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# Base pair dynamic assisted charge transport in DNA

## Abstract

An $`1d`$ model with time-dependent random hopping is proposed to describe charge transport in DNA. It admits to investigate both diffusion of electrons and their tunneling between different sites in DNA. The tunneling appears to be strongly temperature-dependent. Observations of a strong (exponential) as well as a weak distance dependence of the charge transfer in DNA can be explained in the framework of our model.

Electronic transport is a ground to a wide range of important biological processes in DNA. Besides, the phenomenon has a fundamental physical interest, since the transport properties of biomolecules are expected to differ considerably from those of macroscopic conductors. And at last, very recently material scientists also turned their attention to charge migration in DNA for the development of DNA-based molecular technologies.

Although first attempts to measure DNA conductivity , and to give a theory of the phenomenon  have been made almost 40 years ago, the question concerning charge transport through DNA remains unsettled, and there is an impressive quantity of unexplained or partially explained data. Different publications report frequently contradictory results. Two kinds of techniques for getting information on charge transport in DNA are used. First, direct or indirect electrical conductivity measurements on micrometer-long DNA ropes are performed . Experimental results obtained in this technique are ambiguous. DNA conductivity $`\sigma `$ was reported as almost metallic of the order $`10^4\mathrm{\Omega }^1cm^1`$  (in a recent publication  the authors claim they observed even proximity induced superconductivity in DNA) or semiconducting with $`\sigma 0.1\mathrm{\Omega }^1cm^1`$ . Very recently experimental techniques have progressed to the point where the conductivity on individual $`10nm`$ long double stranded molecules was measured  and the result implies that DNA is a good insulator. Clearly this frustrating situation with conductivity measurements means that there are many relevant factors which can influence the charge transport in DNA by different way and which are hardly controlled in real experiments. The second technique, related to fluorescence quenching measurements on DNA strands, doped with donor and acceptor molecules , seems more reliable, and it is our main concern here. In this technique photo-excitation of a donor associated with the stack of base pairs in some fashion, allows transfer of an electron to the stack. The migrating electron is trapped finally at the acceptor site, and charge transfer is monitoring by the yield of a chemical reaction accompanying the trapping process. The transfer rate is usually assumed to be characterized by a simple exponential law $`\mathrm{exp}(\beta x)`$, where $`x`$ is the donor-acceptor separation. Fitting to this law gives values of $`\beta `$ ranging from $`0.1\AA ^1`$ to $`1.4\AA ^1`$.

It is a common wisdom that DNA can be treated as an one-dimensional linear chain of stacked base pairs. We believe, that in the ground state every base pair contains bound electrons only. Then the charge is carried through DNA by excited electrons (or holes) which can jump between the base pairs. Below we propose a simple model which, to our meaning, reflects basic features of the electron transport in DNA. The picture includes the following ingredients:

(i) The excited electron states at the base pairs are separated by energy spacing larger than temperature and therefore thermally are practically not excited;

(ii) Thermal motions of the DNA base pairs are elastic vibrations with a characteristic frequency $`\omega _b`$;

(iii) Efficient charge transfer between neighboring base pairs takes place for rare events;

(iv) The Coulomb interactions between the electrons and holes can be neglected for the description of hopping transport.

Let us explain the point (iii) in more detail. For the static equilibrium DNA helix charge hopping is expected to be negligibly small since there is no significant electronic overlapping between adjacent base pairs. Nevertheless, sometimes, due to thermal fluctuations, exclusively favourable for hopping configurations of the base pairs occur, when an efficient hopping is possible. If the separation between the pairs is larger than the amplitude of their thermal vibrations, then probability of such events (which can be called “contacts”) is small. Duration of the contact can be estimated as the characteristic oscillation time $`\omega _b^1`$.

Now we discuss a correspondence of the assumptions enlisted above and experimental data. As a guide line we use not only data known from the DNA literature but as well the data obtained for a wide range of organic linear chain polymers of stacked planar molecules (for a review see ). The contacts are related to mutual displacements and orientations of adjacent base pairs. Probably, hopping matrix elements are mostly sensitive to the relative rotations (twist fluctuations) of the base pairs (see, e.g., ). The characteristic frequency of these fluctuations, $`\omega _b`$, is usually estimated as being in the region $`10^{11}÷10^{12}s^1`$. A small probability of the contacts is confirmed by experiment showing that the characteristic electronic hopping time $`\tau `$ is larger than $`\omega _b^1`$, in the experiments  $`\omega _b\tau =10^2÷10^3`$. Our first assumption (i) requires $`\mathrm{\Delta }E>T`$, where $`\mathrm{\Delta }E`$ is the spacing in the spectrum of electron excitations for a base pair. The magnitude of $`\mathrm{\Delta }E`$ can be measured directly, for the experiments  $`\mathrm{\Delta }E>500K`$. Therefore the inequality is satisfied. Rough macroscopical estimations of the Coulomb interaction $`U_c`$, as well as ab initio molecular orbital calculations of $`U_c`$, give few $`meV`$ , and thus Coulomb energy appears to be smaller (though of the same order) than $`\mathrm{}\omega _b`$. We believe that it is enough to justify neglecting Coulomb interaction.

The above reasoning leads to an $`1d`$ hopping Hamiltonian for the electrons

$`=\mathrm{}{\displaystyle \underset{i}{}}\left(\xi _ia_i^+a_{i+1}+\xi _i^{}a_{i+1}^+a_i\right).`$ (1)
Here $`a_i`$ and $`a_i^+`$ are electronic annihilation and creation operators at the site (i.e. the base pair) with the number $`i`$, and $`\xi _i`$ are the hopping amplitudes, which are time-dependent quantities. The equations for the Heisenberg operators $`a_i`$ are

$`_ta_i=i\xi _ia_{i+1}i\xi _{i1}^{}a_{i1}.`$ (2)
We assume that different $`\xi _i`$ possess independent statistics, since $`\xi _i`$ are related to independent thermal pair base fluctuations. The hopping matrix element $`\xi _i`$ can be decomposed into a constant part $`\xi _i`$, that describes the coherent charge carrier motion in a completely rigid lattice, and a fluctuating part. Since the probability to jump is appreciable during rare events, the coherent part of $`\xi `$ can be neglected in comparison with its fluctuating part.

Note, that theoretical models based on hopping Hamiltonians similar to Eq. (1) are widely used to describe charge transport in solid state physics (see, e.g., ). For most of problems in this case the description corresponds to electron migration in a steady energy landscape, including thermally activated jumps over barriers and quantum tunneling through the barriers. It is quite different from our case.

We assume that DNA molecules can be treated as homogeneous ones. Though the molecules are constructed from four different nitrous bases, experimental data , as well as numerical first principle calculations  show, that the sequence of base pairs is not a decisive factor which determines electron transport in DNA. Quantitatively this condition can be formulated as $`\delta E<\mathrm{}\omega _b`$, where $`\delta E`$ is an energy spacing between the (lowest excited) electron energy levels at different base pairs. The values of $`\delta E`$, known mainly from numerical electronic structure calculations , are of order of $`meV`$. Thus $`\delta E`$ is smaller than $`\mathrm{}\omega _b`$ for $`\omega _b`$ given above, that justifies the picture. Besides some experiments (see, e.g., ) are performed for artificial homogeneous DNA, where $`\delta E=0`$. One expects that, due to the hopping, electron diffusion occurs on large time scales. For $`\xi `$, treated as a white noise, it was demonstrated in the papers . Though our case is essentially different, there is good reason to believe, that the same behavior should be observed on time scales larger than the hopping time $`\tau `$.

Below, we examine the particular case related to the fluorescence measurements, reported in the papers . The donors are photo-excited and effects, related to the excited electron motion to the acceptors, are monitored. The energetic gaps $`\delta E_d`$ and $`\delta E_a`$ between the donor and the acceptor and the base pairs between them, are crucial for the hopping rate. The values of $`\delta E_d`$ and $`\delta E_a`$ (known mainly from ab initio numerical calculations ) can be estimated as $`10^2meV`$. We see, that the inequalities $`\delta E_d,\delta E_a\mathrm{}\omega _b`$ are satisfied. The electron is always bound to the acceptor site more strongly than to a standard base pair, that is $`\delta E_a>0`$. As to the donors, the sign of $`\delta E_d`$ can be either positive or negative. If $`\delta E_d`$ is negative then a scheme of the electronic charge transfer from the donor to the acceptor is quite simple. Initially, the electron leaves the donor, jumping to the neighbor site, and then jumps between the standard base pairs, trapping finally at the acceptor. The case $`\delta E_d>0`$ is more complicated. In order to have a driving force for the donor–acceptor charge transfer process the final state with the charge bound to the acceptor should be energetically favourable, that is the inequality $`\delta E_a>\delta E_d`$ has to be satisfied. However, there are some base pairs in-between which play the role of the potential barrier for the electron. Therefore there are two possibilities for the electron to come to the acceptor. The first possibility is to jump initially from the donor to the neighbor site and then to move to the acceptor due to multistep hopping over the standard base pairs. The second possibility is the unistep (direct) quantum tunneling from the donor to the acceptor through the barrier.

Since $`\delta E_d\mathrm{}\omega _b`$, the probability for the electron to jump from the donor to the neighboring base pair due to dynamics of $`\xi `$ is negligible. At $`\delta E_d>0`$ such a jump is possible if the electron absorbs a high-frequency phonon with the frequency $`\omega _{ph}\omega _d`$ ($`=\delta E_d/\mathrm{}`$). Correspondingly, at $`\delta E_d<0`$ the electron jump from the donor is accompanied by emitting high frequency phonons. Such dynamical vibrations with periods as short as tens femtoseconds (i.e. phonons with $`\omega _{ph}10^{14}s^1`$) were reported in the literature . Since $`\mathrm{}\omega _{ph}>T`$, occupation numbers of such phonons are small. Thus, for $`\delta E_d>0`$ the probability for the electron to jump from the donor to the neighboring site contains two small factors: the probability of the contact and the probability to absorb the high frequency phonon. It corresponds to the experimental situation where only a small fraction of the electrons are transported from the donor to the acceptor.

When the electron leaves the donor, it starts to jump between the donor and the acceptor. It can return to the donor or can come to the acceptor. If $`\delta E_d<0`$ then the probability to return to the donor is negligible. We assume that even at $`\delta E_d>0`$ the probability of the electron to jump to the donor or to the acceptor is smaller than the probability to jump to the standard base pair. There are two reasons for the assumption. First, the donors and the acceptors have chemical structures, different from the standard base pairs, that hinders for the contacts. Second, the jump has to be accompanied by the phonon emission, that diminishes its probability. The same is valid for the acceptor. Thus before being finally trapped at the acceptor site, the electron jumps many times back and forth over the base pairs between the donor and the acceptor, “smearing out” homogeneously over the all intermediate base pairs. Then the relative probability for the electron to come to the acceptor is determined by the ratio of the probabilities for the electron to jump to the donor and to the acceptor from adjacent base pairs. This relative probability appears to be independent of the separation $`x`$ between the donor and the acceptor. That explains why the rate of charge transfer sometimes is almost insensitive to the relative loading of donors and acceptors (see, e.g., ). The above picture implies, that the total donor-acceptor charge transfer time should be larger than the electronic hopping time $`\tau `$, and it conforms to experimental data (see, e.g., ).

Now we consider the quantum tunneling for the electron, strongly attached to the donor, that is the case $`\delta E_d>0`$. Though the potential barrier depends on time, at the condition $`\delta E_d\mathrm{}\omega _b`$ the probability for the electron tunneling from the donor to the acceptor can be calculated in the adiabatic approximation. To examine the tunneling process, one should consider the quasistationary electron state bound at the donor. In the spirit of our picture we assume $`\xi \omega _d`$. Then the energy of the bound state is close to $`\delta E_d`$. Substituting $`_t`$ by $`i\omega _d`$ in Eq. (2), one obtains for the state

$`a_i={\displaystyle \frac{\xi _{i1}^{}}{\omega _d}}a_{i1}\mathrm{if}i>0,a_i={\displaystyle \frac{\xi _i}{\omega _d}}a_{i+1}\mathrm{if}i<0,`$ (3)
where we used the condition $`\xi \omega _d`$. Then the probability for the electron to be at the site $`n`$ is determined by the average

$`a_n^+a_n=\omega _d^{2n}\left|{\displaystyle \underset{i=1}{\overset{n}{}}}\xi _{i1}\right|^2.`$ (4)
Quantum averaging and averaging over statistics of $`\xi `$ are performed at deriving Eq. (4). Besides at the derivation we substituted $`a_0^+a_01`$ justified by $`a_n^+a_n1`$. Note that the probability (4) is determined by the simultaneous statistics of $`\xi `$. Remind that different $`\xi _j`$ are assumed to be statistically independent. Therefore the average in the right-hand side of Eq. (4) is a product of $`|\xi _j|^2`$. For the standard pairs the quantities can be regarded as site independent ones. Therefore the probability of the electron to be at the nearest to the acceptor site is proportional to $`|\xi |^2^n/\omega _d^{2n}`$ where $`n`$ is the number of the standard pairs between the donor and the acceptor.

The jump of the electron from the bound state to the acceptor is accompanied by the phonon emission. However, the only $`x`$-dependent factor in the probability of the process is related to the average charge occupation number of a site $`n`$ near the acceptor, established above. Thus, we obtain for the probability the exponential law $`\mathrm{exp}(\beta x)`$ with

$`\beta =a^1\mathrm{ln}(\omega _d^2/|\xi |^2),`$ (5)
Here $`\xi `$ is the hopping probability for the standard base pairs and $`a=3.4\AA `$ is the distance between the base pairs in DNA. Note, that $`\omega _d`$ depends on the donor type, whereas the average $`|\xi |^2`$ is mainly related to base pair vibrations. It follows from the above consideration, that the exponential law implies the condition $`\beta >a^1`$. This conclusion is in agreement with the majority of published experimental data. Reported in  the value $`\beta =0.1\AA ^1`$ (thus smaller than $`a^1`$) is, probably, related to an attempt to fit a complex behavior (including two processes: diffusion and tunneling) by a simple exponential law.

Let us stress that the quantum tunneling analyzed above is not a standard (static) tunneling described in textbooks. We have deal with dynamic tunneling which can be effective only when due to fluctuations of $`\xi `$ there occurs some kind of a “bridge” from the donor to the acceptor. The exponential law, we found, is explained in fact by a small probability to have such a bridge, which is realized, when simultaneously many contacts between base pairs occur. In addition, the probability of this kind of tunneling is strongly dependent on the temperature via $`|\xi |^2`$. It is natural to assume that $`\xi `$ exponentially depends on the relative displacement $`u`$ of the neighboring base pairs. Then (in the harmonic approximation) $`\mathrm{ln}|\xi |^2`$ contains the term, proportional to $`u^2`$, which is proportional to the temperature $`T`$. Thus we arrive at the expression

$`\beta a=c_1c_2T,`$ (6)
where $`c_1`$ and $`c_2`$ are temperature-independent factors. They can be extracted from the paper : $`c_14`$, $`c_20.01K^1`$. The values are in agreement with rough estimates $`c_1a/b`$, $`c_2k_B/(M\omega _b^2b^2)`$, where $`k_B`$ is the Boltzmann constant, $`M`$ is the base pair mass, and $`b`$ is an electronic penetration length. It can be estimated as $`b\mathrm{}/\sqrt{mE}1\AA `$, where $`m`$ is is the electron effective mass and $`E`$ is its binding energy at the base pair.

To conclude, for the electron, strongly bound to the donor, we established two different charge transfer mechanisms: diffusion and tunneling. The diffusion leads to the charge transfer probability independent of the donor-acceptor distance $`x`$. However, the probability contains the small factor related to the electron jump from the donor to a neighboring site. The tunneling leads to the exponential dependence of the probability on $`x`$ (with the temperature-dependent length $`\beta ^1`$). Therefore, it is not efficient for large distances. Thus, the exponential law has to be observed for small distances $`x`$ whereas for large distances the charge transfer rate has to be independent of the donor-acceptor distance. Just this kind of behaviour was reported very recently . For the case of the electron weakly bound to the donor the hopping should always dominate over quantum tunneling. That explains why the rate of charge transfer sometimes does not behave exponentially even for small $`x`$ .

Note that in some cases the interaction of light, ionizing radiation or chemically active reagents with DNA can result in loss of an electron at a specific site with formation of a hole. In this case the charge transport through DNA can be provided by holes (see, e.g., ). The key issues for positive charge carrier transport are the same as for the electrons. As far as the physical picture of charge transport is essentially the same for both kind of carriers, it can be described in the framework of the same approach.

The research presented in this publication was made possible in part by RFFR Grant 00-02-17785. Fruitful discussions with A. Iosselevitch, Yu. Evdokimov, V. Golo, D. Bicout, and T. Costi are gratefully acknowledged.


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# The mass ratio distribution of short period double degenerate stars.

## 1 Introduction

Short period double degenerates (DDs) are binary stars in which both stars are white dwarfs. The orbital periods of DDs are hours or days (Maxted & Marsh 1999) so the separation of the stars is only a few solar radii. White dwarfs are the remnants of giant stars which have radii of hundreds of solar radii, much larger than the current size of the binary, so there has clearly been dramatic shrinkage of the binary orbit during the evolution of the binary star. There are several models for the formation of DDs which have been used to predict the properties of this group of binary stars. These usually assume that the most recent episode of orbital shrinkage is due to a common envelope (CE) phase in which a red giant star comes into contact with its Roche lobe and begins to transfer mass to its companion star. This mass transfer is highly unstable, so a “common envelope” forms around the companion and the core of the red giant. The drag on the companion orbiting inside the common envelope leads to extensive mass loss and dramatic shrinkage of the orbit (Iben & Livio 1993). If this CE phase happens while the star is on the first giant branch, the degenerate helium core of the red giant will be exposed and will appear as a white dwarf of unusually low mass, i.e., about 0.4$`M_{}`$, c.f., 0.55 – 0.6$`M_{}`$for a typical white dwarf (Bragaglia et al. 1995). The mass of a white dwarf can be measured directly from its spectrum by comparing the surface gravity, $`\mathrm{log}g`$, and the effective temperature, Teff, to cooling models of white dwarfs. Low mass white dwarfs identified this way are particularly fruitful source of DDs (Marsh, Dhillon & Duck 1995).

The most notable difference between models for the formation of DDs is the way they treat the formation of the first white dwarf. For example, Iben, Tutukov & Yungelson (1997) have predicted the distributions of masses, periods and mass ratios for DDs using a numerical model of the population of close binaries which evolve through either two CE phases or an Algol-like phase (stable mass transfer on a thermal timescale) followed by a CE phase. Han (1998) has produced a similar model but has also explored how the various parameters of the model affect the distribution of periods, mass or mass ratio which are predicted. Han’s model also includes enhanced mass loss in a star as it approaches its Roche limit, an effect which is not incorporated in the model of Iben, Tutukov & Yungelson. It has now been fairly well established that these models do not succesfully predict the distribution of mass ratios for DDs. This problem has been explored on a case-by-case basis by Nelemans et al. (2000). The size of a red giant is related directly to its core mass so they were able to show that for three DDs with measured mass ratios, the standard prescriptions for the first mass transfer phase predict orbits which are too small. They used a parametric approach to describe the first mass transfer phase based on a consideration of the angular momentum balance during this phase, rather than the more usual energy balance arguments used by Iben et al. and Han et al. This parametric approach was incorporated into a model for the population of DDs by Nelemans et al. (2001). They were able to predict a mass ratio distribution which was more consistent with those observed provided that they assumed that very low mass white dwarfs ($`0.3`$$`M_{}`$) cool more rapidly than recent models predict. This assumption is required to avoid the prediction that most binary white dwarfs should have very low masses - a problem common to many of these models.

Measuring mass ratios for DDs is a powerful way to test models of how binary stars interact. Strong obervational tests of these models are desirable because many interesting astrophysical phenomena are the result of interacting binary stars, e.g., black hole binaries, AM CVn binaries, Type Ia supernovae, cataclysmic variables and novae. The properties of these objects have a direct bearing on areas of astronomy other than the study of binary stars themselves, e.g., the evolution of the properties Type Ia supernovae over the history of the Universe is a matter of direct concern when they are used as standard candles to measure cosmological parameters (Umeda et al. 1999).

Several preliminary estimates of the mass ratios and others parameters for WD 0136+768, WD 0957$``$666 and WD 1204+450 have been published elsewhere (e.g., Moran, Marsh & Maxted 1999). The values given here should be used in preference to those earlier estimates although the conclusions discussed above, many of which are based on those preliminary estimates, are not affected in general by the small changes to the values of the mass ratio given here.

## 2 Observations and reductions

Observation of WD 0957$``$666 were obtained with the RGO spectrograph on the 3.9m Anglo-Australian Telescope (AAT) at Siding Spring, Australia. We used a 1200 line/mm grating with the 82cm camera and a 0.8 arcsec slit. The detector used was a TEK charge-coupled device (CCD) with $`1024^2\times 24\mu `$m pixels. The resolution of the spectra is 0.7Å and the dispersion is 0.23Å-per-pixel.

Observations of WD 0136+768 and WD 1204+450 were obtained with the 500mm camera of the intermediate dispersion spectrograph (IDS) on the 2.5m Isaac Newton Telescope (INT) on the Island of La Palma and the ISIS spectrograph on the 4.2m William Herschel Telescope (WHT), also on La Palma. Both spectrographs were used with 1200 line/mm gratings, a 1 arcsec slit and a TEK CCD. The resolution of the IDS spectra is 0.9Å and the dispersion is 0.39Å-per-pixel. The resolution of the ISIS spectra is 0.8Å and the dispersion is 0.40Å-per-pixel.

The dates of observation for each star are given in Table 1 The observing procedure is very similar in each case. We obtain spectra of our target stars around the H$`\alpha `$ line using exposure times of 5–30 minutes. Spectra of an arc lamp are taken before and after each target spectrum with the telescope tracking the star. None of the CCDs used showed any structure in unexposed images, so a constant bias level determined from a clipped-mean value in the over-scan region was subtracted from all the images. Sensitivity variations were removed using observations of a tungsten calibration lamp. The sensitivity variations along the spectrograph slit are removed using observations of the twilight sky in the AAT images because the tungsten calibration lamp is inside the spectrograph. We have occasionally used the same technique for the WHT and INT spectra, though it makes little difference in practice whether we use sky images or lamp images to calibrate these images.

Extraction of the spectra from the images was performed automatically using optimal extraction to maximize the signal-to-noise of the resulting spectra (Marsh 1989). The arcs associated with each stellar spectrum were extracted using the profile determined for the stellar image to avoid possible systematic errors due to tilted arc lines. The wavelength scale was determined from a polynomial fit to measured arc line positions and the wavelength of the target spectra interpolated from the calibration established from the bracketing arc spectra. Uncertainties on every data point calculated from photon statistics are rigorously propagated through every stage of the data reduction.

## 3 Analysis

In this section we describe how we have measured the mass ratios for WD 0957$``$666, WD 0136+768 and WD 1204+450 using a simultaneous fit to the H$`\alpha `$ line in all the available spectra for each star.

### 3.1 WD 0136+768

The spectra clearly show two sharp cores to the H$`\alpha `$ line separated by up to about 150 km s-1 with one core slightly deeper than the other. To determine an approximate value of the orbital period, we cross correlated the spectra against a single Gaussian profile with a full-width at half minimum (FWHM) of 200 km s-1 and measured the position of the peak. This gives an average of the radial velocities of the two stars weighted towards the star with the deeper core. We then calculated the periodogram of the results over 100 000 frequencies between 0.01 and 20 cycles per day. The periodogram is shown in Fig. 1. All the periodograms in this paper show the natural logarithm of the probability ratio P(D$`|`$C+S,$`f`$)/P(D$`|`$C), where P(D$`|`$C+S,$`f`$) is the probability of obtaining the data given that it the sampling of a signal composed of a sine wave with frequency $`f`$ plus a constant, and (P$`|`$C) is probability of obtaining the data given that it the sampling of a constant signal, i.e., the exponent of equation (A4) discussed in Marsh, Dhillon & Duck (1995). The orbital frequency is clearly near 0.7 cycles per day. We then calculated the periodogram of the results over 20 000 frequencies between 0.6 and 0.8 cycles per day, also shown in Fig. 1. There are two peaks of similar significance in this range at 0.69112 and 0.71063 cycles per day.

In order to determine approximate values for the projected orbital velocities of the stars and to identify the correct orbital frequency, we measured approximate radial velocities for both stars using a least-squares fit of two Gaussians profiles with fixed widths of 1.2Å and of fixed depths of 10 percent of the local continuum. A fixed quadratic function was used to account for the shape of the spectrum near the cores and only data within 500 km s-1 of the rest wavelength of H$`\alpha `$ was included in the least-squares fit. After assigning the measured the radial velocities to the correct star for each of the trial frequencies, it was clear from the quality of a least-squares fit of a sine wave to the data that 0.71063 cycles per day is the correct orbital frequency. The fit to these data is shown in Fig. 2.

To measure the radial velocities of the two components more precisely we used a simultaneous least-squares fit to all the spectra of two model profiles, one for each star, in which the position of each model profile is predicted from its time of observation, $`T`$, using the equation $`\gamma _i+K_i\mathrm{sin}(2\pi (TT_0)/P)`$, where $`i=`$1 or 2. We define $`T_0`$ such that star 1 has the deeper H$`\alpha `$ core and is closest to the observer at time $`T_0`$. The projected orbital velocity of star 1 is $`K_1`$ and its apparent mean velocity is $`\gamma _1`$ and similarly for star 2. Note that $`\gamma _1\gamma _2`$ because the apparent mean velocity is the sum of the radial velocity of the system and the gravitational redshift of each star, and this second quantity is different for each star. Each model profile is the sum of a number of Gaussian profiles with independent widths and depths but with the same mean. In this way we are able to determine the shape of the two profiles and the parameters of the two circular orbits, including $`T_0`$ and $`P`$, directly. The resolution of each spectrum is included by convolution of the final model profile for each spectrum with a Gaussian function of the appropriate width and the effects of smearing due to orbital motion are also included.

There are many free-parameters in this fitting process so we used a series of least-squares fits in which first the profile shapes were fixed while the parameters of the orbit were varied and then vice versa, until we had established values for all the parameters which were nearly optimal. Only data within 5000 km s-1 of the rest wavelength of H$`\alpha `$ is included in the least-squares fit. The spectra were normalized using a linear fit to the contiuum either side of the H$`\alpha `$ line prior to fitting. We used four Gaussian profiles to model the broad wings of the H$`\alpha `$ line and the core of star with the deeper core and three Gaussian profiles for the other star. A polynomial is also included in the fitting process to allow for smooth, asymmetric features in the profile. For the final least-squares fit the parameters of the profile shapes and the orbit were all varied independently. The reduced $`\chi ^2`$ value for this fit was rather high because of small changes from spectrum-to-spectrum due to inaccuracies in the normalization process. We corrected for these small offsets by subtracting the mean of the residuals over the fitting regions from each spectrum. We then repeated the fitting process and obtained the results given in Table 2. In fact, this renormalization has a negligible effects on the results. The trailed spectrograms of the data, the fit and the residuals are shown in Fig. 3.

### 3.2 WD 0957$``$666

Bragaglia et al. (1990) first noted the variable radial velocity of WD 0957$``$666 and the absence of any spectral features due to a main-sequence companion in the optical or near-infrared spectrum. They concluded that WD 0957$``$666 is a double degenerate with an orbital period of 1.15 d. Moran, Marsh & Bragaglia (1997) used the AAT data from 1996 described above to show that the correct orbital period is 1.46 h. The core of the H$`\alpha `$ line from the fainter white dwarf in this binary is visible in these spectra. This lead to a mass ratio measurement of $`q=1.15\pm 0.10`$. We obtained additional data of WD 0957$``$666 with the AAT during 1997 to improve the measurement of the mass ratio.

We have used all the spectra of WD 0957$``$666 from 1996 and 1997 with exposure times of 300s to 600s. We normalized the spectra using a linear fit to the continuum either side of the H$`\alpha `$ line. We used the radial velocites predicted by the ephemeris and circular orbit fit of Moran, Marsh & Bragaglia to apply a shift our 1997 data. Visual inspection of the trailed spectrogram shows that ephemeris is reliable, so we proceeded directly to a simultaneous least-squares fit to all the spectra using the same method we employed for WD 0136+768. We found that the quality of the fit is much improved by using three Gaussians for star 2, rather than two Gaussians as Moran, Marsh & Bragaglia used. Only data within 2000 km s-1 of the rest wavelength of H$`\alpha `$ is included in the least-squares fit. The optimum values determined by least-squares for the width and depth of each Gaussian and the parameters of the circular orbits are given in Table 3. The trailed spectrograms of the data, the fit and the residuals are shown in Fig. 4.

### 3.3 WD 1204+450

WD 1204+450 is a low mass white dwarf (Bergeron, Saffer & Liebert 1992) which was first identified as a possible binary by Saffer, Livio & Yungelson (1998). We observed WD 1204+450 with the INT to determine its orbital period. These spectra show two narrow cores to the H$`\alpha `$ line, one slightly deeper than the other, moving in anti-phase by $``$100$`\mathrm{km}\mathrm{s}^1`$ over 6–7 hours. This clearly shows that WD 1204+450 is a double degenerate with a period of $`1.5`$ days but the quality and phase coverage of the INT data is such that it is difficult to determine the exact orbital period from these data alone, particularly since it is hard to identify the deeper core in some of the spectra. We have therefore obtained data with the WHT at slightly better resolution and higher signal-to-noise which has enabled us to identify an unambiguous orbital period as follows.

We first normalized all the spectra using a low-order polynomial fit to the continuum either side of the H$`\alpha `$ line and formed the average of those spectra taken within 2 hours of each other improve their signal-to-noise. We used a least-squares fit to a WHT spectrum in which the cores are clearly distinguished to create a model line profile for each star composed of 4 Gaussian profiles for the star with the deeper core and 3 for the other. We then measured the radial velocity of both components in the 18 spectra available by varying the position of the cores only in a least-squares fit. The least-squares fit was done twice for each spectrum, once with the deep core on the left and once on the right. By comparing the quality of these two fits, both from the chi-squared value and by-eye, we found 13 spectra in which the deeper core could be clearly identified or where the velocities of the two cores are identical to within their uncertainties. The periodogram of the velocities measured from the deeper core calculated over 100 000 frequencies between 0.1 and 10 cycles per day is shown in Fig. 5. The data are sparsely sampled so the periodogram is complex, but there is a single unambiguous peak at an orbital frequency of 0.6240 cycles/day. The periodogram of the radial velocities for the other core gives the same result. The measured radial velocities and a sine wave fit by least-squares to the data for each core are shown in Fig. 6. The next most prominent set of peaks near 1.6 cycles/day are not compatible with the observations taken over a continuous sequence of 6$`\frac{1}{2}`$ hours seen in Fig. 7 starting with a conjunction about 1/3 of the way up the figure and ending near quadrature just over half way up the plot. If the period were near (1/1.6)d these data would cover almost half an orbit and we we then expect to see a second conjunction, which is clearly not the case.

To measure the radial velocities of the two components more precisely we used a simultaneous least-squares fit to all the spectra, i.e., prior to forming the average spectra, of two model profiles, one for each star, in which the position of each model profile is predicted from its time of observation, $`T`$, using the equation $`\gamma _i+K_i\mathrm{sin}(2\pi (TT_0)/P)`$, as before. Only data within 5000 km s-1 of the rest wavelength of H$`\alpha `$ is included in the least-squares fit. The optimum values determined by least-squares for the width and depth of each Gaussian and the parameters of the two circular orbits are given in Table 4. The trailed spectrograms of the data, the fit and the residuals are shown in Fig. 7.

## 4 Discussion

### 4.1 Masses, temperatures and ages

In Table 5 we list the mass ratio $`q=|K_2|/K_1=M_1/M_2`$, where star 1 has the deeper core, for WD 0136+768, WD 0957$``$666 and WD 1204+450 based on the values of $`K_1`$ and $`K_2`$ measured above. We also list measurements of $`q`$ for three other double degenerates where the narrow H$`\alpha `$ core of both stars has been measured. Also given in Table 5 are the orbital period, $`P`$, the ratio of the depths of the H$`\alpha `$ cores, $`l_{\mathrm{H}\alpha }`$, the masses of the two stars, $`M_1`$ and $`M_2`$, estimates of the effective temperatures of the stars, $`T_1`$ and $`T_2`$, and an estimate of the cooling ages of the white dwarfs, $`\tau _1`$ and $`\tau _2`$. We have remeasured $`l_{\mathrm{H}\alpha }`$ for WD 1704$`+`$481.2 from one of the WHT spectra described in Maxted et al. (2000) in which the two cores are clearly resolved using a least-squares fit of multiple Gaussians in which the width of the narrow Gaussians assigned to each core are constrained to have the same width. We also give published mass estimates for the stars based on their temperatures and surface gravities measured from the optical spectrum compared to cooling models for white dwarfs. Where only a single mass from the combined spectrum has been published, we assign individual masses consistent with the mass ratio such that the luminosity weighted mean mass equals the published mass. We take the value of $`l_{\mathrm{H}\alpha }`$ as an estimate of the luminosity ratio since the additional error introduced by this approximation is small compared to the typical uncertainties on the mass estimates ($`\pm `$0.05$`M_{}`$).

WD0135$``$052 is the only binary in Table 5 for which separate effective temperatures have been published for the the two stars. In order to calculate the effective temperatures of the two stars in the other binaries, we compared values of $`l_{\mathrm{H}\alpha }`$ and the effective temperature measured from the combined spectrum to the values predicted by the cooling models of Benvenuto & Althaus (1999) as follows. We used linear interpolation between their grid of models to calculate the radii of the stars as a function of $`T_1`$ and $`T_2`$ for white dwarfs of the appropriate mass. We used the surface brightness values and V$``$R colours tabulated by Bergeron, Wesemael & Beauchamp (1995) combined with the radius and effective temperature calculated from cooling models to calculate the luminosity ratio in the R-band. We then multiplied this ratio by the ratio of H$`\alpha `$ core depths estimated from the effective temperature to get a grid of $`l_{\mathrm{H}\alpha }`$ values. The core depth is taken from a polynomial fit to the depth of the H$`\alpha `$ core versus effective temperature measured from Fig. 3 of Koester & Herrero (1988).

We then assumed that the effective temperature measured from the combined spectrum is the mean of $`T_1`$ and $`T_2`$ weighted by the luminosity on the V-band. The best estimates of $`T_1`$ and $`T_2`$ are then given by intersection of the region of the $`T_1`$$`T_2`$ plane where the predicted value of $`l_{\mathrm{H}\alpha }`$ is the consistent with the observed value and the region where the mean effective temperature is consistent with its observed value. An example is given in Fig. 8 for the case of WD 0136+768. From this figure we see that the uncertainties in the effective temperatures derived are at least 500K. Given the approximations and assumptions used to derive these values, the true uncertainty is probably larger than this, particularly for fainter companions in binaries with large luminosity ratios. Nevertheless, we can estimate the cooling age of the stars given their masses and effective temperatures from the models of Benvenuto & Althaus (1999). The uncertainties on the ages are large since they depend not only on the uncertain mass and effective temperature estimates, but also on the unknown hydrogen layer thickness and other uncertainties in the models. However, we are most concerned here with the relative ages of the two stars, and this is less affected by these systematic errors. We estimate the uncertainty in the relative ages of the stars to be $``$50%.

The exact age we derive for the stars in WD 1704$`+`$481.2 depends on the cooling model used, but we consistently find that star 1 is older than star 2 whichever model we use. Although star 1 has the deeper H$`\alpha `$ core, star 2 is is a more massive CO white dwarf so it is smaller and has cooled faster. This leads to an exception in this case to the general rule that the star with the deeper H$`\alpha `$ core has formed more recently. In all the other cases the star with the deeper core is the younger of the two, as expected.

### 4.2 Comparison to models of DD formation

A full comparison of the observed parameters of DDs to all the available models is beyond the scope of this paper. In this section we re-iterate that the observed mass ratios are not compatible with “standard” models of DD evolution and show that the cooling ages derived above can be a useful test of the feasibilty of models of DD formation.

In Fig. 9 we compare the observed distribution of mass ratios and orbital periods to the distribution predicted by two different models taken from Nelemans et al. (2001), shown as grey-scale images. These predictions include selection effects such as a magnitude limit in the observed sample and the relative luminosity of the two stars. The mass ratio in this case is $`q=m/M`$, where $`m`$ is the mass of the brighter star and $`M`$ is the mass of its companion, so the mass ratio of WD 1704+481.2 is 0.70 according to this definition. We see that models which assume two phases of common-envelope evolution (lower panel) do not predict sufficient DDs with mass ratios near $`q1`$. There is better agreement with the distribution of mass ratios and periods predicted by the model of Nelemans et al. which uses a non-standard parametrization of the first mass transfer phase. However, the number of measured mass ratios is far too small to allow for a more detailed discussion of the relative merits of different cooling models, prescriptions for mass loss, initial distribution of periods and masses, etc.

The non-standard parametrization of the first mass transfer phase used by Nelemans et al. (2001) arises from the case-by-case discussion of the observed properties of DDs by Nelemans et al. (2000) described earlier. They describe scenarios for the formation of WD 0136+768, WD 1101+364 and WD 0957$``$666 based on their proposed model of the first mass transfer phase. These scenarios were devised to explain the observed periods, masses and mass ratios of these DDs. One further test of the feasibility of scenarios which was not expoited in the case of WD 0136+768 and WD 1101+364 was the relative cooling ages of the two white dwarfs. The first mass transfer phase occurs when the more massive star fills its Roche lobe as a result of its rapid expansion at the end of its main-sequence lifetime. This mass transfer phase is assummed not to influence the evolution of the less massive star, so the second mass transfer phase occurs when that star also fills its Roche lobe after its main-sequence lifetime. The time taken for the mass transfer phases is negligible compared to these main-sequence lifetimes, so if the two stars were formed at the same time, we find that their main-sequence lifetimes, $`\tau _{\mathrm{MS},1}`$ and $`\tau _{\mathrm{MS},2}`$, are related to the ages of the white dwarfs, $`\tau _{\mathrm{WD}\mathrm{\hspace{0.17em}1}}`$ and $`\tau _{\mathrm{WD}\mathrm{\hspace{0.17em}2}}`$ by

$$\tau _{\mathrm{MS},1}\tau _{\mathrm{MS},2}\tau _{\mathrm{WD}\mathrm{\hspace{0.17em}2}}\tau _{\mathrm{WD}\mathrm{\hspace{0.17em}1}}$$

where star 1 is the initially less massive star. Since the main-sequence lifetime of a star is strongly dependent on its mass, the observed value of $`\tau _{\mathrm{WD}\mathrm{\hspace{0.17em}2}}\tau _{\mathrm{WD}\mathrm{\hspace{0.17em}1}}`$ is a constraint on the initial mass ratio of the binary, e.g., a larger value of $`\tau _{\mathrm{WD}\mathrm{\hspace{0.17em}2}}\tau _{\mathrm{WD}\mathrm{\hspace{0.17em}1}}`$ implies a larger difference in $`\tau _{\mathrm{MS},1}\tau _{\mathrm{MS},2}`$ which in turn implies a larger difference in the initial masses, i.e., a more extreme initial mass ratio.

We have used the analytical formula of Hurley et al. (2000) to calculate the main-sequence lifetime of a star based on its initial mass for a range of metallicities. For WD 0136+768 Nelemans et al. propose initial masses of 2.25$`M_{}`$ and 2.12$`M_{}`$ so we find $`\tau _{\mathrm{MS},1}\tau _{\mathrm{MS},2}150`$ Myr. This is rather short compared to the difference in cooling ages of $`\tau _{\mathrm{WD}\mathrm{\hspace{0.17em}2}}\tau _{\mathrm{WD}\mathrm{\hspace{0.17em}1}}450`$ Myr. This suggests that the initial masses of these stars differed more than proposed by Nelemans et al. The main-sequence lifetime is very sensitive to the initial mass and the measurements of the white dwarf masses and cooling ages are quite uncertain so it is not possible at this stage to draw more quantitative conclusions. It may even be the case that the scenario for the formation of WD 0136+768 proposed by Nelemans et al. is consistent with the observed properties of this binary given the fairly large uncertainties involved. The same cannot be said in the case of WD 1101+364. In this case, the initial masses of 1.75$`M_{}`$ and 2.30$`M_{}`$ imply a difference in cooling ages of $`800`$ Myr, which is far too long compared to the difference in cooling ages of $`215`$ Myr. Given the relatively small difference in cooling ages seen in this DD, it would appear that a feasible scenario for its formation requires that the initial masses of the stars are more similar to one another than proposed by Nelemans et al. The scenario proposed by Nelemans et al. for the formation of WD 0957$``$666 includes a phase of core helium burning for the more massive star. The observed difference in cooling ages does not constrain the initial mass ratio directly in this case, but Nelemans et al. did show that the relative cooling ages of the two white dwarfs is consistent with the scenario that they propose in this case.

The cooling models for helium white dwarfs are uncertain so one should be careful when drawing conclusions based on quantitative results based on them as we have done for WD0136+768 and WD1101+364. Following a suggestion by a referee, we also considered the models of Driebe et al. (1998). These cooling models cover masses of 0.179$`M_{}`$to 0.414$`M_{}`$, so we were able to apply them to the less massive component of WD0136+768, for example. These models suggest that this white dwarf is about 1.7 Gyr old, much older than the prediction of the Benvenuto & Althaus models. This greater age is the result of a thick hydrogen envelope used in these models. The ages of the stars in WD 1101+364 are increased to 600 Myr and 1.4 Gyr when the models of Driebe et al. are used. Although the difference in the ages is exactly as expected for the scenario outlined by Nelemans et al., the cooling models for these very low mass white dwarfs show hydrogen shell flashes. During these shell flashes the radius of the star increases to $`10R_{}`$, which would result in a further common-envelope phase and loss of some fraction of the thick hydrogen envelope. It is not clear that the models of Driebe et al. are applicable to WD 1101+364 in this case.

## 5 Conclusion

We have determined the mass ratios and orbital periods of the three double degenerate stars WD 0136+768, WD 1204+450 and WD 0957$``$666 by measuring the radial velocities of both stars from the sharp cores of the H$`\alpha `$ line. We have compared the measured mass ratios and orbital periods for these DDs and three others to two models for the formation of DDs, including selection effects, from Neleman’s et al. (2001). We confirm the result that standard models for the formation of DDs do not predict suffucient DDs with mass ratios near 1. We have also shown that the observed difference in cooling ages between white dwarfs in DDs is a useful constraint on the initial mass ratio of the binary.

## Acknowledgments

PFLM was supported by a PPARC post-doctoral grant. CKJM was supported by a PPARC postgraduate studentship. The William Herschel Telescope and the Isaac Newton Telescope are operated on the island of La Palma by the Isaac Newton Group in the Spanish Observatorio del Roque de los Muchachos of the Instituto de Astrofisica de Canarias.


text:
# References

An Electron Paramagnetic Resonance Study of Phase Segregation in Nd0.5Sr0.5MnO3
Janhavi P. Joshi, A. K. Sood and S. V. Bhat 111Corresponding author, Email address: svbhat@physics.iisc.ernet.in
Department of Physics, Indian Institute of Science, Bangalore 560 012, India
Sachin Parashar, A. R. Raju and C. N. R. Rao
Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur P.O, Bangalore 560 064, India

Abstract

We present results of an electron paramagnetic resonance (EPR) study of Nd1-xSrxMnO3 with x = 0.5 across the paramagnetic to ferromagnetic, insulator to metal transition at 260 K (Tc) and the antiferromagnetic, charge ordering transition (TN = Tco) at 150 K. The results are compared with those on Nd0.45Sr0.55MnO3 which undergoes a transition to a homogeneous A-type antiferromagnetic phase at TN = 230 K and on La0.77Ca0.23MnO3 which undergoes a transition to coexisting ferromagnetic metallic and ferromagnetic insulating phases. For x = 0.5, the EPR signals below Tc consist of two Lorentzian components attributable to the coexistence of two phases. From the analysis of the temperature dependence of the resonant fields and intensities, we conclude that in the mixed phase ferromagnetic and A-type antiferromagnetic (AFM) phases coexist. The x = 0.55 compound shows a single Lorentzian throughout the temperature range. The signal persists for a few degrees below TN . The behaviour of the A-type AFM phase is contrasted with that of the two ferromagnetic phases present in La0.77Ca0.23MnO3 . The comparison of behaviour of A-type AFM signal observed in both Nd0.5Sr0.5MnO3 and Nd0.45Sr0.55MnO3 with the two FM phases of La0.77Ca0.23MnO3 , vis-a-vis the shift of resonances with respect to the paramagnetic phases and the behaviour of EPR intensity as a function of temperature conclusively prove that the Nd0.5Sr0.5MnO3 undergoes phase separation into A-type AFM and FM phases.

Key words: Electron paramagnetic resonance, rare earth manganites, phase separation

PACS numbers: 76.30.-v, 75.70.Pa, 72.80.Ga, 71.30.+h

1 Introduction

Manganites of the general formula Re1-xAxMnO3 where Re is a trivalent rare earth ion and A is a divalent alkaline earth ion, exhibit a number of interesting phenomena such as colossal magnetoresistance (CMR), insulator to metal, paramagnetic (PM) to ferromagnetic(FM) or antiferromagnetic(AFM) transitions and charge/orbitally ordered states as a function of x and temperature T . Not surprisingly, they have been the subject of intense study in the last few years. Recent experimental and theoretical studies indicate that manganites undergo intrinsic phase separation (PS) in the CMR regime . PS refers to the spontaneous and competing coexistence of two (or more) different phases such as FM clusters in an AFM background observed in the x-T phase diagram for x $``$ 0.5, of large and intermediate electron bandwidth manganites. A large number of experimental techniques including transport, magnetic, electron microscopy, scanning tunneling microscopy, small angle neutron scattering,  Brillouin scattering,  NMR  and muon spin relaxation measurements, mainly on the prototype manganite La1-xCaxMnO3 have provided evidence for microscopically inhomogeneous FM phases below the Curie temperature (Tc). Recently the Nd1-xSrxMnO3 compound for x = 0.5 is also shown to spontaneously phase segregate . Woodward et al.  using techniques such as x-ray diffraction and neutron diffraction showed a number of interesting features in its phase diagram. It was found that on cooling below Tc, an intermediate A-type AFM phase appeared in addition to the FM phase. Below TN = 150 K, the FM state transforms to a CE-type AFM state in the temperature range of 150 K to 100 K, indicating the presence of FM phase in this temperature range apart from the A-AFM and CE-AFM phases. A study by Ritter et al.  also illustrates coexistence of these three phases at 125 K. It was suggested that such phase segregation aids the field induced structural transitions observed in Nd0.5Sr0.5MnO3 (NSMO0.5) . While most of these studies report the occurrence of PS below Tc, photoemission studies indicated the presence of a phase separated state even above Tc .

Theoretical attempts to understand PS have been mainly through numerical simulations and mean - field calculations. Two different scenarios have emerged, viz electronic phase segregation and disorder-induced mixed state. In the former, a phase separated regime interpolates between the AFM and FM phases while approaching the FM phase by hole doping of the AFM phase. When long-range Coulomb interactions are taken into account, the phase separated domains turn out to be of the order of a few nanometer size as observed in some experiments . However, experimental results of Uehra et al.  indicate the presence of much larger ($``$ micrometer size) domains. It is well known that the A-site cation radius $`<r_A>`$ plays a major role in determining the properties of manganites. It was also found  that the disorder caused by mismatch in the ionic sizes could play a significant role in phase separation as well as in determining the CMR properties. The size of the A-site cation influences the Mn-O-Mn bond angle which in turn affects the hopping rate of the charge carriers. A random distribution in the size of A-site cations leads to a random distribution of the rate of hopping and the random distribution of the exchange coupling constant J which is also determined by the Mn-O-Mn bond angle. A local variation in these parameters, leads the system to be either in FM or AFM state depending on the parameters. On the other hand, creating a large number of FM-AFM interfaces is not energetically favourable. Competition between these two tendencies in a system leads to the formation of clusters much larger than the lattice spacing in which the number of interfaces is reduced and the tendency for local disorder to form either a FM or an AFM phase is partially satisfied. A homogeneous phase would therefore be expected for a compound such as PrCaMnO3 where the A-site cation radii are comparable. As the size disorder grows, the cluster size goes on reducing in the phase separated state. Looking at the ionic radii of various A-site cations in 6-coordinated octahedral structures (Nd : 1.123 A0, Pr: 1.13 A0, Ca : 1.14 A0, Sr : 1.32 A0) one can expect that NdCa or PrCa manganites have more homogeneous phases than NdSr or PrSr manganites which are expected to phase segregate as indeed found experimentally . In spite of a large number of experimental and theoretical studies, a clear and consistent picture of the PS phenomenon is yet to emerge. For example the recent X- band EPR study of Rivadulla et al.  proposes a coexistence of a FM phase with a PM phase in LaCaMnO3 instead of the FM and AFM phases as believed commonly.

Since EPR is a very powerful local probe and is found to be sensitive to the presence of inhomogeneities, we have used the technique to study Nd1-xSrxMnO3 single crystals and powders with a view to investigating the phenomenon of phase separation . We have used samples with x = 0.5 (NSMO0.5) and x = 0.55 (NSMO0.55). The phase diagram of x = 0.5 sample is fairly complex  with coexisting phases in certain regions of the phase diagram. It is a paramagnetic insulator at room temperature. Neutron diffraction studies, however, reveal presence of two-dimensional FM fluctuations  in the paramagnetic state in the vicinity of Tc = 260 K where it transforms to a FM phase. Below 200 K, A-type AFM peaks in the neutron diffraction experiments are observed along with the FM phase indicating a coexistence of FM and A-type AFM phases . The A-type AFM phase consists of FM planes coupled antiferromagnetically to each other and is characterised by the d$`_{x^2y^2}`$ type orbital ordering. Below the Neel temperature TN = 150 K a CE-type AFM state is formed which also coexists with the A-type AFM state . The CE-type state is characterised by 3x2 \- r2/3y2-r2 orbital ordering. The Neel temperature is also the charge ordering temperature in this material. NSMO0.55 on the other hand is not known to show any phase separation. It is a paramagnetic insulator at room temperature and transforms to an A-type AFM state at TN = 230 K with d$`_{x^2y^2}`$ orbital ordering without any charge ordering . We compare the EPR results of NSMO0.55 which does not show any phase segregation with those of NSMO0.5 and find that these two samples behave very differently . To compare and contrast with the results on these two materials we have also studied La0.77Ca0.23MnO3 (LCMO). LCMO (Tc $``$ 230 K) shows phase separation into two ferromagnetic phases, one metallic and the other insulating . Thus we can expect very different behaviour of various lineshape parameters in LCMO from the ones in the Nd0.5Sr0.5MnO3 and Nd0.45Sr0.55MnO3 .

2 Experimental

The single crystals of NSMO0.5 were prepared by the float zone technique. The resistivity measurements show a transition from insulating state to a metallic state at Tc = 260 K. Further transition to an AFM insulating state is observed at TN = 150 K. Magnetization measurements show a sharp increase in the susceptibility at 260 K, which remains practically temperature independent till $``$ 150 K, below which it shows a sharp drop. Single crystals of NSMO0.55 were also prepared by the same method. The resistivity measurements show a monotonic increase with decreasing temperature and a sharp increase at TN = 230 K. The magnetization measurements show a monotonic increase in the susceptibility till 230 K with a sharp fall at this temperature.

The EPR experiments were carried out on both single crystal and powder samples of NSMO0.5 using a Bruker X - band spectrometer (model 200D) equipped with an Oxford Instruments continuous flow cryostat (model ESR 900). Similar experiments were carried out on a single crystal and powdered single crystal of NSMO0.55 and LCMO. The spectrometer was modified by connecting the X and Y inputs of the chart recorder to a 12 bit A/D converter which in turn is connected to a PC enabling digital data acquisition. With this accessory, for the scan-width typically used for our experiments i.e 6000 Gauss, one could determine the magnetic field to a precision of $``$ 3 Gauss. For single crystal study the static magnetic field was kept parallel to the c-axis of the crystals. The temperature was varied from 4.2 K to room temperature (accuracy: $`\pm 1K`$) and the EPR spectra were recorded while warming the sample. For measurements on powder the samples obtained by finely crushing the single crystals of the respective materials , were dispersed in paraffin wax. During all the experiments a speck of DPPH was used as a g-marker whose signal was subsequently subtracted digitally to facilitate lineshape fitting.

3 Results and Discussion

Figure 1 shows a few typical EPR signals of those recorded from the powder sample of NSMO0.5 in the temperature range from 290 K to 80 K. The signal intensity goes on decreasing below 150 K and below 80 K the signal becomes too weak to analyse. As can be seen from the figure the relatively narrow EPR lines in the PM phase become broad below Tc. Further they show considerable variation in the lineshapes as a function of temperature. Based on the nature of the lineshapes, we have divided the whole temperature range into five different regions and have fitted appropriate lineshape functions to the signals in each region. In figure 1 we have indicated the region to which the respective signals belong. The method of analysis followed for each region is described below.

1. In the temperature range between 290 K and 255 K (the signals at 290 K and 277 K in figure 1), the signals are narrow and are well fitted to the derivative of a single Lorentzian described by equation:

$$\frac{dP}{dH}=\frac{d}{dH}(\frac{\mathrm{\Delta }H}{(HH_0)^2+\mathrm{\Delta }H^2})$$
$`(1)`$
where $`\mathrm{\Delta }`$ H is the linewidth and H0 is the center field.
2. Distorted signals are observed in the temperature range of 250 K to 200 K as shown by data for 210 K. These signals are also quite broad and therefore they have to be fitted with the derivative of Lorentzian consisting of two terms given by equation

$$\frac{dP}{dH}=\frac{d}{dH}(\frac{\mathrm{\Delta }H}{(HH_0)^2+\mathrm{\Delta }H^2}+\frac{H}{(H+H_0)^2+\mathrm{\Delta }H^2})$$
$`(2)`$
where the first term represents signal response due to the clockwise polarized component of microwaves and the second term represents the signal due to the anticlockwise polarized component of the microwaves . In this temperature range, we found that we could obtain better fits by using two Lorentzian functions with different linewidths and center fields, each described by equation 2.
3. Much broader signals are observed in the temperature range from 200 K to 155 K which could be very well fitted to the lineshape function as described in (2) above consisting of two Lorentzians (signal at 180 K shown in figure 1).

The separation into regions two and three has been made based on the quality of fits which we have obtained using the same equation in the two regions. It can be clearly observed that the quality of fits continuously goes on improving as the temperature is reduced in region 2 till 200 K (note the difference between the experimental curve and the fitted curve at 240 K and 210 K), indicating an evolution of lineshapes which results in the lineshapes of region 3.
4. In the temperature range between 150 K to 100 K we observe the development of a distortion in the signal close to zero field (indicated by a circle on the signal at 140 K in figure 1). The signals in this range could not be fitted either to a single Lorentzian as in region 1 or to two Lorentzians as in regions 2 and 3. However if the data set in the low field region is excluded we could fit these signals to a single Lorentzian.
5. Undistorted broad signals between 100 K and 80 K are observed which fit excellently to a single Lorentzian (equation 2)(signal at 80 K shown in figure 1).

In Figures 2a and 2b we plot the center fields (H0) and linewidths obtained from the lineshape fits as described above as a function of temperature. The vertical dotted lines show the different regions in which we categorized the different temperature ranges from 80 K to 290 K. As can be seen from Figure 2a, the center field at 290 K is 3407 Gauss ($`\pm `$ 3 Gauss) corresponding to ‘g’=1.976 which is less than the free electron ‘g’ value. In region 2 where we have fitted the signal to two Lorentzians, H0 of one of the components is less than H0 in region 1 (component ‘P’). The H0 of this component goes on decreasing with decreasing temperature upto 200 K. The H0 of the second component (component ‘Q’) on the other hand is greater than the H0 in region 1 and it shows a weak temperature dependence and increases as the temperature is reduced. In the third region these two components have opposite temperature dependences to that in region 2. The ‘P’ component shows an increase in H0 as the temperature is reduced remaining less than the H0 value in region 1. Component ‘Q’ on the other hand shows a decrease as a function of decreasing temperature. In region 4 the single H0 of the Lorentzian fitted to the signal excluding the low field region, shows a non-monotonic behaviour and has a magnitude less than that in region 1. In region 5, H0 is practically temperature independent.

As can be seen from Fig. 2b, the linewidth of the single Lorentzian fitted to the signals in region 1 shows an increase as a function of decreasing temperature. This increase continues in regions 2 and 3 for both the Lorentzian components ‘P’ and ‘Q’ fitted in these regions. In region 3 at a temperature 170 K $``$1.1 TN a peak in the linewidth is observed. Below this temperature in region 3 linewidths of both the signal components decrease with decreasing temperature. In regions 4 and 5 it again increases as a function of decreasing temperature. It is noteworthy that unlike the other manganites studied before  signals do not disappear in the antiferromagnetic phase i.e below TN = 150 K.

Figure 3 shows the signals from the single crystal of NSMO0.5 at different temperatures. At temperatures from 290 K to 260 K the signals have Dysonian lineshapes which progressively distort as the temperature is lowered below 260 K and evolve into very broad lines presumably consisting of more than one signal. A distortion near the zero field similar to signals in the powder sample appears in these signals as well below 150 K. The line further broadens, decreases in intensity as the temperature is reduced below 100 K. Below $``$ 80 K the signal becomes very broad with a signal to noise ratio too poor for analysis. The signals down to 270 K could be fitted to the Dysonian lineshape .

$$\frac{dP}{dH}=\frac{d}{dH}\frac{\mathrm{\Delta }H+\alpha (HH_0)}{(HH_0)^2+\mathrm{\Delta }H^2}$$
$`(3)`$
where $`\alpha `$ is the asymmetry parameter representing the ratio of the absorption component to the dispersion component of the response. However it was not possible to fit the signals below that temperature to any of the following models: (i) single Lorentzian with two terms, to take into account both left and right circularly polarised microwave fields. (ii) two Lorentzians (accounting for phase segregation) with two terms each to take into account both left and right circularly polarised microwave fields. (iii) single Dysonian with two terms to take into account both left and right circularly polarised microwave fields. (iv) two Dysonians (accounting for phase segregation) with two terms each to take into account both left and right circularly polarised microwave fields. Keeping in mind the fact that the signals from the powder of the same sample could be adequately fitted, we conclude that the inability to do so in case of the single crystal samples is due to the effect of the multidomain structure which may be present.

In the inset of figure 4 we show few representative signals obtained from powder sample of LCMO. The resonance fields obtained by fitting these signals (to a single Lorentzian described by eq. 1 in the paramagnetic phase and to two Lorentzians, each described by eq. 2, below 165 K) are also shown in the figure.

Figure 5 shows the signals from the powder sample of NSMO0.55 from 200 K to 290 K. Below 200 K the signal is too weak to analyse. The signals are narrow and are symmetric. They are fitted to the Lorentzian lineshape and the fitting parameters thus obtained, viz, H0, peak to peak linewidth $`\mathrm{\Delta }`$Hpp are plotted in Fig. 6 as a function of temperature. As shown in Fig. 6a the linewidth monotonically decreases as the temperature is reduced till 210 K below which it shows a sharp increase. The minimum in the linewidth occurs at 210 K. Here again, we observe a signal in the AFM state which is A-type. The resonance fields H0 plotted in fig. 6b show a weak temperature dependence throughout the temperature range increasing till 210 K and then shows a decrease. The g value obtained from the resonance fields is less than the free electron g value and remains so throughout the temperature range. The intensity shows a peak at 210 K and then decreases sharply. It roughly follows the temperature dependence shown by dc susceptibility.

In figure 7, we plot the double integrated intensities of different signal components in the three materials for the sake of comparison.

Based on an analysis of the different lineshapes of the powder signals of NSMO0.5 we make the following observations. In region 1, the signals fit very well to the derivative of a single Lorentzian. Clearly, the sample is monophasic and homogeneous. Neutron diffraction measurements  also show that the sample is paramagnetic and monophasic in this region. The ‘g’ value obtained from the EPR experiments is smaller than the free electron ‘g’ value as expected for a CMR manganite in contrast with the hole doped CO manganites where ‘g’ values are greater than the free electron values. Linewidths in this region are much smaller than those of the CO manganites studied by us earlier in their paramagnetic state . As we go into region 2, the quality of the fits to the derivative of single Lorentzian deteriorates. This may be understood in terms of the building up of FM correlations as verified by neutron diffraction  and by the two-dimensional nanoscopic structural correlations as proposed by Kiryukhin et al.  based on x-ray diffraction experiments. Presence of such fluctuating FM correlations may cause distortion of a Lorentzian signal due to the fluctuating internal fields. We have fitted these signals to the derivative of Lorentzians containing two components. The center fields corresponding to these two components have magnitudes shifted above and below the center field in the PM region. We attribute this behaviour to the presence of A-type AFM (component Q) and FM (component P) phases in the sample, respectively. Detailed evidence will be provided below in support of this assignment.

Now we would like to consider another possibility which could possibly give rise to a multiline spectrum in the ferromagnetic state. It has been observed in single crystal specimen of ferromagnetic metals like Nickel  and Iron  that a multiline complex spectrum results due to the magnetic anisotropy of the ferromagnetic sample. When the applied magnetic field is oriented away from the easy axis, the two components of magnetisation, one driven by the torque of the anisotropy field and the other due to the applied magnetic field, can cause the splitting of the EPR spectrum. Similar splitting was observed in a polycrystalline ferrite sample by Schlomann et al.  who have studied the temperature dependence of the resulting EPR spectrum. This happens when the anisotropy fields are large with respect to the resonant field. However the situation in manganites is different. A study of the effect of magnetic anisotropy on EPR signals of manganites has been carried out by Lofland et al.  in single crystalline La1-xSrxMnO3 and they estimate the anisotropy field to be $``$ 160 Gauss. The anisotropy field in NSMO0.5 could not be very different from that in La1-xSrxMnO3 since the two are structurally similar high bandwidth manganites. Therefore, the anisotropy field in NSMO0.5 is much less than the resonance field which is $``$ 3000 Gauss.

Schlomann et al.  have done the temperature study of split signals in ferrites. They observe that due to magnetic anisotropy of their ferrite samples, the splitting of their signals increases as the temperature is decreased. However, both the components of the signal shift towards the low field side as a function of decreasing temperature and the intensity of the low field component continuously increases. Our observations in NSMO0.5 are qualitatively very different from these as seen from Fig. 2a. The intensity of the two signal components also does not follow the trend as seen by Schlomann et al. Moreover, the two line structure observed in the polycrystalline samples is due to a powder pattern  and does not fit to two Lorentzian lineshape functions. Because of these reasons we believe that the observed splitting of the EPR signal cannot be attributed to the magnetic anisotropy in NSMO0.5. In a recent work Shames et al.  derive similar conclusion for their EPR study on La1-xCaxMnO3 (x=0.5)

Another complicating factor in magnetically ordered materials, namely, the demagnetizing fields due to possibly different sized and shaped particles does not seem to be significant in our experiments. As mentioned by Lofland et al.  and Patil et al.  demagnetizing fields cause a shift in the position of the DPPH signal. Throughout the temperature range, we did not observe any change in the DPPH position, even across Tc when the demagnetizing factors were expected to come into picture.

As seen in Fig. 2b, the linewidths in the regions 2 and 3 are much larger compared to those in CO manganites probably due to the large distribution of internal fields in the FM state. The linewidths of the AFM component are also large as expected, and are comparable to linewidths of the FM phase. A peak in the linewidth in region 3 appears at nearly 1.1TN. In region 4, only CE-type and A-type phases are expected to be present according to the neutron diffraction studies of Kajimoto et al. . However the signals in this region show distortion near the zero field. This is the temperature range just below TN. The lineshape has been fitted to the part of the signal excluding this distortion. The temperature dependence of the center field is non-monotonic showing a peak at 130 K. The linewidth also shows a non-monotonic temperature dependence in region 4, passing through a minimum at 130 K. Below 100 K i.e in region 5 according to the neutron diffraction studies of Kajimoto et al. and Woodward et al. A-type and CE-type phases are present. The signal observed in this region, a broad but a single Lorentzian fits very well to equation 2. We can attribute this signal to the A-type AFM phase or the FM phase which gradually converts to CE phase since CE-type AFM phase does not give an EPR signal as shown by our previous studies in CO manganites Pr0.6Ca0.4MnO3 and Nd0.5Ca0.5MnO3 . The linewidth in this region increases monotonically with center field being practically temperature independent. We shall come back to the origin of these signals in the subsequent discussion.

From the above analysis of results of NSMO0.5 powder, it is clear that the EPR lineshapes are very sensitive to the magnetic inhomogeneity of the sample. The analysis of the single crystal data was made difficult by large linewidths, large internal field effects and the sensitivity of the signals to the orientation of sample with respect to the magnetic field. Fitting of the highly distorted signals below Tc was practically impossible. Below 100 K, only a part of the line could be recorded in the available field range as can be seen from Fig. 3.

In the previous discussion of the EPR results on NSMO0.5, we have presented two important results, (1) EPR presents evidence for phase segregation and (2) This phase segregation in NSMO0.5 involves, separation into a ferromagnetic phase and an A-type antiferromagnetic phase. In the following we provide additional evidence to support these conclusions. We present EPR results on La0.77Ca0.23MnO3 (LCMO), which is known to phase separate into two ferromagnetic phases  and on Nd0.45Sr0.55MnO3 (NSMO0.55) which is known to undergo a transition to a homogeneous A-type AFM phase.

EPR in LCMO

As can be seen from the inset of fig. 4, the EPR signals in LCMO from room temperature to 225 K (Tc $``$ 230 K) are narrow (denoted by symbol ‘A’) and can be fitted to the Lorentzian lineshape function given by eqn 1. The signals in the range 225 K - 170 K (see for example the signal at 210 K) seem to be consisting of two components. The narrow signal component ‘A’ observed in this temperature range represents the presence of residual paramagnetic phase. The ferromagnetic phase gives rise to the broad signal component ‘B’. The component ‘A’ decreases in intensity with decreasing temperature and the component ‘B’ increases in intensity resulting in a lineshape shown at 165 K. The signals from 165 K down to lowest temperature however could be very well fitted to two Lorentzians each represented by eqn 2. We have obtained the resonanant fields and the double integrated intensity from these fits. The resonance fields plotted in fig. 4 are practically temperature independent in the paramagnetic phase. In the ferromagnetic phase however, both the signal components show a resonance field shifted to lower field side compared to that in the paramagnetic phase as expected from a ferromagnetic phase. This is consistent with the earlier evidence from NMR experiments  that the two phases at this composition are ferromagnetic (one being insulating and another being metallic.) It is to be noted that we start observing the signatures of phase separation at a higher temperature than the NMR studies. We believe that this is because of the different timescales of the two techniques, EPR being a much faster probe than NMR. A very important point to note here is that the shift of resonance fields in LCMO in the phase separated regime is very different from that of NSMO0.5, in that, one of the two signals (marked as ‘Q’) in NSMO0.5 shifts to a resonanant field higher than the resonant field in the paramagnetic phase and the other signal (marked as ‘P’) shifts to a lower field than the signal in the paramagnetic phase. This low field shift indicates that component ‘P’ is obviously from the ferromagnetic phase present in the sample in this temperature range. We propose that the high field signal component in region 2 and 3 in fig. 2a is indeed due to A-AFM phase which is present in the sample in that temperature range. To substantiate this claim we now discuss the results of NSMO0.55 which is a single phasic homogeneous sample but goes into an A-AFM phase.

EPR in NSMO0.55

Figure 6 presents the EPR parameters $`\mathrm{\Delta }`$Hpp and H0 obtained from the Lorentzian fits to the signals of NSMO0.55.

Throughout the temperature range in which we observe the EPR signal, we see that the signal is a single Lorentzian as expected for a homogeneous powder sample. It may be noted that we observe a signal below the Neel temperature unlike the CO manganites studied before  but similar to NSMO0.5 which has an A-type AFM phase below 200 K. We would also like to mention here that the resonance field of the component Q of NSMO0.5 also has a ‘g’ value smaller (as indicated by the shift of the signal towards higher fields) than the paramagnetic ‘g’ value similar to NSMO0.55 signals. Further, the temperature dependence in the two cases is also qualitatively similar which supports our interpretation that the component Q of NSMO0.5 signals is due to the A-type AFM phase.

Finally, we analyse the intensities of the EPR signals in the three materials studied here. As can be seen from fig. 7a, in case of NSMO0.5, the EPR intensity in the PM phase shows a weak temperature dependence as expected for the PM phase. The intensity of both the signal components below Tc rises very sharply. However, below 200 K which is reported to be the Neel temperature of A-AFM phase , the intensity of the component Q drops very rapidly. A similar sharp drop of intensity below 210 K is also seen in NSMO0.55 (fig. 7b). On the other hand the intensity of the P component shows a much broader peak indicating nearly temperature independent intensity down to 150 K. The FM phase in the temperature range of 240 K to 150 gradually changes over to CE phase below 150 K . Ritter et al.  have also observed the presence of FM phase at 125 K. Hence it is to be expected that the signal intensity of the component P drops gradually as the amount of FM phase in the sample decreases gradually. The resonance fields of these signals are below PM values. Hence we conclude that the behaviour in regions 4 and 5 of fig. 2a and 2b in the temperature range of 150 K to 80 K are to be attributed to the residual FM phase in the sample.

In marked contrast to this behaviour is the behaviour of intensity of the two phases in LCMO. (fig. 7c) The intensity of these two phases remains practically temperature independent down to very low temperature as is to be expected for any FM phase which remains stable down to very low temperature.

In conclusion, the present study of x=0.5 and 0.55 compositions of Nd1-xSrxMnO3 and La0.77Ca0.23MnO3 demonstrates that EPR can be used as a powerful diagnostic tool for investigating phase segregation in manganites.

While this paper was about to be submitted, we came to know of the work by Rivadulla et al.  which also reports briefly on their EPR study of Nd0.5Sr0.5MnO3. While both of our works report the presence of a mixed phase in this compound, Rivadulla et al. conclude that ferromagnetic and paramagnetic phases are present below Tc while we believe for the reasons described in detail in this paper, the mixed phase consists of FM and A-type antiferromagnetic phases.

4 Acknowledgments

AKS and SVB thank Department of Science and Technology and University Grant Comission for financial support. JJ thanks CSIR, India for a fellowship and F. Rivadulla for helpful critical comments.

Figure Captions

FIGURE 1:

EPR spectra of a powder sample of Nd0.5Sr0.5MnO3 for a few representative temperatures. The solid circles are experimental data and the solid line shows the fit to the appropriate equation as described in the text. The numbers on the left of each spectrum indicate the region to which it belongs. The region indicated by a circle at 140 K is excluded from fitting.
FIGURE 2

Temperature dependence of (a) the center fields H0 and (b) the linewidths $`\mathrm{\Delta }`$H obtained from the fits to EPR spectra of powder Nd0.5Sr0.5MnO3. The vertical dotted lines indicate different regions in which the temperature range is divided. The two signal components obtained by the fits are indicated by the letters P and Q in both Fig. a and b.
FIGURE 3

EPR spectra of a single crystal sample of Nd0.5Sr0.5MnO3 at a few representative temperatures. The solid circles are the experimental data points. The smooth lines shown at some temperatures are fits to (i)a single Dysonian lineshape function (290 K and 270 K) and (ii) two Dysonians (245 K) (equation 3).
FIGURE 4

The resonance fields of La0.77Ca0.23MnO3 powder signals plotted as a function of temperature. The inset shows a few representative signals from La0.77Ca0.23MnO3 powder. The signal component denoted by ‘A’ represents the signal from the paramagnetic phase and the one denoted by ‘B’ represents the signal from the ferromagnetic phase. The solid circles in the inset are the experimental data and the solid lines are the fits to the appropriate equations described in the text.
FIGURE 5

EPR spectra of a powder sample of Nd0.45Sr0.55MnO3 at a few representative temperatures. The solid circles are the experimental data and the solid lines are fits to the Lorentzian lineshape (equation 3) .
FIGURE 6

Temperature variation of the lineshape parameters for the powder sample of Nd0.45Sr0.55MnO3 (a) linewidth(b) H0 obtained from the fits to equation 1. The inset shows the g values calculated from H0.
FIGURE 7

The normalised double integrated intensity (area under the curve) of the EPR signal components plotted as a function of temperature for (a) NSMO0.5 (b) NSMO0.55 (c) LCMO samples. The lines are guides to the eye.