transfer integrals $`t`$ between the molecular orbitals. Some of these are shown in Fig. 4. As we have two molecules, a $`2\times 2`$ matrix will have to be diagonalized:

$$\left[\begin{array}{cc}\epsilon (𝐤)eT_1& T_2\\ T_2& \epsilon (𝐤)T_1\end{array}\right]$$
(1)
Here $`T_1`$ and $`T_2`$ denote the sums of the diagonal and off-diagonal transfer integrals, multiplied with the appropriate phase factors, respectively. $`\epsilon (𝐤)`$ are the eigenvalues and $`e`$ accounts for the fact the the molecules are inequivalent. $`\epsilon (𝐤)`$ is required to follow the DFT result of Fig. 3 as close as possible.

As is evident from the figure, the fit follows the DFT result very well. All transfer integrals are listed in Table I. By far the most important ones are $`t_𝐚`$, $`t_{(𝐚+𝐛)/2}`$ and $`t_{(𝐚𝐛)/2}`$. For the HOMO (LUMO) the values are: $`t_𝐚`$ = 31 (-41) meV, $`t_{(𝐚+𝐛)/2}`$ = -56 (-90) meV and $`t_{(𝐚𝐛)/2}`$ = 91 (90) meV. All the others are very small.

The effective mass is easily calculated with the help of the analytic expression for the fit. In Fig. 5 the hole effective mass $`m^{}`$, calculated from:

$$\frac{^2\epsilon (k)}{k^2}=\frac{\mathrm{}^2}{m^{}}$$
(2)
is plotted for all directions in the plane. Note the large anisotropy. The largest value, 58 me, occurs for the $`𝐚`$ direction.

Below we’ll further discuss the band structure near the M point (i.e. the point where the valence band maximum and conduction band minimum occur) and explain the mechanism behind the large anisotropy. The molecular orbitals, HOMO and LUMO, are plotted in Fig. 6. They are both $`\pi `$-systems, having a nodal plane coinciding with the plane of the molecule. Along the LMA the HOMO alternatingly has maxima and minima that are slightly more apart than the length of one ring-unit of the molecule. This pattern leads to 4 nodal surfaces “perpendicular” to the LMA. Additionally there’s one more nodal plane containing the LMA.

The LUMO doesn’t have such a nodal plane. It has two more nodal surfaces “perpendicular” to its LMA. Again the wave function extrema are approximately one ring-unit apart.

Fig. 7 shows a schematic representation, in a plane perpendicular to the LMA, of the HOMO-derived crystal orbitals at the M point. At M the phase of the wave function changes by 180, both for a translation over $`𝐚`$ and $`𝐛`$. However, in Fig. 7 all 4 molecules at the corners have the same phase. This is because the staircase (slant) in the layer gives rise to a shift of the molecule at each step. This results (see the preceding paragraph) in an additional phase change of approximately 180.

Depending on the phase of the central molecule, either the low or high band at M is selected. In Fig. 7(b) all three important transfer integrals give a bonding contribution. Indeed, this is the most bonding eigenstate within the band complex and thus corresponds to the minimum at M. Fig. 7(a) depicts the most antibonding situation (the top of the valence band): The transfers $`(𝐚+𝐛)/2`$ and $`(𝐚𝐛)/2`$ are maximally anti-bonding. Transfer $`𝐚`$ is still bonding. Due to frustration no solution with anti-bonding overlap for all three transfers is possible.

The frustration can also explain the large anisotropy in the effective mass. Moving along $`𝐚`$ ($``$ $`𝐚^{}`$) two conduction channels are possible: One directly via $`t_𝐚`$, the other via a “double hop” \[$`t_{(𝐚+𝐛)/2}`$ and $`t_{(𝐚𝐛)/2}`$\]. Moving away from M, the double hop will force the bands in a downward curvature, which is counteracted by the direct channel. This explains why the band becomes flat. By contrast, moving along $`𝐛^{}`$ in reciprocal space, the channel along $`𝐚`$ drops out and a cosine-shaped band results, indicative of alternate $`(𝐚+𝐛)/2`$ and $`(𝐚𝐛)/2`$ hops.

The LUMO bands mimic the HOMO bands in a very special way: They appear as the “mirror” image of the HOMO bands on the energy axis (Fig. 3). This peculiar feature is due to the LUMO’s slightly different nodal structure (it lacks the second mirror plane containing the LMA). Therefore the top point at M has all three transfers antibonding, whereas frustration now occurs for the most bonding point at the bottom of the conduction band (where the $`𝐚`$ “hop” is still antibonding). Thus the large anisotropy of the hole effective mass is “mirrored” in the electron effective mass. The analogy between the HOMO and LUMO band complex is not complete: E.g., the avoided crossing along M-$`\mathrm{\Gamma }`$ only occurs for the HOMO and the total width of the LUMO complex is slightly larger than that of the HOMO complex.

### B Bandstructure of the 3D Crystal

The band structure of the full 3D crystal (Fig. 8) strongly resembles that of the 2D layer. The shape of the bands for the most dispersive, $`𝐚^{}`$ and $`𝐛^{}`$ directions is essentially the same. Some differences are apparent though: (a) the top of the valence band is not at M \[($`\frac{1}{2}`$,$`\frac{1}{2}`$,0)\], but at (0.375, 0.5, 0.075). Moreover, as is evident from the top panel of Fig. 8, the band doesn’t have a parabolic shape. The deviations are small however.

The conduction band minimum now occurs near H. (b) A small band dispersion occurs along $`𝐜^{}`$.

Fig. 9 depicts the hole effective mass, directly calculated from the band structure using finite differences. We cannot rely on a TB fit, as it cannot capture the bump at (0.375, 0.5, 0.075). For directions close to $`𝐚^{}`$ the effective mass was not calculated, due to the locally non-parabolic nature of the band. For the other directions the picture is very similar to the 2D analogon. For $`𝐜^{}`$ we obtain: $`m_𝐜^{}^{}`$ = 5.2 me.

Our results may be compared with a recent extended Hückel (EH) band structure calculation on the pentacene single crystal. The agreement between the EH and our first-principles results is quite good. The EH study reports the band structure for a limited number of lines in the BZ ($`\mathrm{\Gamma }`$-X, $`\mathrm{\Gamma }`$-Y, $`\mathrm{\Gamma }`$-Z) and therefore doesn’t consider the special situation near M.

## V Discussion & Conclusions

Band structure calculations for the pentacene single crystal reveal HOMO and LUMO bandwidths of $``$ 600 and 700 meV respectively. Consistently, (hole) effective masses as low as 1.7 me (for m$`_b^{}`$) are found. Even $`m_𝐜^{}^{}`$ (5.2 me) is rather low, in spite of the apparent flatness of the bands for the $`𝐜^{}`$ direction. Within the molecular layers a competition between different conduction paths results in a large anisotropy of both the hole and the electron effective mass, the charge carriers being orders of magnitude heavier for the $`𝐚^{}`$ (than for the $`𝐛^{}`$ direction).

Our calculations do not take into account the coupling with lattice degrees of freedom. At lower temperatures the electron-phonon coupling may renormalize the charge-carrier’s bandwidth. At higher temperatures the bandwidth renormalization and mobility reduction may differ for different directions, thus affecting the anisotropy. For anthracene, recent first-principles calculations indeed show a directionally dependent bandwidth renormalization. However, as it is so pronounced, we expect much of the effective mass anisotropy to survive, also at higher temperatures, as long as coherent band-like transport is dominant.

## Acknowledgments

We thank Dr. P.A. Bobbert for useful discussions and making available Ref.  prior to publication. This work is part of the research programme of the ’Stichting voor Fundamenteel Onderzoek der Materie (FOM)’, which is financially supported by the ’Nederlandse Organisatie voor Wetenschappelijk Onderzoek (NWO)’.


text:
# Abundance Anomalies in the X-ray Spectra of the Planetary Nebulae NGC 7027 and BD +30°3639

## 1 Introduction

The optically emitting gas of planetary nebulae (PNs) is illuminated and ionized by the radiation from the central hot star, which is evolving to become a white dwarf (WD). The shaping of the optical nebula, formed from the envelope of the progenitor asymptotic giant branch (AGB) star, is a more complicated process, with many open questions (Kastner, Soker, & Rappaport 2000). Of particular interest is whether a binary companion is required to form non-spherical nebulae, or whether single AGB stars can blow axisymmetrical winds and form axisymmetrical PNs. According to Soker & Rappaport (2000) one of the processes by which a companion can shape a PN is by accreting from the wind of the AGB progenitor; if an accretion disk is formed around the compact companion, then a jet-like bipolar outflow (or collimated fast wind, CFW) can result. When the jet material is shocked, it heats up and may emit in the X-ray band. Another ingredient in the shaping process is the fast wind from the central star, blown during the post-AGB and PN stages (Kwok, Purton, & Fitzgerald 1978). The shocked fast wind is expected to emit in the X-ray band. In particular, an intermediate-velocity ($`500\mathrm{km}\mathrm{s}^1`$) wind during the post-AGB phase may explain many of the observed properties of the X-ray emitting gas in PNs (Soker & Kastner 2003).

Processes behind the extended X-ray emission are tied to the shaping processes of PNs (Kastner et al. 2002), and although not all shaping processes will lead to X-ray emission, the X-ray properties of PNs may hint at the nature of their progenitor (Soker & Kastner 2003). With this goal in mind, we present a re-analysis of the spatially extended X-ray spectra of two PNs, BD +30°3639 (PN G064.7+05.5) and NGC 7027 (PN G084.9-03.4). Material relevant to these PNs is summarized in our earlier papers announcing the detection of extended X-ray emission from them (Kastner et al. 2000; Kastner, Vrtilek, & Soker 2001), and a study of the X-ray morphologies of these two PNs (Kastner et al. 2002). The observations are described in §2. In §3, we describe our spectral analysis, and in §4 we present the results, emphasizing the large differences in the abundances of some elements between the X-ray emitting gas and the optical nebula. In $`\mathrm{\S }4`$ we suggest explanations for these findings, focusing on magnesium (Mg) in NGC 7027, and neon (Ne) in BD +30°3639.

## 2 Observations

Chandra observed NGC 7027 for 19.0ksec and BD +30°3639 for 18.5ksec with the Advanced CCD Imaging Spectrometer (ACIS) (Garmire et al. 1988) as the focal plane instrument. For both observations the Science Instrument Module was translated and the telescope was pointed such that the telescope boresight was positioned near the center of the spectroscopy CCD array (ACIS -S); the objects where imaged on the central back-illuminated CCD (S3), which provides moderate spectral resolution of $``$4.3 at 0.5 keV and $``$9 at 1.0 keV. Analyses of these data have already appeared in Kastner et al. (2000,2001). Data from these observations were reprocessed by the Chandra X-ray Center (CXC) subsequent to the publication of our earlier papers and the analyses presented here were performed on the reprocessed files. Each spectrum was extracted using the Chandra Interactive Analysis of Observations (CIAO) software within a region judged to contain all the X-ray flux from the nebula. We note that the current extraction (CIAOv2.2.1) reflects upgrades to the calibration system that were made after our previous papers on these systems were published. The extracted events are aspect-corrected, bias-subtracted, graded, energy-calibrated and limited to grade 02346 events (ASCA system). For both observations, the background count rate from a large, off-source annulus region (30- and 50-pixel radii) was negligible in comparison to the source count rate.

## 3 Spectral Analysis

The low photon statistics and limited energy range characteristic of these spectra make it difficult to derive abundances for these objects on the basis of X-ray spectra alone. Here we model the spectra using, as guidance, abundances derived from studies in the optical, ultraviolet, and infrared. We used the VMEKAL (Mewe, Lemen, & van den Oord 1986) code as incorporated into XSPEC v11.0 (Arnaud, Borkowski, & Harrington 1996) to generate model spectra that are appropriate for optically thin thermal plasma in ionization equilibrium. When abundance values for elements that are fit by VMEKAL are not available we set the abundance to Solar. In this we differ from our original papers (Kastner et al. 2000, 2001) where unspecified abundances were set to zero for elements heavier than Mg.

### 3.1 NGC 7027

The X-ray spectrum of NGC 7027 shows emission that peaks at approximately 0.9 keV and 1.3 keV and drops off at approximately 1.4 keV. No significant emission was detected below 0.5 keV and above 2.0 keV, hence we restrict our fits to the energy range 0.5-2.0 keV.

Nebular abundances reported by Bernard Salas et al. (2001) using ISO and optical observations produced a fair fit (Fig. 1), but do not adequately account for features between 0.6-0.7 keV and $``$1.3 keV. We attribute the feature at 0.65 keV to a blend of O lines. We note that while the nebula has been reported to be somewhat depleted in O (Bernard Salas et al. 2001; Beintema et al. 1996; Keyes, Aller, & Feibelman 1990; Middlemass 1990), the stellar wind of NGC 7027 is expected to show a greatly enhanced O abundance (Hasegawa, Volk, & Kwok 2000). This high O abundance could explain the feature at 0.6 keV. However, we emphasize that, while Kastner et al. (2001, 2002) ascribe the X-ray emission to the action of a fast wind, no such fast wind has yet been detected for this nebula. The feature at $``$ 1.3 keV requires enhanced Mg abundance; we were unable to find alternative explanations for this feature. We thus fit our X-ray spectrum starting with nebular abundances as determined by Bernard Salas et al. (2001) but allowing O and Mg to be free. The resulting fit (Fig. 2 and Tables 1,2) requires O enhanced to 9 times solar and Mg enhanced to 3 times solar.

In all cases we allowed the intervening column density NH to be a free parameter. Best-fit values of $`N_H`$ (Table 2) are consistent with our previous results and with the typical value of $`A_V`$ toward NGC 7027 (Kastner et al. 2001,2002); however, the temperature is a factor of $`2.8`$ larger, if the abundances of elements above Mg in NGC 7027 are Solar as assumed here. A higher temperature implies that the fast wind material that was shocked and formed the presently X-ray emitting gas was blown at a somewhat higher speed, and/or the adiabatic cooling, studied by Soker & Kastner (2003), was less efficient. ”

### 3.2 BD +30°3639

Like NGC 7027, past analysis of BD +30°3639 suggests that this PN’s X-ray emission arises primarily from wind and/or nebular material (Kastner et al. 2000). Here, we perform several tests to determine whether the observed X-ray spectrum is consistent with reported nebular and/or stellar wind abundances. The extracted spectrum shows distinct peaks near 0.5 keV and 0.95 keV. No significant emission was detected below 0.3 keV and above 1.5 keV. We restrict our fits to the energy range 0.3-1.5 keV.

We first assume nebular abundances reported from optical and ultraviolet observations by Pwa, Pottasch, & Mo (1986), Aller & Hyung (1995), and Grevesse & Sauval (1998). The best-fit parameters are listed in Table 2 and the model is shown in Figure 3. We then use abundances reported for the stellar wind by Arnaud et al. (1996). The stellar wind abundances provide a significantly better fit than the nebular abundances but strong features near 0.95 and 0.6 keV remain (Figure 4). We then attempted to fit the X-ray spectrum starting with the stellar wind abundances but allowing O and Ne to be free parameters. This resulted in an acceptable fit ($`\chi ^2=1.5`$) with O enhanced to 3.6 times solar and Ne enhanced to 21 times solar. Although this Ne enhancement is not predicted by studies at longer wavelengths, it is consistent with earlier X-ray studies (Arnaud et al (1996); Kastner et al. (2000)) suggesting that the feature at 0.9 keV can only be fit with an enhanced Ne abundance. The model is shown overlaying the data in Figure 5, and the best-fit parameters are listed in Tables 1, 2. Our best-fit value for T is 0.7 times higher and for NH two times higher than that obtained by Kastner et al. (2001), whose result for $`N_H`$ is consistent with the measured optical obscuration of the nebula ($`A_V`$) given a conversion between $`N_H`$ and $`A_V`$ appropriate for the interstellar medium. Our result for $`N_H`$ would therefore suggest that the gas to dust ratio in this nebula is elevated over that of the interstellar medium, along lines of sight toward the X-ray-emitting gas.

## 4 Discussion and Conclusions

NGC 7027 and BD +30°3639 show strong emission features that require enhanced Mg abundance relative to solar (to fit lines at $``$1.3 keV) for NGC 7027, and enhanced Ne abundance relative to solar (to fit lines at $``$0.9 keV) for BD +30°3639 (Kastner et al. 2000; Kastner et al. 2001). Both of these results are surprising since abundance values for the nebular and stellar wind material obtained at other wavelengths indicate depleted Mg and Ne (Beintama et al. 1996; Keyes & Aller 2001; Middlemass 1990).

### 4.1 Neon in BD +30°3639

Kastner et al. (2000) proposed that the high abundance of Ne found in BD +30°3639 results from the central star which itself is a carbon-rich Wolf-Rayet (\[WC\]) object (Grosdidier et al. 2000). Here we suggest that the source of the large abundance of Ne in BD +30°3639 is a nova eruption on an oxygen-neon-magnesium (ONeMg) WD companion. Novae in cataclysmic variables, which are thought to occur on the surface of ONeMg WDs, are known to eject material with Ne abundance up to $`300`$ times the solar abundance, and the total ejected mass is $`>10^510^4M_{}`$ (Starrfield et al. 1998). The estimated mass in the X-ray emitting gas in BD +30°3639 is $`2\times 10^5M_{}`$ (Kastner et al. 2000). Therefore, a nova eruption can easily account for the $`21`$ times solar Ne abundance. The Mg abundance in such nova eruptions is typically a factor of $`550`$ times lower than the Ne abundance (Starrfield et al. 1998). Therefore, it is not surprising we do not detect the Mg line in the spectrum of BD +30°3639.

The shaping of some bipolar PNs by nova eruption on a WD companion has been proposed by Soker (2002), who reviews many routes for the formation of bipolar PNs, several involving novae eruptions. The accretion rate onto the WD cannot be too high in that case, so the orbital separation cannot be too small. We do note that an accretion disk may mix Ne in the ejected jets even when there is steady nuclear burning. Observations supporting this proposed scenario come from symbiotic systems. Some symbiotic systems are known to experience nova outbursts (such systems are referred to as ”symbiotic novae”; e.g., RX Puppis, Mikolajewska et al. 1999), and some bipolar symbiotic nebulae appear to have gone through an eruptive mass loss event, possibly due to a nova eruption, as in the cases of V1016 Cyg (Corradi et al. 1999) and He 2-104 (Corradi et al. 2001). For the symbiotic nova RX Puppis, Mikolajewska et al. (1999) argue for an orbital separation of $`>50\mathrm{AU}`$. Although the bright ionized region of BD +30°3639 has a general elliptical shape, high resolution radio molecular-line imaging has revealed the presence of two, oppositely-directed “bullets” of fast-moving, dense gas, suggestive of the action of collimated outflows or jets (Bachiller et al. 2000). To conclude, we propose that the central star of BD +30°3639 has a massive, $`M_{\mathrm{WD}}1M_{}`$ ONeMg WD companion, at an orbital separation of $`550\mathrm{AU}`$.

### 4.2 Magnesium in NGC 7027

In principle, peculiar abundance in the X-ray emitting gas of NGC 7027 could also result from material ejected from a WD companion; indeed, Kastner et al. (2001) attributed the emission peak near 0.9 keV to Ne lines (whereas here they are modeled as a complex of lines of highly ionized Fe). However, we suggest a simpler explanation. The nebular abundances derived from previous studies of NGC 7027 are for the gas in the optical nebulae, and do not include metals locked in dust particles. NGC 7027 is known to have a significant amount of dust in the nebular shell (Sanchez Contreras et al. 1998) hence it is expected that many metals will be depleted in the gas phase. However, in the X-ray emitting gas we don’t see this depletion, which implies that the dust in this medium was either destroyed or was never formed.

Assuming that the Mg abundance in the X-ray emitting gas is that of the wind lost by the progenitor, then the depletion in this nebula is by a factor of $`3.0/0.585`$ (Table 1). Mg depletion in PNs is well established. For example, in the galactic PN NGC 3918, Harrington, Monk, & Clegg (1988) find depletion by a factor of 3. Dopita et al. (1997) find Mg depletion by a factor of $`20`$ in PNs in the Magellanic Clouds and note that Mg is not expected to be formed or destroyed during the evolution of these PNs (since an ONeMg WD is not formed), and that the magnesium resides in dust grains which are not destroyed by the UV radiation of the central star. The depletion fraction we find, then, implies that the star was born with a Mg abundance of $`3`$ times the solar value. This is feasible, since the distance of NGC 7027 from the galactic center is similar to that of the sun, and it is close to the galactic plane. Mg abundance of $`3`$ times solar are found in the solar neighborhood and closer to the galactic center (e.g., Smartt et al. 2001).

In addition, a high Mg abundance due to destruction of dust is unlikely because the destruction time of the dust in this PN is likely to be longer than the time elapsed since the star left the AGB, which we deduce in the following way. The destruction time of dust particles in the temperature range $`5\times 10^5K<T_x<5\times 10^7K`$ depends weakly on the temperature (Draine & Salpeter 1979; Smith et al. 1996). However, the destruction time depends on the grain size. For the PN NGC 3918, for example, Harrington et al. (1988) find that $``$ 50% of the dust mass is in dust particles of size $`a>0.1\mu \mathrm{m}`$. In NGC 7027, the dust grains may be much larger, with sizes of $`a>0.1\mu \mathrm{m}`$, and up to $`a520\mu \mathrm{m}`$ (Sanchez Contreras et al. 1998). Scaling from Draine & Salpeter (1979) for values appropriate here, in particular grain sizes of $`0.1\mu \mathrm{m}`$ (Jura 1996), we find the destruction time of dust in NGC 7027 is longer than

$$\tau _d1500\left(\frac{n_e}{150\mathrm{c}\mathrm{m}^3}\right)^1\left(\frac{a}{0.1\mu \mathrm{m}}\right)\mathrm{yr}$$

For an ISM distribution of grain sizes the destruction time at a pressure of $`P10^9`$ cm-3 K, as in the X-ray emitting gas of NGC 7027, is $`2500`$ yr, according to the calculation of Smith et al.(1996). The nebular dust cannot be destroyed in the shock, since the shock moving through the optical-nebular gas is relatively slow. The dynamical age of NGC 7027 is $`<1000`$ yr (Masson 1989; Latter et al. 2000). We conclude that the dust can’t be destroyed, even if the nebular gas is heated to $`10^7`$ K. Because the dust cannot be destroyed for this PN, we speculate that the X-ray emitting gas results from wind segments which never formed dust. These segments could result either from a post-AGB wind or a CFW blown by an accreting companion (for discussion of these possibilities see Soker 2002).

We would like to thank our referee, Dr. R. Corradi for his thoughtful comments. H.M. was supported by the NSF REU program at SAO. S.D.V. was supported in part by NASA Grant NAG5-6711. J.H.K. acknowledges support for this research provided by NASA/CXO grants GO0–1067X and GO2-3009X to RIT. N.S. acknowledges support from the US-Israel Binational Science Foundation and the Israel Science Foundation.

## 5 References

Aller, L. H. & Hyung, S. 1995, MNRAS, 276, 1101

Arnaud, K., Borkowski, K. J., & Harrington, J. P. 1996, ApJ, 462, L75

Bachiller, R.; Forveille, T.; Huggins, P. J.; Cox, P.; Maillard, J. P. 2000, A&A 353, L5

Bernard Salas, J., Pottasch, S. R., Beintema, D. A., & Wesselius, P. R. 2001, A&A, 367, 949

Beintema, D. A. et al. 1996, A&A, 315, L253

Corradi, R. L. M., Ferrer, O. E., Schwarz, H. E., Brandi, E., & Garcia, L. 1999, A&A, 348, 978

Corradi, R. L. M., Livio, M., Balick, B., Munari, U., & Schwarz, H. E. 2001, ApJ, 553, 211

Dopita, M. A. et al. 1997, ApJ, 474, 188

Draine, B. T. & Salpeter, E. E. 1979, ApJ, 231, 77

Garmire, G. P., Nousek, J., Burrows, D., Ricker, G., Bautz, M., Doty, J., Collins, S., & Janesick, J. 1988, Proc. SPIE, 982, 123

Grevasse, N. & Sauval, A. J. 1998, Space Science Reviews, 85, 161

Grosdidier, Y., Acker, A.i, & Moffat, A. F. J. 2000, A&A, 364, 597

Harrington, J. P., Monk, D. J., & Clegg, R. E. S. 1988, MNRAS, 231, 577

Hasegawa, T., Volk, K., & Kwok, S. 2000, ApJ, 532, 994

Jura, M. 1996, ApJ, 472, 806

Kastner, J., Li, J., Vrtilek, S., Gatley, I., Merrill, K., & Soker, S. 2002, ApJ, in press

Kastner, J., Soker, N., & Rappaport, S. 2000, ASP Conference Series, Vol. 199. Eds. J. H. Kastner, N. Soker, and S. Rappaport

Kastner, J. H., Soker, N., Vrtilek, S. D., & Dgani, R. 2000, ApJ, 545, L57

Kastner, J. H., Vrtilek, S. D., & Soker, N. 2001, ApJ, 550, L189

Keyes, C. D., Aller, L. H., & Feibelman, W. A. 1990, PASP, 102, 59

Kwok, S., Purton, C. R., & Fitzgerald, P. M. 1978, ApJ, 219, L125

Latter, W. B., Dayal, A., Bieging, J. H., Meakin, C., Hora, J. L., Kelly, D. M., & Tielens, A. G. G. M. 2000, ApJ, 539, 783

Masson, C. R. 1989, ApJ, 336, 294

Mewe, R., Lemen, J.R., & van den Oord, G.H.J. 1986, A&AS, 65, 511

Middlemass, D. 1990, MNRAS, 244, 294

Mikolajewska, J., Brandi, E., Hack, W., Whitelock, P., A., Barba, R., Garcia, L., & Marang, F. 1999, MNRAS, 305, 190

Pwa, T. H., Pottasch, S. R., & Mo, J. E. 1986, A&A, 164, 184

Sanchez Contreras, C., Alcolea, J., Bujarrabal, V., & Neri, R. 1998, A&A, 337, 233

Smartt, S. J., Venn, K. A., Dufton, P. L., Lennon, D. J., Rolleston, W. R. J., & Keenan, F. P. 2001, A&A, 367, 86

Smith, R. K., Krzewina, L. G., Cox, D. P., Edgar, R. J., & Miller, W. W. I. 1996, ApJ, 473, 864

Soker, N. 2002, MNRAS, 330, 481

Soker, N. & Kastner, J. H. 2003, ApJ, in press, (astro-ph/0209139)

Soker, N. & Rappaport, S. 2000, ApJ, 538, 241

Starrfield, S., Truran, J. W., Wiescher, M. C., & Sparks, W. M. 1998, MNRAS, 296, 502

Table 1: Abundances used in fits

|  | NGC 7027 | | BD+30o3639 | | |
| --- | --- | --- | --- | --- | --- |
| Element | BSPBWa | This paperb | AHc | ABHd | This papere |
| He | 1.08 | 1.08 | 1 | 1 | 1 |
| C | 1.69 | 1.69 | 1.1 | 354 | 354 |
| N | 1.71 | 1.71 | 1.0 | 9.1 | 9.1 |
| O | 0.55 | 9.2$`\pm 2`$ | 0.44 | 1.26 | 4.2$`\pm 0.3`$ |
| Ne | 0.83 | 0.83 | 0.01 | 10.5 | 19.3$`\pm 1.4`$ |
| Na | 0.58 | 0.58 | 1 | 1 | 1. |
| Mg | 0.58 | 3.0$`\pm 1`$ | 1 | 1 | 1. |
| Si | 0.17 | 0.17 | 1 | 1 | 1 |
| S | 0.51 | 0.51 | 0.33 | 1 | 1 |
| Ar | 0.63 | 0.63 | 0.05 | 1 | 1 |
| Fe | 1 | 1 | 1 | 0 | 0 |
| $`\chi _\nu ^2`$ | 2.0 | 0.9 | 9.3 | 2.1 | 1.2 |

aBernard Salas et al. (2001) nebular abundances.

bAs in BSPBW but with abundances for O and Mg allowed to be free.

cAller & Hyung (1995) nebular abundances.

dArnaud et al. (1996) stellar wind abundances.

e As in ABH but with O and Ne allowed to be free.