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# Modified spin-wave study of random antiferromagnetic-ferromagnetic spin chains

## I Introduction

The renormalization group (RG) approach of Wilson wilson74  provided a framework in which to understand the behavior of various phases of thermodynamic systems in terms of trajectories and RG flows in Hamiltonian space. In addition, it provided a scheme, to calculate, in principle, the behavior in the vicinity of critical and fixed points, by linearizing the flow equations. The method has proved to be powerful in providing an understanding of uniform (translationally invariant) systems, an exact implementation of the Wilson method in systems with quenched random disorder has been relatively restricted. Thus, for example, while the method has been successfully applied to the Anderson localization problem in ($`2+ϵ`$) dimensions, wegner76  generalization to include electron-electron interactions belitz94  have had limited success, because of the complications such as the existence of local moments milovanovic89 ; bhatt92  which are left out in such long-wavelength approaches to the problem. Another class of problems where a large amount of work has been done dhbb  is based on the random antiferromagnetic (AF) spin-1/2 chain in one dimension, where it has been shown fisher94  that a perturbative real space renormalization group (RSRG) scheme becomes asymptotically exact, as has been explicitly verified in a number of cases, such as the random XY chain, where it can be mapped on to a model of free fermions. mckenzie96

Another issue where less attention has been given, is the range of validity of the asymptotic results of the linearized RG equations. In most models of uniform systems, a few iterations of the RG equations leads to the vicinity of the appropriate fixed point. Consequently, a study of the RG trajectory from the region in the vicinity of an critical fixed point to a stable fixed point, usually yields a relatively quick crossover behavior. However, in a study of a three dimensional model related to the 1D random AF chain, bhatt82  it was found that the system did not settle down to a fixed-point-like behavior over several orders of magnitude in temperature; instead there was a slow, logarithmic in temperature, evolution in the behavior. Indeed, it has been claimed recently motrunich00  that the true low temperature behavior of the model is likely different. Unfortunately, such a change cannot be experimentally investigated, because smaller terms in the full Hamiltonian (such as hyperfine coupling to nuclear spins), and dipolar couplings, which have been neglected in the idealized model, will modify the behavior at such (exponentially low) temperatures. Nevertheless, it raises the issue that in models with quenched disorder, the true asymptotic fixed point behavior, may not be practically reached, at least in some cases, making “relevant” (in the RG sense) irrelevant in any practical sense. It is therefore of considerable interest to examine models with quenched disorder where crossovers between short length scale and long length scale behavior can be studied in some detail.

One model, which has received extensive attention in recent years, is the random antiferromagnetic-ferromagnetic (AFM-FM) spin chain. furusaki94 ; westerberg95 ; furusaki95 ; westerberg97 ; hida97 ; frischmuth97 ; frischmuth99 ; hikihara99  The study of such systems has been motivated by the discovery of novel one-dimensional (1D) random spin systems. One example of such materials is Sr3CuPt1-xIrxO6nguyen96  alloy of the pure compounds Sr3CuPtO6 (antiferromagnet) and Sr3CuIrO6 (ferromagnet). Such a system is interesting due to the interplay between quantum fluctuations and disorder; the latter can not be treated as a perturbation, as it is often found to change the low-energy spectra dramatically or even to destabilize the pure phases. Theoretical and numerical methods used to study random antiferromagnetic-ferromagnetic spin chains have been largely inherited from the study of random antiferromagnetic (AFM) chains (with AFM coupling only). ma79 ; fisher94 ; hyman96  In particular, the real-space renormalization group (RSRG) approach westerberg95 ; westerberg97  revealed a Curie-like temperature dependence in the susceptibility of a random AFM-FM spin-1/2 chain at low temperatures. In the RSRG picture, the Curie behavior occurs because spins correlate, due to the existence of ferromagnetic couplings, to form clusters whose average size and effective spin grow in a random walk fashion at low temperatures. Therefore, the random AFM-FM spin-1/2 chain belongs to a different universality class from that of the random AFM spin-1/2 chain, whose ground state is known as a random singlet phase, in which singlets can be formed over large distance. The RSRG results have been supported by various other numerical techniques, such as quantum Monte Carlo (QMC) simulation frischmuth97 ; frischmuth99 ; ammon99  and density matrix renormalization group (DMRG) method. hida97 ; hikihara99

In the RSRG method, one decimates the spins that are coupled by the strongest coupling in the system, and renormalizes the couplings among the remaining spins perturbatively. In this procedure new effective couplings and effective spins may also be generated. This procedure, which in general lowers the overall energy scale of the problem at hand, is repeated so that excitations at lower and lower energy scales are probed. Its quantitative accuracy relies on the presence of strong randomness, as in the case of strong randomness the strength of the strongest and typical couplings are well separated, ensuring the accuracy of a perturbative calculation. In real systems, however, the randomness can be very weak, especially when it is not introduced intentionally. In this case the RSRG is not expected to be quantitatively reliable in its early stages. It has been arguedfisher94 ; westerberg97  that the strength of disorder grows as the energy scale is lowered, thus in the low-energy (or equivalently, low-temperature) limit, the RSRG results become correct or even asymptotically exact. Nevertheless in this case one expects the thermodynamic properties of the system to be dominated by the physics of the pure chains at high temperature, and crossover to the randomness dominated regime (where the RSRG results apply) at very low temperatures.

In the present work we study the thermodynamic properties of the random AFM-FM chain, with mostly uniform FM coupling and a small concentration of (impurity) AFM bonds, using the modified spin-wave method. We also compare the results of modified spin-wave method with those of exact diagonalization in small systems to demonstrate the accuracy of the former. Our motivation comes from the following considerations. First of all, as discussed above, when the concentration of the impurity bonds is small, the randomness is rather weak and the RSRG results are not reliable at high temperatures. The modified spin-wave method allows us to treat the high and low temperature regimes on equal footing, and in particular, address the crossover between these two regimes. This makes it possible to compare theory with experiments for the entire temperature range, when the randomness is weak. Secondly, the modified spin-wave method has so far been applied to study pure spin models only. While very successful in those cases, it has not yet been used to study random spin systems. By working out a number of technical issues that one faces when applying it to random spin problems, and demonstrate its accuracy in the present problem, we lay the ground for the application of this powerful method to other random spin problems. Thirdly, as discussed in the opening paragraphs, it is of general interest to study models where the short distance (high temperature) and long distance (low temperature) behavior are controlled by different fixed points in the renormalization group sense, and address the crossover between the two limiting cases quantitatively; our model is such an example, and we hope our study will stimulate future research on this important issue.

Our results are summarized as follows. We find that the spin susceptibility of our system follows that of a pure ferromagnetic chain at high temperatures, and crosses over to $`1/T`$ dependence at low temperatures predicted by the RSRG, with a coefficient that agrees with the RSRG result essentially exactly. We also find that the crossover temperature depends mainly on the impurity bond concentration, while the width of the crossover depends mainly on the impurity bond strength; we determine their dependences semiquantitatively. We also demonstrate that the results of the modified spin-wave method is asymptotically exact in certain limiting cases, and quite accurate in the entire temperature range by comparing them with exact diagonalization results in the systems.

The paper is organized as follows. In Sec. II, we describe the model we study, as well as the qualitative physics expected from the model. In Sec. III, we introduce the modified spin-wave theory for the random AFM-FM spin chains. We present the numerical results of the theory in Sec. IV, with emphasis on the effects impurity bond strength, impurity concentration, as well as finite-size effects of our numerical study on the spin susceptibility. Finally, our results are summarized in Sec. V. Readers interested in the comparison of the modified spin-wave theory to exact diagonalization results will find details in Appendix A and B for simple cases like single ferromagnetic segment and two coupled segments.

## II The qualitative picture

We consider the following Hamiltonian for a random spin-$`S`$ chain

$$H=\underset{i}{}J_i𝐒_i𝐒_{i+1},$$
(1)
where the coupling strength $`J_i`$ is randomly chosen according to the distribution

$$P(J)=(1p)\delta (J+J_F)+p\delta (JJ_{AF}).$$
(2)
$`J_F`$ and $`J_{AF}`$ are the coupling strengths of the ferromagnetic and antiferromagnetic bonds, respectively. $`p`$ is the concentration of the antiferromagnetic impurity bonds. We are primarily interested in the dilute doping regime, i.e., $`p1`$, so that we have long ferromagnetic spin segments, separated by antiferromagnetic bonds. The number of spins in a spin segment ($`N_s`$) is random, with an exponential distribution

$$P(N_s)=p(1p)^{N_s1}.$$
(3)
Therefore, the average number of spins per segment is $`N_s=1/p`$. From real space renormalization group studiesma79 ; bhatt82 , we understand that a strong antiferromagnetic bond tends to lock the two adjacent spins into a singlet (which is inert at temperatures of interest), and the singlet thereby generates a weaker effective AF coupling between the two spins next to the singlet (see Appendix B). Therefore, for simplicity, we consider weak antiferromagnetic coupling ($`J_{AF}<J_F`$) only without losing generality.

The temperature dependence of magnetic susceptibility $`\chi `$ per spin is qualitatively known. We assume the Zeeman term $`H^{}=\mu H_zS_i^z`$ and set $`\mu =k_B=1`$ for simplicity. At high temperatures ($`TJ_F`$), the spins behave independently. Therefore, we expect an ordinary Curie contribution of

$$\chi _{HT}=\frac{S(S+1)}{3T},$$
(4)
from each spin. When $`TJ_F`$, the spins within each ferromagnetic segment become correlated. Takahashi takahashi85  obtained the following low temperature expansion for spin-1/2 ferromagnetic chain (of infinite length)

$$\chi _{FM}=\frac{1}{4}\left[\frac{0.1667J_F}{T^2}+\frac{0.581J_F^{1/2}}{T^{3/2}}+\frac{0.68}{T}+O\left(T^{1/2}\right)\right]$$
(5)
using the Bethe-ansatz integral equations. The factor of $`1/4`$ is added here due to an extra factor of 2 in the Zeeman energy terms in the original paper. Therefore, susceptibility of each segment rises as temperature decreases, crossing over from $`1/T`$ to $`1/T^2`$. In the case of $`J_{AF}=0`$, $`\chi `$ crosses over back to Curie behavior at lower temperatures, when each segment of finite length acts like a block spin with frozen internal excitations. When $`T`$ drops below the typical spin-wave excitation gap of a typical segment

$$\mathrm{\Delta }_{SW}J_FS\left(\frac{2\pi }{\overline{N}_s}\right)^2,$$
(6)
we expect

$$\chi _{BS}\frac{c_{BS}}{T}=\frac{1}{N}\underset{s}{}\frac{N_sS(N_sS+1)}{3T}.$$
(7)
Here $`\overline{N}_s`$ is the typical length of a ferromagnetic segment. In the thermodynamic limit, we obtain the Curie constant for locked block spins to be

$$c_{BS}=\frac{S^2}{3}\frac{2p}{p}+\frac{S}{3},$$
(8)
using segment-size distribution in Eq. 3. At $`p=0.1`$, we obtain $`c_{BS}=7/4`$ for $`S=1/2`$. $`c_{BS}`$ decreases with increasing impurity concentration $`p`$ and is always (unless $`p=1`$, i.e. in the pure antiferromagnetic case) greater than the high temperature Curie constant (in Eq. 4)

$$c_{HT}=\frac{S(S+1)}{3}=\frac{1}{4},\mathrm{for}S=\frac{1}{2},$$
(9)
expected at high temperatures.

When the end spins of neighboring segments are coupled with weak antiferromagnetic coupling $`J_{AF}`$, the block spins (originating from the ferromagnetic segments) interact with weak effective couplings. For two segments with $`N_1`$ and $`N_2`$ spins, we obtain the effective coupling

$$J^{}=\frac{J_{AF}}{N_1N_2},$$
(10)
by projecting the coupling to the block-spin space using Wigner-Eckart theorem. Not surprisingly, long segments are weakly coupled. In the RSRG approach,furusaki95  one starts with two strongly coupled segments and decimates the segments to a $`S^{}=|N_1N_2|S`$ spin, and renormalize its couplings with neighboring segments. The spin-wave excitations within each segment, considered in our modified spin-wave approach, are in general neglected in the RSRG approach, which is, therefore, valid only at low enough temperatures. By including these spin-wave excitations, we can not only demonstrate that the Curie susceptibility (predicted by RSRG) in a AFM-FM spin-1/2 chain at low temperatures is indeed the result of correlated ferromagnetic segments, but estimate the temperature scale at which the low temperature Curie behavior occurs as well. Since the renormalized couplings may become ferromagnetic, clusters start to grow in a random walk fashion as segments couple to neighboring segments as we lower the temperature. As in a typical random walk problem, we expect the average spin $`\overline{S}_l`$ and the average size $`\overline{l}`$ of such clusters of spins satisfy

$$\overline{S}_l\overline{l}^{1/2},$$
(11)
so that as far as magnetic susceptibility per spin $`\chi `$ is concerned, the scaling behavior of $`\overline{S}_l^2`$ and $`\overline{l}`$ cancels, leading to

$$\chi _{LT}=\frac{c_{LT}}{T}=\frac{1}{3T}\frac{\overline{S}_l^2}{\overline{l}}\frac{1}{T}.$$
(12)
By statistical analysis,westerberg97  one finds the low-temperature Curie constant to be

$$c_{LT}=\frac{S^2}{3}\frac{1p}{p},$$
(13)
in the large cluster-size limit. This result coincides with the classical result for the susceptibility per spin at low temperatures. furusaki94 ; nguyen96  Compared with Eq. 8, we find that antiferromagnetic impurity bonds reduce the low-temperature Curie constant by

$$\mathrm{\Delta }c=c_{BS}c_{LT}=\frac{S^2}{3p}+\frac{S}{3}.$$
(14)
On the other hand, for small $`p`$ (or low concentration of AF bonds), we have $`c_{LT}>c_{HT}`$; this simply reflects the fact that the dominant interaction in the system is ferromagnetic, which enhances spin susceptibility. Thus in the cases we are interested in, we have

$$c_{HT}<c_{LT}<c_{BS}.$$
(15)
We should note here that unless $`J_{AF}`$ is very small, there may not be a temperature range in which $`\chi \chi _{BS}=c_{BS}/T`$; this is because the neighboring segments can start developing correlations due to $`J_{AF}`$ before the intrasegment spin-wave excitations are frozen out by temperature. We will actually study mostly this case in this work, and focus mainly on the crossover from the pure ferromagnetic chain behavior directly to the asymptotic low temperature behavior with $`c_{LT}`$ as the Curie coefficient. We do this partly because in real systems $`J_{AF}`$ is often comparable to $`J_F`$, and partly for the sake of simplicity. Our method, however, is capable of handling very small $`J_{AF}`$ and the regime with $`c_{BS}`$ being the Curie coefficient.

## III The modified spin-wave approach

The conventional spin-wave theory gives the exact spin-wave spectra of Heisenberg ferromagnets at $`T=0`$. At finite temperature however, the theory leads to difficulty in one-dimensional quantum ferromagnets, the number of spin waves diverges when external magnetic field goes to zero. This difficulty has its root in the Mermin-Wagner theorem, which dictates that there cannot be long-range order in 1D at finite temperature. By imposing a constraint that the total magnetization be zero (thus fulfilling the Mermin-Wagner theorem), Takahashitakahashi86  introduced a chemical potential (equivalence to a uniform magnetic field) for the spin waves and successfully obtained the low-temperature properties of the ferromagnets in one dimension, as well as in two dimensions. The beauty of this modified spin-wave theory is that it gives correct asymptotic thermodynamic behavior at both large and zero temperature limit, as well as fairly accurate crossover behavior at intermediate temperatures. The modified spin-wave theory have further succeeded in two-dimensional antiferromagnetstakahashi89 ; tang89  and one-dimensional ferrimagnets.yamamoto98  For one-dimensional antiferromagnets, the modified spin-wave theory predicted a gap in the spin-wave spectrum,rezende90  consistent with the Haldane gap in integer-spin chains.haldane83

In this paper, we extend its applicability to ferromagnetic spin chains with dilute antiferromagnetic impurities. In the dilute impurity limit, a spin chain consists of ferromagnetic spin segments, coupled antiferromagnetically. The application of the modified spin-wave theory to the random antiferromagnetic-ferromagnetic spin chains is, therefore, mainly based on our observation that ferromagnetic spin segments can be well described by the modified spin-wave theory (see Appendix A). We found that, for magnetic susceptibility of a finite spin chain, the modified spin-wave theory gives noticeable difference from the exact diagonalization result only at two temperature crossovers. The crossover at higher temperatures describes the switching on of the couplings between individual spins, which is of little interest in the competition between different segments. On the other hand, the maximum error of the modified spin-wave theory is roughly 5%, for a chain of up to 14 spins, near the lower-temperature crossover when the spin chain becomes locked into one block spin. For a finite spin chain, the translational symmetry is broken. Therefore, one, in principle, needs to introduce a local chemical potential (or a local field) for each spin to ensure the magnetic moment of the spin be zero. Fortunately, we can apply a periodic boundary condition to each ferromagnetic spin segment, so that only one chemical potential is needed throughout the segment. We emphasize that the use of periodic boundary condition reduces the computational complexity without changing the essential physics. This is particularly true when we have very dilute impurities so that the average ferromagnetic segment length is large.

For the nearest-neighbor Heisenberg Hamiltonian, Eq. 1, we apply Holstein-Primakoff transformation

$$\{\begin{array}{ccc}S_i^{s+}\hfill & =\hfill & \sqrt{2Sa_i^sa_i^s}a_i^s,\hfill \\ S_i^s\hfill & =\hfill & a_i^s\sqrt{2Sa_i^sa_i^s},\hfill \\ S_i^{sz}\hfill & =\hfill & Sa_i^sa_i^s.\hfill \end{array},$$
(16)
for segments with odd index $`s`$, and

$$\{\begin{array}{ccc}S_i^{s+}\hfill & =\hfill & a_i^s\sqrt{2Sa_i^sa_i^s},\hfill \\ S_i^s\hfill & =\hfill & \sqrt{2Sa_i^sa_i^s}a_i^s,\hfill \\ S_i^{sz}\hfill & =\hfill & a_i^sa_i^sS.\hfill \end{array},$$
(17)
for segments with even index $`s`$. This way, we introduce a distinct species of boson for each segment. The Hamiltonian, in the linear spin-wave approximation, becomes

$`H=E_0`$ $`+`$ $`J_FS{\displaystyle \underset{s=1}{\overset{M_s}{}}}{\displaystyle \underset{i=1}{\overset{N_s}{}}}\left(a_i^sa_i^s+a_{i+1}^sa_{i+1}^sa_i^sa_{i+1}^sa_{i+1}^sa_i^s\right)`$ (18)
$`+`$ $`J_{AF}S{\displaystyle \underset{s=1}{\overset{M_s1}{}}}\left(a_{N_s1}^sa_{N_s1}^s+a_1^{(s+1)}a_1^{(s+1)}+a_{N_s1}^sa_1^{(s+1)}+a_1^{(s+1)}a_{N_s1}^s\right),`$
where $`M_s`$ is the number of ferromagnetic segments, and $`N_s`$ the number of spins in the $`s`$-th segment. The total number of spins is, therefore, $`N=_{s=1}^{M_s}N_s`$. Note $`(N_s+1)0`$, reflecting the periodic boundary condition imposed on each segment.

In the linear spin-wave approach, the quadratic Hamiltonian is soluble by a generalized Bogoliubov transformation for bosons, a generalization of Ref. colpa78, . The procedure can be written compactly in a matrix format. Denote the original boson operators by a vector

$$x=(a_1^1,a_2^1,\mathrm{},a_{N_1}^1,a_1^2,a_2^2,\mathrm{},a_{N_2}^2,\mathrm{})^T.$$
(19)
The Hamiltonian can be written as

$$H=const.+x^{}x,$$
(20)
where

$$=J_FS\left(\begin{array}{cccccccccc}2& 1& & 1& & & & & & \\ 1& 2& \mathrm{}& & & & & & & \\ & \mathrm{}& \mathrm{}& 1& & & & & & \\ 1& & 1& 2+J_{AF}/J_F& J_{AF}/J_F& & & & & \\ & & & J_{AF}/J_F& 2+J_{AF}/J_F& 1& & 1& & \\ & & & & 1& 2& \mathrm{}& & & \\ & & & & & \mathrm{}& \mathrm{}& 1& & \\ & & & & 1& & 1& 2+J_{AF}/J_F& J_{AF}/J_F& \\ & & & & & & & J_{AF}/J_F& 2+J_{AF}/J_F& \mathrm{}\\ & & & & & & & & \mathrm{}& \mathrm{}\end{array}\right),$$
(21)
is a $`N\times N`$ matrix. The Hamiltonian matrix is basically a 3-diagonal matrix, with extra (-1)’s at the corners of each block (of a spin segment). The rest of the matrix elements (left unspecified in Eq. 21) are zeros. Introduce the generalized Bogoliubov transformation:

$$x=V\gamma ,$$
(22)
where $`V`$ is a $`N\times N`$ matrix and $`\gamma `$ a vector of the set of boson operators ($`\alpha `$’s)

$$\gamma =(\alpha _1^1,\alpha _2^1,\mathrm{},\alpha _{N_1}^1,\alpha _1^2,\alpha _2^2,\mathrm{},\alpha _{N_2}^2,\mathrm{})^T,$$
(23)
that diagonalizes $``$, i.e.,

$$V^TV=E,$$
(24)
in the compact matrix format, where $`E`$ is a diagonal matrix,

$$E_{N\times N}=diag(\epsilon _1^1,\epsilon _2^1,\mathrm{},\epsilon _{N_1}^1,\epsilon _1^2,\epsilon _2^2,\mathrm{},\epsilon _{N_2}^2,\mathrm{},\epsilon _{N_{M_s}}^{M_s})$$
(25)
with its diagonal elements being the energies of the corresponding bosons after the Bogoliubov transformation. The boson commutation relation requires

$$VPV^T=P,$$
(26)
where $`P`$ is a generalized para unit matrix (inheriting the notation from Ref. colpa78, ) of the form

$$P_{N\times N}=diag(\stackrel{N_1}{\stackrel{}{1,1,\mathrm{},1}},\stackrel{N_2}{\stackrel{}{1,1,\mathrm{},1}},\mathrm{})$$
(27)
For fermions, on the other hand, the fermionic commutation relations lead to the orthonormalization condition, which can assume the same equation as Eq. 26, except that $`P`$ becomes an $`N\times N`$ unit matrix. We need to find out a solution $`V`$ for bosons, which simultaneously satisfies Eq. 24 and 26; this can be done with the help of generalized matrix diagonalization. Unlike fermionic diagonalization, the existence of such a solution is not guaranteed, unless spin segments are decoupled, i.e. $`J_{AF}=0`$. Such unfortunate situations are, in general, associated with modes of zero energy, which then leads to divergent number of bosons (or divergent magnetization). In the case of a single ferromagnetic chain, Takahashi takahashi86  introduced a chemical potential (or a magnetic field) to overcome the difficulty. In this case, we need to introduce to the Hamiltonian a set of $`M_s`$ local chemical potentials, one for each segment, to find a solution. These chemical potentials are chosen such that the magnetization of each spin segment (equivalently, of each spin with periodic boundary condition) is zero. These constraints, which have the physical significance of restoring the rotational symmetry, ensure that the number of bosons be finite at finite temperatures. The thermodynamic quantities can be calculated from the excitation energies $`\epsilon `$’s and the transformation matrix $`V`$. In particular, magnetic susceptibility per site $`\chi `$ can be written as

$$\chi =\frac{1}{3TN}\underset{s=1}{\overset{M_s}{}}\underset{i=1}{\overset{N_s}{}}\stackrel{~}{n}_i^s\left(\stackrel{~}{n}_i^s+1\right),$$
(28)
where $`\stackrel{~}{n}_i^s`$ is the occupation number for the boson correspond to operator $`\alpha _i^s`$ and excitation energy $`\epsilon _i^s`$,

$$\stackrel{~}{n}_i^s=\alpha _i^s\alpha _i^s=\frac{1}{e^{\epsilon _i^s/T}1}.$$
(29)
## IV Results for magnetic susceptibility

Figure 1 shows the static magnetic susceptibility $`\chi `$ per spin of a 600-spin ferromagnetic chain, with 59 antiferromagnetic impurity bonds, which divide the chain into 60 ferromagnetic segments, i.e., $`p=0.1`$. The impurity bonds ($`J_{AF}=0.5`$) are put randomly with the constraint that the total magnetization of the corresponding classical ground state is zero. This guarantees that $`\chi `$ drops to zero at zero temperature. The susceptibility curve shows three temperature regimes. For $`T/J_F>3`$, result can be fit to a high-temperature Curie law (Eq. 4), suggesting that spins behave independently. For $`0.2<T/J_F<3`$, $`\chi `$ rises with decreasing temperature, following Eq. 5. This implies that spins start to correlate, forming independent ferromagnetic segments. The antiferromagnetic coupling is still too weak to affect thermodynamics of the random spin chain at these temperatures. Below $`T=0.2J_F`$, $`\chi `$ is in good agreement with

$$\chi =\frac{c_{LT}}{T},c_{LT}=\frac{3}{4},$$
(30)
the low-temperature Curie behavior expected by the RSRG approach (Eq. 13 for $`p=0.1`$). We point out that the Curie constant of independent block spins (Eq. 8) is expected to be $`c_{BS}=7/4`$ for $`p=0.1`$. Therefore, the low-temperature Curie constant is indeed reduced by antiferromagnetic couplings between ferromagnetic segments. We note that $`\chi `$ deviates from Eq. 30 below $`T=0.02J_F`$. We believe this is an artifact due to finite size (we have only 600 spins), since there are no more segments to decimate. $`\chi `$ bends down as we specially require that $`\chi `$ go to zero at zero temperature. Since the number of iterations required to find a solution for the generalized Bogoliubov transformation grows significantly at low temperatures (nearly 1000 iterations at $`T=0.005`$), we were unable to approach temperatures much lower than $`T=0.01`$ or to calculate many samples on our regular workstations. It is worth pointing out that we can identify the crossover temperature from the ferromagnetic spin-chain physics to random spin-chain physics as the cross point of Eq. 30 and 5. In the dilute doping limit (small $`p`$), we have

$$T_x=J_F\frac{p}{1p}\left[0.50+3.04\sqrt{\frac{p}{1p}}+O\left(\frac{p}{1p}\right)\right]$$
(31)
For $`p=0.1`$, $`T_x=0.168J_F`$.

Figure 2 shows the susceptibility per spin $`\chi `$ of spin chains of 20, 30, and 40 ferromagnetic segments (i.e., with 19, 29, and 39 antiferromagnetic impurity bonds, respectively). The average ferromagnetic segment length is fixed at 8 spins ($`p=1/8`$), so that the lengths of the corresponding spin chains are 160, 240, and 320, respectively. The antiferromagnetic coupling $`J_{AF}`$ is chosen again to be 0.5. $`\chi `$ is averaged over 10-20 random realizations depending on size. For $`0.2<T/J_F<1`$, $`\chi `$ roughly follows the low-temperature (compared with $`J_F`$) expansion of a single ferromagnetic chain (Eq. 5). From now on, we neglect the thermodynamics at $`T>J_F`$ (although it is capable of being calculated within our theory), since it is trivial and not the interest of this paper. Below the crossover temperature $`T_x0.2`$, $`\chi `$ deviates from the pure chain susceptibility, and obeys a Curie law. The range of the Curie susceptibility extends to lower and lower temperature when we have more segments (from 20 to 40 in Fig. 2), therefore longer chain, for a fixed impurity concentration. At $`N_s=40`$, this range extends beyond one decade for $`p=1/8`$. We point out that the Curie constant obtained from Fig. 2 ($`c=0.67`$) is roughly 15% larger than predicted by Eq. 13. This should be viewed as a mixture of both the RSRG-predicted behavior and the ferromagnetic-chain physics. The reason will become clear later after we explore the impurity concentration dependence of the Curie behavior.

The antiferromagnetic coupling strength $`J_{AF}`$ determines the temperature scale at which the ferromagnetic segments couple to their nearest neighbors. The smaller $`J_{AF}`$ is, the lower the temperature at which RSRG results are valid becomes, leading therefore to an increasingly wider crossover from the physics of a pure ferromagnetic chain. Figure 3 shows the sample averaged magnetic susceptibility per spin $`\chi `$ for $`J_{AF}=0.3`$ and 0.5 for spin chains of 30 ferromagnetic segments. The average number of spins in each segment is 12 spins ($`p=1/12`$). The dashed line corresponds to a Curie constant $`c=11/12`$, expected by Eq. 13 for $`p=1/12`$. Although the system size (360 spins) is probably not large enough, one can nevertheless identify the Curie behavior for $`J_{AF}=0.5`$ around $`T=0.05`$ and for $`J_{AF}=0.3`$ around $`T=0.02`$. Note that $`\chi `$ for $`J_{AF}=0.3`$ is greater than that for $`J_{AF}=0.5`$ at low temperatures. This is expected because decimated spin segments, in the RSRG language, contribute less to the magnetic susceptibility than the sum of original segments, and because the decimation happens at lower temperatures for smaller $`J_{AF}`$. For very small $`J_{AF}`$, we expect the system crosses over from a ferromagnetic regime at high temperatures, first, to an (almost) independent block-spin regime at lower temperatures, characterized by a Curie constant as in Eq. 8. There is another crossover, at very low temperatures (dependent on $`J_{AF}`$), from the independent block-spin regime to the RSRG regime, characterized by a smaller Curie constant as in Eq. 13.

We have also studied the dependence of the magnetic susceptibility on the impurity concentration, or equivalently, average number of spins in each segment. Qualitatively, the larger number of spins within each segment increases the magnetic susceptibility per spin, since $`\chi N_s^2`$ for a ferromagnetic $`N_s`$-spin segment (for large $`N_s`$). As a consequence, the Curie constant is expected to increases with the average number of spins in each segment, or more precisely, as in Eq 13. This trend is shown in Fig. 4, where we plot the averaged susceptibility per spin for 30-segment spin chains, with 8, 12, and 16 spins per segment on average, respectively. The three dashed lines are the low-T Curie behavior the RSRG approach expected (Eq. 13). As is pointed out in earlier paragraph, our data is in significant disagreement with Eq. 13 for $`p=1/8`$. For $`p=1/16`$, one finds that $`\chi `$ follows Eq. 13 from $`T=0.015J_F`$ to $`0.04`$, the regime antiferromagnetic impurity bonds are dominating. The Curie regime shifts to $`0.02<T/J_F<0.08`$ for $`p=1/12`$. This is consistent with Eq. 10 that longer segments have relatively weaker effective intersegment coupling. The trend suggests that for $`p=1/8`$ the Curie regime would occur above $`T>0.1J_F`$, which coincides with the regime where intersegment coupling is important. Therefore, we believe the discrepancy between our data and Eq. 13 reveals a collective contribution from the ferromagnetism with each segment and the antiferromagnetism between segments. This demonstrates that inappropriate parameters can kill (or lead to the wrong) RSRG physics. We note that the crossover regime (deviating from both Eq. 4 and the $`1/T`$-law) becomes wider for smaller $`p`$. This is again consistent with the translation between low concentration and weak effective intersegment coupling, which, we have demonstrated, leads to wider crossover regime.

## V Conclusion

In the study of the random AFM-FM (nearly ferromagnetic) spin-1/2 chain, the modified spin-wave theory allows us to obtain the thermodynamic properties over a broad temperature range (on logarithmic scale). We have studied systems as large as 600 spins, with up to 60 ferromagnetic segments, for temperature ranges of over three orders of magnitude. At very high temperatures, the spins are independent; correlation starts to develop within each ferromagnetic segments as temperature drops, giving rise to characteristics of a pure ferromagnetic chain. At low temperatures, the observation of the Curie-like behavior reveals the regime where ferromagnetic segments are correlated into clusters, whose size grows with decreasing temperature. Therefore, we can study, fairly systematically, in the modified spin-wave theory the crossover between the high-temperature Curie behavior (independent spins) and low-temperature Curie behavior (correlated spin segments).

System size is important in observing the low-temperature Curie behavior, since it determines whether the RSRG scaling regime can be reached. Our study has found that the modified spin-wave theory gives results in accordance with the RSRG argument for chains of several hundred spins (after averaging over random bond distribution). The study of the effects of impurity bond strength shows that the low-temperature Curie regime can be consistently pushed to lower temperatures by decreasing the antiferromagnetic impurity bond strength.

In the dilute doping regime, we have studied the effects of impurity concentration on the low-temperature thermodynamics. The results are again in fairly good agreement with the RSRG prediction. The exception happens at higher concentration ($`p=1/8`$), where we believe the intrasegment ferromagnetic coupling and the intersegment antiferromagnetic coupling take actions at about the same temperature regime, leading to a mixed behavior which appears to look like a different Curie behavior. Further explorations using other methods would be very useful to confirm our explanation.

In our study, both weak impurity bonds and low impurity concentration give rise to a wide crossover from the ferromagnetic spin-chain regime to the random spin-chain regime. Although the modified spin-wave theory limits us to only a portion of the whole random spin-chain space, we believe such wide crossover can be generic and it can prevent the real RSRG behavior from being observed at reasonably low temperatures. In fact, the RSRG study of random spin chains westerberg97  has pointed out the possibility of having a crossover region of more than five orders of magnitude before the true RSRG scaling regime can be reached. A quantum Monte Carlo study of the random AFM-FM spin-1/2 chain ammon99  has confirmed that a region of weakly interacting spin segments can exist, whose crossover to the low-temperature scaling regime is marked by a (somewhat small) peak in the specific heat.

The main difficulty of directly comparing our results with experiments seem to be that quasi-1D Heisenberg ferromagnetic systems are rare since there usually exist interchain couplings which lead to three-dimensional (3D) ordering at low temperatures. For Sr3CuIrO6, long-range (presumably 3D) order develops at 20.1 K without signature of 1D magnetism. irons00  Recently, however, effects of magnetic impurities on the quasi-1D ferromagnetic spin chain have been reported for organic radical alloy, ($`p`$-CDpOV)1-x($`p`$-BDpOV)xmukai99  whose interchain-intrachain coupling ratio is as small as $`J^{}/J=3.7\times 10^3`$. This may open a door where the low-temperature Curie susceptibility of the RSRG origin can be observed in ferromagnetic bond dominated random spin chains.

## VI Acknowledgments

This work was supported by NSF grants No. DMR-9971541 (X.W. and K.Y.), No. DMR-9809483 (R.N.B.), the state of Florida (X.W.), and the Alfred P. Sloan Foundation (K.Y.)

## Appendix A Modified spin-wave theory for ferromagnetic spin segments

In Takahashi’s original paper takahashi86 , the modified spin-wave theory is aimed at ferromagnetic spin chains with infinite length. Nevertheless, the theory can be easily applied to a finite-size ferromagnetic spin chain with periodic boundary conditions. This only changes the continuous spin-wave spectrum to a discrete spectrum. Therefore, for an $`N`$-spin ferromagnetic chain, we can write the self-consistent equations for the single (global) chemical potential $`\mu `$:

$`NS`$ $`=`$ $`{\displaystyle \underset{k}{}}\stackrel{~}{n}_k,`$
$`\stackrel{~}{n}_k`$ $`=`$ $`{\displaystyle \frac{1}{e^{[ϵ(k)\mu ]/T}1}},`$ (32)
where the discrete spin-wave energy spectrum is

$$ϵ(k)=2JS(1\mathrm{cos}ka),k=\frac{2\pi i}{Na},i=0,1,\mathrm{},N1.$$
(33)
The magnetic susceptibility per spin can be expressed as

$$\chi =\frac{1}{3TN}\underset{k}{}\stackrel{~}{n}_k(\stackrel{~}{n}_k+1).$$
(34)
Analytical results, which turn out to be exact, can be obtained for both high and low temperature limit. In the high temperature limit, $`\stackrel{~}{n}_k=S`$ is a constant. Self-consistent Eqs. A give

$$\mu =T\mathrm{ln}\left(1+S^1\right).$$
(35)
Therefore, we have

$$\chi =\frac{S(S+1)}{3T},$$
(36)
which is the exact result for independent spins. In the low temperature limit, only $`k=0`$ mode can be excited, i.e. $`\stackrel{~}{n}_k=NS\delta _{k,0}`$. Self-consistent Eqs. A give

$$\mu =T\mathrm{ln}\left(1+N^1S^1\right).$$
(37)
Therefore, we have

$$\chi =\frac{S(NS+1)}{3T},$$
(38)
which is the exact result for the ferromagnetic ground state with maximum spin.

Figure 5 shows $`\chi `$ for ferromagnetic spin-1/2 chains of finite length $`N=4`$ and 14. The modified spin-wave theory results agree very well with exact results for both sizes. The largest descrepency (less than 15%) occurs around $`T=J_F`$, at which independent spins start to correlate. This regime is of less interest for the purpose of this paper. In both the high temperature limit ($`T>10J_F`$) and the low temperature limit ($`T<\mathrm{\Delta }_{SW}`$), the modified spin-wave theory gives exact results. This is a very impressive result since the spin-wave theory is in principle developed around $`T=0`$, describing the low temperature excitations of the ferromagnetic spin chain. In addition, we are able to show that boundary conditions have only weak effects on the rapidly changing susceptibility. In particular, behavior in the high temperature limit and the low temperature limit remains unchanged.

## Appendix B Coupling between two ferromagnetic spin segments

The problem of two ferromagnetic spin segment coupled by an antiferromagnetic bond is a special case of more general random spin chains. For small systems, we can compare our modified spin-wave theory with exact diagonalization. Figure 6 shows the susceptibility for two ferromagnetic segments ($`J_F=1`$) coupled with a $`J_{AF}=0.01`$ antiferromagnetic bond. The numbers of spins in the two segments are $`N_1=6`$ and $`N_2=7`$. Three regimes where the susceptibility obeys $`1/T`$-law are well-defined in Fig. 6. The corresponding pictures from high to low temperature are independent spins, two independent spin segments, completely locked spins, respectively. The susceptibility can be fit very well to the Curie law obtained from the simple pictures. In these Curie regimes, the modified spin-wave theory gives exact results. Discrepancies between the modified spin-wave results and exact results can only been noticed at the two crossover regimes between them. Crossover temperature scales can be roughly estimated by the smaller spin-wave gap $`\mathrm{\Delta }_{SW}`$ of the two segments and the effective antiferromagnetic coupling $`J^{}`$ between the two segments, as marked by arrows in Fig. 6.

In the RSRG scheme, one introduces an effective antiferromagnetic coupling $`J^{}`$ between the two segments, which replaces the coupling between the two neighboring end spins. By inspecting the energy spectrum of the two-segment system in Fig. 7, one can explore the validity of the replacement. At low enough temperatures ($`T<\mathrm{\Delta }_{SW}`$), the finite spin-wave excitations are frozen within each segment. Therefore, only $`k=0`$ modes are relevant when the two segments couple with the effective $`J^{}`$. This results a group of lowest energy levels ($`S=1/2`$, 3/2, …, 13/2), which are separated from higher energy levels by a energy gap ($`\mathrm{\Delta }_{SW}`$). The gap is expected to become comparable with the width of the $`k=0`$ energy levels, when $`J_{AF}`$ is close to $`J_F`$, when RSRG argument becomes less accurate. For small $`J_{AF}`$, these $`k=0`$ modes obtained from the exact diagonalization are in good agreement with the effective levels in the RG picture (the inset of Fig. 7). The difference in energy levels given by the two methods grows with increasing $`J_{AF}`$. Nevertheless, the agreement in the susceptibility obtained from the two methods still persists even when $`J_{AF}J_F`$, as long as $`T\mathrm{\Delta }_{SW}`$, which poses a temperature restriction on the RSRG scheme.


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# G-quartet biomolecular nanowires

## Abstract

We present a first-principle investigation of quadruple helix nanowires, consisting of stacked planar hydrogen-bonded guanine tetramers. Our results show that long wires form and are stable in potassium-rich conditions. We present their electronic bandstructure and discuss the interpretation in terms of effective wide-bandgap semiconductors. The microscopic structural and electronic properties of the guanine quadruple helices make them suitable candidates for molecular nanoelectronics.

Guanine (G) supramolecular systems receive great attention because of their peculiar structural and electronic properties: G molecules have the capability of forming a variety of self-assembled structures (helices, ribbons, tubes), both in solution and in the solid state garbesi ; acta , and G-rich DNA sequences exhibit efficient long-range electron transfer properties jortner . Among the different G aggregates, in this letter we focus on tubular sequences of G-quartets garbesi , whose formation is driven by the presence of alkali cations: such tubes are often labeled as G-quadruplexes or G-wires afm . The building block of a tube is the tetrameric G-quartet (G4) garbesi , which is a planar aggregate of four hydrogen-bonded guanines arranged in a square-like configuration, as shown in Figure 1a. Each G4 contains four carbonyl oxygen atoms pointing towards the center of the square. By stacking on top of each other, these tetramers form a tube-like column with a central cavity, that easily accomodates monovalent cations. X-ray and Nuclear Magnetic Resonance (NMR) data of both hydrophylic and lipophylic G-quadruplexes reveal that one cation is symmetrically located between any two G4 planes (Figure 1b), and coordinated with eight nearest-neighbor O atoms luisi ; gottarelli2 . G4 stacks exhibit a surprisingly high stability in different chemical conditions garbesi ; luisi ; gottarelli2 .

Besides the biochemical aspects garbesi , G-rich systems are attracting increasing interest in applied physics as functional elements in molecular electronics joachim . For example, guanine aggregates have been used to devise new conducting nanoscale materials, whose electronic features are typical of wide-gap semiconductors danny ; rinaldi . Whereas recognition is a fingerprint of all the nucleic acid bases, guanine plays a key role to enhance charge migration jortner ; schuster , because of its low ionization potential, and is suitable for electronic applications.

In this letter, we present a first-principle investigation of the structural and electronic properties of extended G-wires, free-standing or intercalated by K+ ions. Our results show that in K-rich conditions G4 helices are thermodinamically stable, consistently with X-ray and NMR experiments luisi ; gottarelli2 . Although the single-particle bandstructure identifies the localized character of the electron wavefunctions, the calculated density of states (DOS) is consistent with a model of a semiconducting nanowire, which hosts extended channels for electron/hole motion. The peaks in the effective band-like DOS result from the energy spreading of the single-molecule energy levels. To our knowledge, this is the first theoretical prediction of the electronic properties of the extended tubular G-wires.

We performed first-principle total-energy calculations based on a Car-Parrinello-like scheme fhi , with all the atoms free to relax towards the minimum energy configuration. The electronic structure is described in the frame of plane-wave pseudopotential DFT dft , using the BLYP blyp  exchange-correlation functional: this scheme gives a correct description of H-bonding in molecular systems water . The accuracy of the computational technique was tested on isolated G molecules and on self-assembled G-ribbons nastri . The quadruplexes are simulated by the use of periodically repeated supercells (24.3$`\times `$24.3$`\times `$10.1 Å3), containing three stacked C4-symmetric G4 tetramers (Figure 1b), separated by 3.4 $`\AA `$ and rotated by 30 (Figure 1c) along the stacking direction. The starting atomic configuration in our simulations was that resulting from the X-ray analysis of the G-quadruplex d(TG4T) luisi . Neighboring replicas of the basic structural unit are laterally separated by vacuum, while a continuous wire is formed with its axis perpendicular to the tetrameric planes. Theoretical studies showed that the external backbone in helical nucleotide structures is not involved in transport phenomena ladik . Thus, we believe that our calculations for the G4 stacks are well representative of principal electronic features of real systems.

We studied two different G4 columns: the tube containing K+ ions along the axis in the inner cavity is labeled 3G4/K+ nota , the empty tube is labeled 3G4. The formation energy $`E^{form}`$ of each system, relative to that of isolated G molecules, as a function of the Fermi level ($`E_F`$) and of the chemical potential of K ($`\mu ^K`$), may be calculated after a thermodynamic approach successful for the study of defects in semiconductors vandewalle , as

$$\mathrm{\Delta }E^{form}=\mathrm{\Delta }E^{tot}\mathrm{\Delta }n^K\mu ^K\mathrm{\Delta }n^eE_F.$$

Etot is the calcutated total energy, nK is the number of K atoms, ne is the number of excess electrons with respect to charge neutrality: for 3G4 (3G4/K+) $`\mathrm{\Delta }n^K=\mathrm{\Delta }n^e=0`$ ($`\mathrm{\Delta }n^K=+3`$, $`\mathrm{\Delta }n^e=3`$). In the formula, $`\mu ^K`$ and EF depend on the conditions under which the material is formed and must be determined on the basis of physical constraints. To obtain Figure 1d, we assumed $`\mu ^K=\mu _{bulk}^K`$, equivalent to fixing K-rich conditions. Under this assumption, the relative formation energy is a linear function of the Fermi level, and its slope is determined by the charge state $`\mathrm{\Delta }n^e`$. Figure 1d shows the relative formation energy of the isolated G molecules, the 3G4 and the 3G4/K+ wires, as a function of $`E_F`$: for a given value of $`E_F`$, the lowest energy curve identifies the most favorable phase. The plot reveals that the G columns are energetically favorable with respect to isolated guanine molecules, due to the stability effect of the several hydrogen bonds. The 3G4/K+ structure is more stable than the 3G4 structure for $`E_F`$ less than 1 eV: the energy gain is 1.8 eV/G4 for $`E_F`$=0. As we discuss in the following paragraph, the G-wires exhibit an energy bandgap between the HOMO and the LUMO, and the condition $`E_F`$=0 corresponds to pinning the Fermi level at the top of the occupied energy levels. This condition is consistent with the abundance of metal cations, that may act as electron acceptors. Under these circumstances, the high stability of the K+-containing columnar structures is in agreement with the experimental evidence that the quadruplexes form only in the presence of metal cations garbesi ; luisi ; gottarelli2 . We find that the empty 3G4 tube is unfavorable with repect to isolated G4 tetramers by 1.4 eV/G4, and the inclusion of K+ ions stabilizes the columnar phase also with respect to the free tetramers. We attribute this effect to electrostatic K+-O- interactions that counterbalance the strong K+-K+ repulsion stability . A K+ concentration smaller that 1/G4 would break this equilibrium and would not be sufficient to induce the formation of the G-wires. Our results agree with cluster quantum-chemistry calculations gu .

The electronic bandstructure of the 3G4/K+ tube is shown in the right panel of Figure 2, while the left panel illustrates the DOS of both the K+-filled (bottom) and the empty (top) tubes. For other G stacks nastri , $`\pi `$-$`\pi `$ coupling may give rise to delocalized Bloch-type orbitals, whose band dispersion depends on the relative rotation angle between nucleobases in adjacent planes. In the guanine quadruplexes, the C4 symmetry increases the spatial $`\pi `$-$`\pi `$ overlap with respect to a segment of G-rich B-DNA, and we might expect an enhancement of the band-like behavior. Instead, our results reveal a different mechanism. For both filled and empty G4 columns, we find that the inter-plane $`\pi `$ superposition is not sufficient to induce the formation of delocalized orbitals along the axis of the quadruplex: The right panel in Figure 2 shows that the bands of the 3G4/K+ column are flat, typical of supramolecular systems in which the orbitals remain localized at the molecules. The bandstructure identifies the presence of band-multiplets, each constituted of 12 energy levels. The 12 electron orbitals associated to a multiplet have identical character and localize on the 12 guanines in the unit cell. The energy levels in a multiplet are separated by an average energy difference of 0.02 eV, smaller than the room-temperature energy kBT: therefore, the coupling with the thermal bath allows the G-localized neighboring orbitals of a multiplet to interact, producing an effective delocalized orbital. The resulting DOS (Fig. 2), obtained with a gaussian broadering to the calculated one-electron energy eigenvalues, shows filled and empty effective bands, separated by a gap of 3.3 eV and 3.5 eV for the 3G4 and the 3G4/K+ tubes, respectively. Each of the five peaks labeled with letters in Figure 2 takes origin from one G orbital: For instance, peak a is the convolution of the $`\pi `$-like HOMO’s of the 12 unit guanines. The amplitude of this peak is 0.3 eV for both wires. The only meaningful difference that we note between 3G4 and 3G4/K+ is a downward shift of the $`\sigma `$-like peak b in 3G4/K+. By a comparative analysis of a similar shift for $`\sigma `$-like orbitals of the G-ribbons nastri , resulting upon the introduction of electrostatic interactions, we attribute the downward shift of the $`\sigma `$-like peak b in the 3G4/K+ tubes to the electrostatic attractive interaction induced by the inclusion of the K+ ions.

We show in Figure 3 countour plots of the HOMO convolution (peak a of the DOS) of 3G4/K+ in a plane containing (top) and perpendicular to (bottom) the axis of the quadruple helix. The side-view contour plot shows the formation of an extended orbital in the outer side of the nucleobase stack, due to C-N bonds, that constitutes a channel for electron mobility along the helical axis. The contour plots also reveal that the K species is fully ionized, and therefore the inner cavity of the column is free of charge. Thus, conductivity in the G-wires may not be attributed to metallic bonds between the K atoms, neither to their ionic motion, because of the high stability of the structure.

By means of first-principle calculations, we have demonstrated the stability of columnar structures based on guanine stacks, in the abundance of K+ ions. The $`\pi `$-$`\pi `$ coupling does not induce extended states and dispersive energy bands. However, the energy separation between neighboring localized states is so small that coupling can be easily induced, e.g., by room-temperature thermal hopping. Therefore, 3G4/K+ tubes under suitable conditions, are expected to exhibit an effective behavior of wide-bandgap semiconductors. This feature, along with the possibility of forming extended stacked wires at the nanoscale length, makes them appealing for the development of biomolecular electronics.

This work was supported by INFM through Progetto Calcolo Parallelo, and PRA-SINPROT.


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# Four New 𝛿 Scuti Pulsators from a Variability Survey of 131 Stars

## 1 Introduction

$`\delta `$ Scuti stars are pulsating A-type or F-type stars with mass $`M1.52.5M_{}`$ that lie in the classical Cepheid instability strip. They are usually on or near the main sequence (luminosity class V - III; Guzik 1997), and they pulsate radially, as well as non-radially in pressure (p) and sometimes gravity (g) modes. The pulsation instability is driven by opacity changes related primarily to the second ionization of He ($`\kappa `$-mechanism; Gautschy & Saio 1996). The photometric oscillations of the high-amplitude $`\delta `$ Scuti stars (HADS), which are defined as those with $`\mathrm{\Delta }V>0.3`$ mag (Breger, 2000), are generally dominated by the radial fundamental mode. In contrast, the variations seen in the lower-amplitude $`\delta `$ Scuti stars consist of multiple non-radial and radial p- (and g-) mode oscillations. Most $`\delta `$ Scuti stars are Population I objects, some of which show chemical peculiarities (Rodríguez & Breger 2001; Morgan & Abt 1972).

In the course of a search for rapid optical variations in symbiotic binary stars, Sokoloski, Bildsten, & Ho (2001; hereafter SBH) observed 131 stars in the fields of 35 symbiotic stars, primarily in the northern hemisphere. We describe here the serendipitous discovery of variability in 4 of these stars, referred to as SBCF 1-4. One new variable object, SBCF 1, is quite clearly a $`\delta `$ Scuti star, and given their oscillation periods and colors, the three others are probably $`\delta `$ Scuti stars as well. A fifth star from the sample, SAO 31628, was found to be an eclipsing binary, and the observations and ephemeris for this system are presented in Sokoloski & Stone (2000). SBCF 1 has a 0.0198-d pulsation period, which is shorter than all but 3 of the 636 $`\delta `$ Scuti stars (with periods ranging from 0.0156 to 0.2878 d) listed in the catalogue of Rodríguez et al. (2000). Very rapidly pulsating main-sequence $`\delta `$ Scuti stars, such as this one, can potentially be useful targets for study and mode identification, since good frequency coverage can be obtained with a smaller temporal baseline than for the more slowly pulsating systems. Analysis of the pulsation frequencies of $`\delta `$ Scuti stars provides an opportunity to test models of stellar structure and evolution, estimate the ages of stars, and determine the distances to stars through the use of a period-luminosity(-color-metallicity) relationship. To perform this asteroseismology, however, it is necessary to identify the oscillation modes (i.e., the spherical harmonic degree $`l`$, the azimuthal order $`m`$, the radial degree (overtone) $`n`$ or $`k`$, and whether the mode is a p mode, g mode, or mixed).

A new generation of survey experiments are being planned or are under way that are geared specifically to the broad study of variable stars or asteroseismology, such as the GAIA space mission (Perryman et al. 2001), STARE (Stellar Astrophysics & Research on Exoplanets; Brown & Kolinski 1999), ROTSE (the Robotic Optical Transient Search Experiment; see Akerlof et al. 2000), ASAS (the All Sky Automated Survey; Pojmański 2000), the Hungarian Automated Telescope (Bakos 2001), the Faint Sky Variability Survey (Groot et al. 1999), the Panoramic Optical Imager Project (POI; Kaiser et al. 2002), and eventually the Large-aperture Synoptic Survey Telescope (LSST; Tyson & Angel 2001). Large numbers of new $`\delta `$ Scuti variables are expected to be found as a result of these projects (Eyer & Cuypers, 2000). Estimates, however, are often based upon previous large surveys, such as Hipparcos, that are not sensitive to short-period pulsations, so there is much uncertainty in these predictions for new $`\delta `$ Scuti stars. Although our survey was very small compared to Hipparcos, we were sensitive to shorter-period pulsations, and so this work provides a glimpse of the variability fraction of short-period variable stars outside of open clusters (where most previous small surveys with similar sensitivity have been done).

We briefly describe our survey in §2. The observations and results for the individual new variable stars are presented in §3 through §6, and we discuss our conclusions in §7.

## 2 Observations

Between 1997 and 1999, we performed a variability survey at UCO/Lick Observatory, with the 1-m Nickel telescope, in order to search for rapid variations in symbiotic binary stars. Details of these observations and the aperture photometry can be found in SBH. We were sensitive to oscillations with periods in the range of a few minutes to several hours, and amplitudes down to a few mmag. Only stars with $`B14`$ mag were considered. The periods for the pulsating variable stars discovered in this way range from approximately 0.02 to 0.1 d, and the full $`B`$-band oscillation amplitudes ranged from 10 to 75 mmag.

On 2001 November 18 (UT is used throughout this paper), to follow up on one of the variable star discoveries, we obtained a moderate-resolution spectrum of SBCF 1 using the Echellette Spectrograph and Imager (ESI; Sheinis et al. 2000) on the 10-m Keck II telescope. A single 300-s exposure in good conditions with a 1$`\mathrm{}`$ slit gave a spectral resolution of $`75`$ km s-1 over the range 3950-10400 Å. In order to get better spectral coverage in the near-ultraviolet, we re-observed the object on 2002 January 18 for 300 s with the Low Resolution Imaging Spectrometer (LRIS; Oke et al. 1995) mounted on the 10-m Keck I telescope. The $`0.7^{\prime \prime }`$ slit provided a resolution of 3.3 Å over a wavelength range of 3350-5380 Å on the blue arm of the spectrograph and 2.0 Å over 5700-7000 Å on the red arm. The slit was aligned with the parallactic angle to minimize the effects of atmospheric dispersion (Filippenko, 1982) for both observations. Each two-dimensional exposure was processed using the standard CCD reduction packages in IRAF111IRAF is distributed by the National Optical Astronomy Observatories, which are operated by the Association of Universities for Research in Astronomy, Inc., under cooperative agreement with the National Science Foundation.. Flux calibration and removal of telluric absorption features (Wade & Horne, 1988) were accomplished in IDL using our own tasks (Matheson et al. 2000). The individual ESI orders were reduced separately and then rebinned to a common wavelength scale before being added together.

## 3 SBCF 1: A Very Short Period Pulsator

In the field of the symbiotic system AX Persei, we found an oscillating star with a dominant period of 0.0198 d, and a total peak-to-peak amplitude of 35 mmag. This star does not have an SAO or HD number (in the USNO-A2.0 catalogue, it is designated 1425-02166463), so we shall follow a recommendation from the IAU (L. Dickel, private communication) and refer to it as SBCF 1. It is roughly 0.8 mag fainter than AX Per (in quiescence) in both of our observations. From Munari et al. (1992), the $`B`$ magnitude of AX Per in quiescence is 13.0, so the $`B`$ magnitude of SBCF 1 is approximately 13.8 (see Table 1 for the average magnitudes of the new variable stars). There is no object in the SIMBAD database at this position. The finder charts for this and the other new $`\delta `$ Scuti stars are shown in Figure 1, and the coordinates of all objects are listed in Table 1.

We show the light curves from our two observations of SBCF 1 in Figure 2. The first observation, on 1998 January 23, was done under cloudy conditions. Consequently, the light curve from this night has data gaps and is of generally poor quality. During the second observation, however, on 1998 Septempber 15, the conditions were good, and the signal is clear. Furthermore, the 1998 September 15 observation was performed with a more sensitive CCD, and so we were able to obtain higher temporal resolution. The light curve from this date reveals that the oscillation amplitude is variable, and that the object is therefore multi-periodic. In fact, at least two oscillation periods can be identified using the phase dispersion minimization method (Stellingwerf 1978), one at $`0.0198\pm 0.0001`$ d, and another at $`0.0265\pm 0.0006`$ d. The 0.0198-d oscillation has an amplitude of 24 mmag, as determined by folding the light curve with that period, and the 0.0265-d oscillation has a smaller amplitude of roughly 10 mmag peak-to-peak, using the same folding method. Both oscillations have near-sinusoidal profiles. Folding the light curve from January, and again using the phase dispersion minimization method, we recover an oscillation with period $`P=0.0197\pm 0.0002`$ d, consistent with the stronger of the two oscillations detected in 1998 September. The parameters for SBCF 1 and the other new variable stars are listed in Table 2.

The spectrum of SBCF 1 is shown in Figure 3. The strong Balmer series and lack of He lines indicate that this is an A-type star. The strength of the Ca II K $`\lambda `$3934 feature, the Balmer line equivalent widths, and visual comparison of the metallic lines with spectral standards in the online digital spectral atlas of R. O. Gray (http://nedwww.ipac.caltech.edu /level5/Gray/frames.html) all indicate spectral type A2. SBCF 1 is therefore a very short period $`\delta `$ Scuti star. In fact, the dominant period of 0.0198 d is shorter than that of any of the 192 $`\delta `$ Scuti stars listed in the catalog of López de Coca et al. (1990), and all but 3 of 636 the stars listed in the catalog of Rodríguez et al. (2000).

To investigate the luminosity class, we examined the Balmer-line profiles and the equivalent width of the O I $`\lambda `$7774 line. We estimated the rotational line broadening by looking at the half-intensity width of the Mg II $`\lambda `$4481 line in our first, higher resolution Keck spectrum. Comparing the $`\lambda `$4481 half-intensity value of 2.8 Å to the half-intensity widths of the standard stars with similar spectral types listed in Slettebak et al. (1975), we find $`v\mathrm{sin}i=115\pm 5`$ km s-1. The Balmer-line profiles indicate that the star is not significantly evolved. The small O I $`\lambda `$7774 equivalent width of 0.7–0.8 Å confirms that SBCF 1 is a main-sequence star (Jaschek & Jaschek 1987), and the spectral type is thus A2V. Luminosity class V is in fact expected, since $`\delta `$ Scuti stars with low amplitudes and short periods are generally not evolved (Rodríguez & Breger 2001). Furthermore, the measured value of $`v\mathrm{sin}i`$ for SBCF 1 is very close to the average value for early A main-sequence stars (Jaschek & Jaschek 1987). From the Schlegel, Finkbeiner, & Davis (1998) dust map, the reddening toward SBCF 1 is $`E(BV)=0.23`$ mag. Taking the absolute magnitude $`M_V=+1.3`$ mag for an A2 main-sequence star (Schmidt-Kaler 1982), $`A_V=0.7`$ mag, and the measured apparent magnitude, we find that SBCF 1 is roughly 2 kpc away. This distance estimate justifies the assumption that SBCF 1 is behind the full column of extinction, given its Galactic latitude of $`8^{}`$.

For a spectral type A2V, we can estimate the pulsation constant

$`Q=\mathrm{\Pi }(M/M_{})^{1/2}(R/R_{})^{3/2}`$
(where $`\mathrm{\Pi }`$ is the pulsation period, $`R`$ is the stellar radius, and $`M`$ is the stellar mass; Christensen-Dalsgaard 1993). Using the expression $`\mathrm{log}Q=6.454\mathrm{log}f+0.5\mathrm{log}g+0.1M_{bol}+\mathrm{log}T_{eff}`$ (where $`f`$ is the pulsation frequency in cycles/day, $`M_{bol}`$ is the bolometric magnitude, and $`T_{eff}`$ is the effective temperature; Breger & Bregman 1975), and taking $`\mathrm{log}[g/(\mathrm{cm}\mathrm{s}^2)]=4.2`$, $`M_{bol}=+1.1`$ mag, and $`\mathrm{log}(T_{eff}/\mathrm{K})=3.953`$ (Schmidt-Kaler 1982), we find $`Q0.010`$ for the 0.0198-d oscillation, and $`Q0.014`$ for the 0.0265-d oscillation. These values are obviously only approximate, since $`g`$, $`M_{bol}`$, and $`T_{eff}`$ are all very uncertain, but they are nonetheless interesting. $`Q`$ is low and therefore suggests high-degree non-radial or high-order radial oscillations. Non-radial oscillations with high $`l`$ value are not expected to have the relatively large amplitude that we observe (Balona & Dziembowski 1999), so the oscillations are probably high-overtone radial pulsators. High-overtone, low spherical harmonic degree pulsations (e.g., $`l=1`$ or $`l=2`$) are also a possibility (J. Guzik, private communication). Koen et al. (1999) presented a similar argument for high-order radial oscillations in another very short period $`\delta `$ Scuti star, HD 23194 ($`P`$ = 0.0204 d).

## 4 SBCF 2 (GSC 02137-00847)

Contained in the field of the symbiotic star BF Cygni is the star SBCF 2 (= GSC 02137-00847 = TYC 2137 847 1). There is no indication from the SIMBAD database that this star is variable, but a quick look at the three light curves in Figure 4 reveals very significant oscillations. The variations are not simply repeatable, as we would expect for a binary, so they are likely due to stellar pulsation. ¿From the light curves, it is also apparent that more than one pulsation mode is present, and that the peak-to-peak amplitude in $`B`$ can reach more than 70 mmag. The first light curve, from 1997 Apr 6, can be fit with a sine curve with period 0.064 d and peak-to-peak amplitude of 74 mmag. The second and third light curves, from 1997 Jul 11 and 1998 Jul 1, each require two sine components. From the 1997 Jul 11 observation, we find sinusoidal oscillations with $`P=0.06`$ d (55 mmag peak-to-peak) and $`P=0.12`$ d (32 mmag peak-to-peak), but since the 0.012-d period is close to the length of the latter observation, we consider the detection marginal. We fit the longest light curve, from 1998 July 1, with a double sine wave, and find periods of 0.094 d (35 mmag peak-to-peak) and 0.060 d (36 mmag peak-to-peak). Given the uncertainty in the measured periods, it is possible that the 0.064-d oscillation on that day is consistent with the 0.06-d oscillations detected on the other nights. Longer observations are clearly needed to determine the number of modes present in this star, although it is clear that there are at least two. According to the General Catalogue of Variable Stars (Kholopov et al. 1992), pulsating variable stars with periods in this vicinity include $`\delta `$ Scuti stars, with periods in the range 0.01 to 0.2 d (Rodríguez et al. 2000 put the upper limit at $`0.3`$ d, and list the shortest period as 0.0156 d), and the SX Phe stars. The SX Phe stars, however, generally have amplitudes greater than 0.25 mag (McNamara 1997), so SBCF 2 is unlikely to fall in this category.

From the Tycho-2 main catalogue (Høg et al., 2000), the magnitudes for this object are $`B_T=11.537\pm 0.069`$ mag and $`V_T=11.092\pm 0.076`$ mag. Converting these values to the Johnson system (using the expressions from the Tycho catalogue description), we find $`V=11.05\pm 0.083`$ mag, $`BV=0.38\pm 0.09`$ mag, and thus $`B=11.43\pm 0.12`$ mag. The reddening from Schlegel et al. (1998) at the position of SBCF 2 is $`E(BV)=0.287`$ mag, so for this star, $`0.06(BV)_00.47`$ mag. This range of $`(BV)_0`$ corresponds to an A- or F-type star, which is exactly what we expect for a $`\delta `$ Scuti pulsator. Therefore, given the oscillation period, light-curve shape, intrinsic color $`(BV)_0`$, and pulsation amplitude (which ranges from 3 mmag to 0.9 mag in $`V`$ for $`\delta `$ Scuti stars), we conclude that SBCF 2 is a $`\delta `$ Scuti star. Using absolute magnitudes and extinctions corresponding to spectral types within the allowed range, the calculated distance to SBCF 2 is at least 250 pc.

## 5 SBCF 3 (GSC 01619-02513)

In the field of the symbiotic star AS 360 (= QW Sge), the star SBCF 3 (= GSC 01619-02513) oscillated with a peak-to-peak $`B`$-band amplitude of 30 mmag, and a period of 2.1 hr. We show the light curve for this star in Figure 5. There is no object in the SIMBAD database at this position. In the USNO-A2.0 catalog, the $`B`$ magnitude of this star (USNO-A2.0 1050-14753932) is listed as 12.8, and the $`R`$ magnitude as 12.4, giving a color for SBCF 3 of $`BR=0.4`$ mag. The intrinsic color for SBCF 3 is therefore $`(BR)_00.4`$ mag; if it is a main-sequence star, SBCF 3 must therefore be spectral type A or earlier. Since an A-type star has a radius roughly two or more times that of the Sun, such a star cannot fit within the Roche lobe of a binary with either a 2-hr or 4-hr orbital period (the orbital period of an ellipsoidal variable would be twice the photometric period). To fit within the Roche lobe of a 2-hr binary, a star would need $`M<0.3M_{}`$. The oscillation period of 2.1 hr and the restriction on the spectral type indicate that SBCF 3 is likely to be a $`\delta `$ Scuti star.

## 6 SBCF 4 (GSC 03645-01592)

SBCF 4 (= GSC 03645-01592 = TYC 3645 1592 1) is the only star within $`7\mathrm{}`$ of Z And whose brightness is within 2 or even 3 mag of Z And. In the Tycho catalogue, photometry for GSC 03645-01592 is given as $`B_T=11.64\pm 0.06`$ mag and $`V_T=11.38\pm 0.076`$ mag. Converting to Johnson magnitudes, we find $`B=11.6\pm 0.1`$ and $`V=11.4\pm 0.1`$ mag. Because of the interesting 28-minute oscillation in Z And (Sokoloski & Bildsten 1999), we observed this field many times. The paucity of suitable comparison stars, however, made high-quality light curves difficult to produce. An example, which was constructed using an ensemble average of 2 very faint comparison stars, is shown in Figure 6. The signal-to-noise ratio is lower than for the other light curves, but variability at the level of about 40 mmag peak-to-peak is evident. The variability amplitude of this star was not constant from observation to observation (i.e., month to month), and on at least one occasion, the variations were undetectable. When variations were present, the oscillation period for SBCF 4 was roughly 2 hr. With an intrinsic color $`(BV)_00.3`$ mag, the spectral type of this star must be F0 or earlier. As with SBCF 3, a star with such an early spectral type could not fit within the Roche lobe of a binary with the observed (or twice the observed) period. Therefore, with an A- or early-F-type spectrum, and an oscillation period of 2 hr, this star is an excellent candidate $`\delta `$ Scuti star.

## 7 Discussion

We analyzed light curves for 131 stars with $`B`$ magnitude less than 14, that had a typical temporal resolution of 1 minute or shorter. Out of these objects, we found four new pulsating variable stars. The short-period $`\delta `$ Scuti star SBCF 1 is potentially a good candidate for further study, since mode identification might be accomplished with less observing time than for the longer period $`\delta `$ Scuti stars. SBCF 1 is not as bright as some of the other $`\delta `$ Scutis that have been targets for serious asteroseismological efforts, but with the availability of larger telescopes and more sensitive CCDs, the opportunity to use a shorter temporal baseline, and therefore less complex window function, becomes increasingly important. For example, using differential CCD photometry and a 1-m telescope, we were able to obtain the same level of photometric precision (several mmag per point) for SBCF 1 as Viskum et al. (1998) had in their study of FG Vir that resulted in the identification of eight oscillation modes of that star. In addition, unevolved, core H-burning $`\delta `$ Scuti stars have pulsation spectra that are theoretically predicted to be less dense than shell H-burning, evolved $`\delta `$ Scuti stars (Michel et al. 2000). Asteroseismological studies of this object could thus help achieve broad goals such as testing theories of stellar structure and evolution, and extending the period-luminosity relation to low-amplitude pulsating stars (Petersen & Christensen-Dalsgaard 1999).

Nearly all currently known $`\delta `$ Scuti stars with oscillation amplitudes below 20 mmag or periods below 0.05 d have been found by individual observers or small collaborations (Rodríguez & Breger 2001). Therefore, in contrast to the longer period variables that are easily detected by, for example, Hipparcos, MACHO, and OGLE, very little statistical information is currently available about the prevalence of stellar variability in this parameter range. In fact, the studies which heretofore have been most sensitive to rapid, low-amplitude oscillations have primarily examined stars in open clusters, where the detection rate is a function of cluster age222Some other unknown factor also affects the detection rate in clusters. No $`\delta `$ Scutis at all were found out of 68 stars in the instability strip in NGC 7226 (Viskum et al. 1997). (since a different amount of the isochrone will pass through the instability strip for different ages). Therefore, small surveys such as this one, with the ability to detect variations on time scales as short as a few minutes, can provide information that, when considered with large survey results, should improve the predictions of the number of variable stars that will be found with the new generation of searches.

Our discovery rate for low-amplitude pulsators of 3% is higher than the rates that were found with Hipparcos (1%; Eyer 1999), OGLE (0.04 \- 0.08%; Udalski et al. 1994, 1995a,b; Eyer 1999), or MACHO ($`<`$ 0.032%; Cook 1997). The difference between these results could be due to the small-number statistics for our survey, or to our better sensitivity in the more highly populated $`\delta `$ Scuti period and amplitude parameter ranges. The number of $`\delta `$ Scuti stars found with Hipparcos dropped off below $`\mathrm{\Delta }V40`$ mmag (Rodríguez & Breger, 2001), and the OGLE and MACHO surveys are not sensitive to pulsations with amplitude less than 0.1 mag (Rodríguez et al. 2001).

The typical periods of $`\delta `$ Scuti stars may be even more relevant for explaining our higher detection rate. The peak of the distribution of all $`\delta `$ Scuti stars with period lies between 0.05 and 0.1 d, and more than 10% of known $`\delta `$ Scuti stars have pulsation periods less than 0.05 d (Rodríguez & Breger, 2001). We had excellent sensitivity to variables with periods in this range. Hipparcos, on the other hand, because of its sampling, discovered very few $`\delta `$ Scuti stars with pulsation period less than 0.1 day, and practically none with pulsation period less than 0.05 day. To put our results in the context of other surveys, ASAS looks for variables at a cadence of one day, and they have detected pulsating stars with periods only down to 0.13 d. The ROTSE all-sky survey found a firm lower limit of 0.2% for the variability fraction in the first analysis of part of their survey, but they are insensitive to oscillations with amplitude less than 0.1 mag (in addition to some period limitations from obtaining data points only twice per day; Akerlof et al. 2000).

We would like to thank to Dimitar Sasselov, Scott Kenyon, and Yanqin Wu for useful discussions, as well as Joyce Guzik, Paul Bradley, and a very thourough anonymous referee for their critical reading of the manuscript. We are also grateful to Jason Aufdenberg, Bob Kurucz, and Anne Bragg for assistance with the initial spectral analysis of SBCF 1. We acknowledge the assistance of the staffs of the Lick and Keck Observatories. The W. M. Keck Observatory is operated as a scientific partnership among the California Institute of Technology, the University of California, and NASA; it was made possible by the generous financial support of the W. M. Keck Foundation. This research was supported by NASA via grant NAG 5-8658 and by the NSF under grants PHY-9907949, AST-0196422, AST-9987938, and INT-9902665. L.B. is a Cottrell Scholar of the Research Corporation. and A.V.F. is a Guggenheim Foundation Fellow.