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# New Constraints on the Energetics, Progenitor Mass, and Age of the Supernova Remnant G292.0+1.8 Containing PSR J1124-5916

## 1 Introduction

$`\mathrm{𝐶ℎ𝑎𝑛𝑑𝑟𝑎}`$ has been advancing our understanding of core-collapse supernovae by revealing their collapsed cores and their outflows, the distribution of supernova ejecta, and their interaction with the interstellar medium (ISM). Increasing the sample of SNRs with a hybrid morphology (i.e. Composite-type SNRs) helps address questions related to the birth properties and evolution of neutron stars and SNRs in the ISM.

G292.0+1.8 (MSH 11-54) offers a unique laboratory to address these questions because of its hybrid morphology, its youth, and its size. This SNR is one of three Oxygen-rich remnants in our Galaxy. It was first discovered in the radio band (Milne 1969; Shaver & Goss 1970), where it exhibits a centrally-filled morphology indicative of the presence of a PWN. $`\mathrm{𝐸𝑖𝑛𝑠𝑡𝑒𝑖𝑛}`$ and $`\mathrm{𝐸𝑋𝑂𝑆𝐴𝑇}`$ X-ray observations classified the remnant as a type-II explosion of a massive star (Hughes & Singh 1994). $`\mathrm{𝐶ℎ𝑎𝑛𝑑𝑟𝑎}`$ observations led to the discovery of the long-sought PWN (Hughes et al. 2001; Safi-Harb & Gonzalez 2001) surrounding a candidate pulsar. An imaging study of the SNR with $`\mathrm{𝐶ℎ𝑎𝑛𝑑𝑟𝑎}`$ (Safi-Harb & Gonzalez 2001; Park et al. 2002) traced the distribution of the ejecta. The remnant has a morphology similar to Cas A on small scales (Hwang, Holt, & Petre 2001), however, no Fe-K line-emission was detected.

The discovery of the PWN in G292.0+1.8 prompted a deep search for radio pulsations and led to the discovery of a 135 ms pulsar coincident with the $`\mathrm{𝐶ℎ𝑎𝑛𝑑𝑟𝑎}`$ X-ray point source (Camilo et al. 2002a). The pulsar has a derived spin-down luminosity $`\dot{E}`$ of 1.2$`\times `$1037 erg s-1, a surface magnetic dipole field strength of 1$`\times `$1013 G, and a characteristic age of 2,900 yrs. To date, the only estimate of the age of this SNR is from optical studies of the high-velocity material coincident with the PWN (Murdin & Clark 1979). The age of 1,600 years is a factor of 1.8 less than the characteristic age of the pulsar.

In this Letter, we present the first detailed spatially resolved spectroscopy of the $`\mathrm{𝐶ℎ𝑎𝑛𝑑𝑟𝑎}`$ observation in order to infer the intrinsic parameters of the supernova explosion and its associated pulsar and PWN. In §2, we briefly summarize the observation and present our sub-arcminute spatially resolved spectroscopy of the SNR and the embedded PWN. In §3, we discuss our results and infer the energetics of the supernova explosion, the mass of the progenitor, the SNR’s age, the pulsar’s transverse velocity and the pulsar wind parameter. We also report the first evidence for spectral softening of the power law index of the PWN with increasing distance from the pulsar.

## 2 Sub-arcminute spatially resolved spectroscopy

G292.0+1.8 was observed with the S3-chip of the Advanced CCD Imaging Spectrometer (ACIS) on board $`\mathrm{𝐶ℎ𝑎𝑛𝑑𝑟𝑎}`$ on March 11, 2000, at a CCD temperature of -120oC. We corrected for Charge Transfer Inefficiency (CTI) by applying the $`\mathrm{𝑐𝑡𝑖𝑐𝑜𝑟𝑟𝑒𝑐𝑡𝑖𝑡}`$ tool to the event 1 raw data (Townsley et al. 2000). A new event 2 file was then obtained by screening the data using standard $`\mathrm{𝐶𝑖𝑎𝑜}\mathit{2.2}`$ routines. The resulting exposure time was 38 ksec.

### 2.1 SNR

To perform spatially resolved spectroscopy of the SNR, we selected the 23 bright regions shown in Fig. 1 (left). In this image, the broadband emission from the SNR was divided into soft (0.3–1.15 keV, red), medium (1.15–2.15 keV, green) and hard (2.15–10.0 keV, blue) contributions, each smoothed with a gaussian with $`\sigma `$=1$`\stackrel{}{\mathrm{.}}`$5 . The PWN is clearly visible in blue near the center of the SNR. We fitted the spectra of the remnant in the 0.5–8.0 keV range using the non-equilibrium ionization (NEI) model, $`\mathrm{𝑣𝑝𝑠ℎ𝑜𝑐𝑘}`$ (Borkowski, Lyerly, & Reynolds 2001) in version 11.0.1 of the XSPEC package (Arnaud 1996). This model is appropriate for modeling plane-parallel shocks in young SNRs whose plasma has not reached ionization equilibrium. It is characterized by the shock temperature, $`kT`$, and the ionization timescale, $`n_et`$, of the plasma. Here, $`n_e`$ is the post-shock electron density and $`t`$ is the time since the passage of the shock. $`t`$ can then be used as a lower estimate on the SNR age. Since the remnant is ejecta-dominated, we allowed the abundances to vary.

One-component NEI model fits yielded an average temperature for the selected regions of 0.9$`\pm `$0.3 keV, with minimum and maximum values of 0.6 and 1.7 keV, respectively. The ionization timescale varied across the SNR from $``$1011 to 1013 cm-3 s. These values indicate that the emission from the ejecta contains a wide range of temperatures and ionization states. The highest ionization state values are associated with regions 1, 3, and 9 (see Fig. 1, left), indicating that the plasma has reached ionization equilibrium in the southeast. Relative abundances were well constrained in these models and were used to derive the abundance ratios discussed in §3.2.

We subsequently attempted two-component model fits. This was motivated by the expectation of a high-temperature and a low-temperature plasma associated with the supernova blast wave and reverse shock, respectively (see e.g. Safi-Harb et al. 2000). While the overall fits were slightly improved, the abundances could not be well constrained due to the large number of free parameters. The derived average temperatures for the hot and cool components were 1.05$`\pm `$0.34 keV and 0.37$`\pm `$0.18 keV, respectively. These are lower than 1.64$`{}_{0.2}{}^{}{}_{}{}^{+0.3}`$ keV, as reported by Hughes & Singh (1994) from their one-component NEI model fit to the $`\mathrm{𝐸𝑖𝑛𝑠𝑡𝑒𝑖𝑛}`$ and $`\mathrm{𝐸𝑋𝑂𝑆𝐴𝑇}`$ data. The discrepancy is probably due to the contamination by the previously unresolved PWN.

### 2.2 PWN

$`\mathrm{𝐶ℎ𝑎𝑛𝑑𝑟𝑎}`$ observations of PWNe have shown that 1) PWNe harbor torus-like and jet-like structures indicating equatorial and polar outflows, and 2) the power law photon index steepens away from the pulsar, as expected from synchrotron and expansion losses (see e.g. Safi-Harb 2002 for a review). By examining this PWN, we find evidence of an arcsecond-scale east-west elongation and an extension to the south (see Fig 1, right), hinting at structures associated with the deposition of the pulsar’s wind energy into its surroundings. To search for spectral variations, we divided the inner $`45^{\prime \prime }`$ of the PWN into four concentric rings to obtain enough counts to extract a spectrum. As reported by Hughes et al. (2001), the spectrum of the PWN is heavily contaminated by thermal emission from the SNR. In order to minimize this contamination, we used a nearby region as background and restricted the fit to the 1.5–7.0 keV range, thus reducing the contamination by Oxygen, Neon, and Magnesium ejecta. Using a power-law model, we find that the photon index ($`\mathrm{\Gamma }`$) steepens away from the pulsar (see Table 1). This result is expected from synchrotron losses and is reminiscent of Crab-like nebulae (e.g. Safi-Harb et al. 2001).

## 3 Discussion

### 3.1 Distance

From our one- and two-component fits, we derive an average value of $`N_H`$=(0.5 $`\pm `$ 0.1)$`\times `$1022 cm-2 for the remnant. We can use this value to verify previous estimates for the distance to G292.0+1.8. The extinction per unit distance in the direction of the remnant can be estimated from the contour diagrams given by Lucke (1978): $`E_{BV}/D`$$``$0.2 mag kpc-1. Using the relation $`N_H/A_V`$=1.79$`\times `$1021 cm-2 mag-1, which translates into $`N_H/E_{BV}`$=5.55$`\times `$1021 cm-2 mag-1 (Predehl & Schmitt 1995), we derive a distance of 3.6–5.5 kpc. A distance of 4.8 kpc, as used in the previous studies, is then a good approximation and is adopted in the following discussion.

### 3.2 Supernova Parameters

We subsequently use our NEI model fits to derive the supernova parameters. In the standard picture of X-ray emission from young SNRs, the soft component arises from shocked ejecta and the hard component is usually attributed to the blast wave shocking the surrounding medium. Our spatially resolved spectroscopy indicates that most of the regions in the SNR (except for the PWN, the outermost regions and the eastern ‘belt’-like filament near the SNR center) are well fitted with a one-component NEI ($`\mathrm{𝑣𝑝𝑠ℎ𝑜𝑐𝑘}`$) model with high metal abundances (with respect to solar), indicating that these knots are the shocked ejecta associated with the explosion of a massive star. Nucleosynthesis yield as a function of the progenitor’s mass has been numerically computed by Woosley and Weaver (1995) and several others. In order to derive the progenitor’s mass, we use the abundance ratios from our NEI model fits in the 0.5–8.0 keV band to the ejecta-dominated regions. In Fig. 2, we plot the average values for these ratios along with their rms scatter. Over-plotted are the predicted ratios from nucleosynthesis models for progenitors of 25, 30, 35 and 40 M. We then conclude that the measured abundance ratios are consistent with a progenitor’s mass of 30–40 M.

Regions 20 to 23 selected in our analysis are of special interest (see Fig. 1, left). Region 20 is part of a set of sharp circumferential filaments surrounding the bulk of the ejecta-dominated X-ray emission. Regions 21, 22 and 23 are part of an outer faint ridge of emission delimiting the SNR. We believe that these latter regions indicate the location of the blast wave shocking the surrounding medium for the following reasons: 1) as shown in Table 2, the abundances derived for region 21 using one-component models are consistent with ISM abundances (sub-solar) and are the lowest ones throughout the remnant, while those derived for region 20 are contaminated by ejecta; 2) the outermost emission is absent in the equivalent width maps which reveal the ejecta (Park et al. 2002); and 3) even two-component model fits to regions 21–23 require sub-solar abundances, which is not the case for region 20, where both components require above-solar abundances.

In order to estimate the SNR age, we will adopt our more reliable one-component fits to regions 21–23 in the 0.5–8.0 keV band. The corresponding SNR size would be r$``$$`4.2^{}`$=5.9 pc (at 4.8 kpc). In the following example, we will use the parameters derived for region 21 shown in Table 2. The observed emission measure (EM) of 0.09$`\pm `$0.02 (after scaling it to the SNR volume) corresponds to: $``$$`n_e`$$`n_H`$dV=1014(4$`\pi `$D2)(EM) = (2.5$`\pm `$0.6)$`\times `$1058 cm-3. If the emission volume V=$`f`$$`V_{tot}`$, where $`f`$ is the filling factor, we find an upstream density $`n_0`$ = (0.23$`\pm `$0.03) $`f^{1/2}`$ cm-3. From our fit parameter $`n_0t`$, obtained from the $`\mathrm{𝑣𝑝𝑠ℎ𝑜𝑐𝑘}`$ model, we find a shock age of $`t`$=(2,500$`{}_{700}{}^{}{}_{}{}^{+1100}`$)$`f^{1/2}`$ years. Similarly, we derive the parameters for regions 22 and 23 and summarize them in Table 3. For a reasonable filling factor of 0.25, the shock age varies from 1,250–4,450 years. The discrepancy between these ages suggests that the northeastern regions are shocked at earlier times that the western regions, probably due to an inhomogeneous medium. This complication makes the determination of the SNR parameters in this manner uncertain.

In order to estimate the global properties of the SNR independently of the small-scale density variations, we attempted to fit the spectrum of the whole remnant. We found this to be extremely difficult using the entire 0.5–8.0 keV band and various combination models with up to three components. This difficulty is due to the large number of NEI components needed to account for the variations in temperature and ionization time-scale of the ejecta, as indicated in our spatially resolved spectroscopy described above. However, restricting the fit to the 2.0–8.0 keV range (to remove the contamination from O, Ne, Mg and Si ejecta) and excluding the pulsar and its PWN, we found that a two-component model ($`vpshock+sedov`$) provides an acceptable fit for the overall spectrum with $`\chi `$$`{}_{\nu }{}^{}{}_{}{}^{2}`$(dof)=1.17(197); $`\mathrm{𝑠𝑒𝑑𝑜𝑣}`$ is an NEI model that accounts for the hot thermal emission from the SNR interior and is based on the Sedov dynamics (Borkowski et al. 2001). The $`\mathrm{𝑣𝑝𝑠ℎ𝑜𝑐𝑘}`$ model was used to characterize the emission from the Sulfur ejecta, while the $`sedov`$ model was used to characterize the blast wave component (abundances of 2/3 solar with equal electron and ion temperatures). In Table 4, we summarize the SNR parameters estimated from using equations (4a-4f) in Hamilton et al. (1983). The derived tabulated value of $`n_0`$ is consistent within the various uncertainties with that derived from the observed emission measure. The SNR age, $`t`$(Sedov)=2,400–2,850 yrs, is comparable to the average value derived from regions 21–23 above. This age represents a more reliable estimate for the age of the remnant since the contamination from ejecta has been minimized and the effect of an inhomogeneous medium has been averaged. In addition, this age is in close agreement with the pulsar’s characteristic age of 2,900 years. This agreement strengthens the pulsar/SNR association and relaxes the need for invoking a very slow initial spin period or a non-canonical value for the braking index of the pulsar (Camilo et al. 2002a).

### 3.3 Pulsar Wind Nebula Parameters

As noted by Hughes et al. (2001), the pulsar and its PWN are not located at the geometrical center of the remnant. The offset was attributed to either a high transverse velocity for the pulsar or slower expansion of the SNR toward the south-east. From the offset ($``$$`1^{}`$) they calculate a transverse velocity for the pulsar of $``$770($`d_{4.8}/t_{1600}`$) km s-1, where $`d_{4.8}`$ is the distance in units of 4.8 kpc and $`t_{1600}`$ is the age of the remnant in units of 1,600 yrs. Using our new estimate of 2,600$`{}_{200}{}^{}{}_{}{}^{+250}`$ yrs for the age we obtain a transverse velocity for the pulsar of 470$`\pm `$40 $`d_{4.8}`$ km s-1. This value is in excellent agreement with recent estimates of the mean birth velocity of pulsars (450$`\pm `$90 km s-1, Lyne & Lorimer 1994). The nearly east–west extension and jet-like structure extending to the south (see Fig. 1, right) could be indicative of a toroidal and collimated outflows reminiscent of Crab-like PWNe.

In the Kennel & Coroniti (1984) model, the synchrotron nebula is produced by the confinement of a relativistic wind injected by the pulsar into its surroundings. The radius of the standing shock, $`R_s`$, is estimated by equating the pressure of the pulsar’s wind, $`\dot{E}`$/(4$`\pi `$c$`R_s^2`$), with the pressure in the nebula, $`P_n`$=$`B_n^2`$/$`4\pi `$. $`B_n`$, the nebular magnetic field, can be approximated from its equipartition value, $`B_{n,eq}`$. Using the average luminosity and spectral index for the PWN, we estimate a value of $`B_{n,eq}`$1$`\times `$10-4 G. With the measured $`\dot{E}`$=1.2$`\times `$1037 ergs s-1 (Camilo et al. 2002a), we obtain a shock radius of $`R_s`$$``$$`3^{\prime \prime }`$ at 4.8 kpc. Alternatively, we can estimate the shock radius using the thermal pressure in the SNR interior as a confining pressure. This average pressure can be estimated as 2$`n_e`$$`kT`$ $``$ 6.9$`\times `$10-9 erg cm-3; which yields a shock radius of $`1^{\prime \prime }`$ . The inner circle shown in Fig. 1 (right) shows the estimated upper value of $`R_s`$. An interesting parameter than can also be derived from $`\mathrm{𝐶ℎ𝑎𝑛𝑑𝑟𝑎}`$ studies of PWNe is the pulsar wind magnetization parameter, $`\sigma `$, defined as the ratio of the Poynting flux to the particles flux, which can be estimated as $`\sigma (R_s/R_n)^2`$. Using a shock radius $`R_s`$$``$$`1^{\prime \prime }`$$`3^{\prime \prime }`$ and a nebular radius $`R_n`$$``$$`30^{\prime \prime }`$$`45^{\prime \prime }`$, we find that $`\sigma `$$``$5$`\times `$10-4–0.01, indicating a particle dominated wind.

The properties of the PWN can thus be derived from the Kennel & Coroniti model. The value derived for the pulsar wind magnetization parameter in this manner is comparable to that derived for other PWNe of similar properties (Safi-Harb 2002). It is worth noting that the properties of the pulsar and the PWN in G292.0+1.8 are strikingly similar to those of the pulsar discovered in the Crab’s cousin, G54.1+0.2 (Camilo et al. 2002b, Lu et al. 2002). The lack of ejecta and a shell in the latter SNR (and in a handful other plerions of comparable age) indicates that the classification of plerionic-type SNRs is to a large extent linked to the nature of the progenitor star, the explosion energy, and the environment.

This research made use of NASA’s Astrophysics Data System (ADS), and of archival data obtained from the $`\mathrm{𝐶ℎ𝑎𝑛𝑑𝑟𝑎}`$ X-ray Center. We thank G.G. Pavlov for his help at the early stage of this work, and for useful comments on the manuscript. The authors acknowledge support by the Natural Sciences and Engineering Research Council of Canada (NSERC). M.E.G. is a PGS A fellow, and SS-H is a University Faculty Award (UFA) fellow.


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# The ⁵𝐷 term origin of the excited triplet in LaCoO3

## Abstract

We provide the proof for the $`{}_{}{}^{5}D`$ term origin of an excited triplet observed in the recent electron-spin- resonance (ESR) experiments by Noguchi et al. (Phys. Rev. B 66, 094404 (2002)). We have succeeded to fully describe experimental ESR results both for the zero-field $`g`$-factor, of 3.35, and the splitting $`D`$ of 4.90 cm-1, as well as for the magnetic field applied along different crystallographic directions within the localized electron atomic-like approach as originating from excitations within the lowest triplet of the $`{}_{}{}^{5}T_{2g}^{}`$ octahedral subterm of the $`{}_{}{}^{5}D`$ term. In our atomic-like approach the d electrons of the Co3+ ion in LaCoO3 form the highly-correlated atomic-like 3$`d^6`$ system with the singlet $`{}_{}{}^{1}A_{1}^{}`$ ground state (an octahedral subterm of the $`{}_{}{}^{1}I`$ term) and the excited octahedral $`{}_{}{}^{5}T_{2g}^{}`$ subterm of the $`{}_{}{}^{5}D`$ term. We take the ESR experiment as confirmation of the existence of the discrete electronic structure for 3$`d`$ electron states in LaCoO3 on the meV scale.

PACS No: 76.30.Fc; 75.10.Dg : 73.30.-m;

Keywords: electronic structure, crystal field, spin-orbit coupling, LaCoO3

Submitted 24.12.2002 to Phys. Rev. B.

(24.12.2002)

1. Introduction

LaCoO3 attracts much attention in recent 50 years due to its non-magnetic ground state and the significant violation of the Curie-Weiss law at low temperatures often discussed in terms of successive changes of spin states with the increasing temperature. A great number of band-structure calculations , yielding the continuous energy spectrum for 3$`d`$ states spread over 6 eV, as well as crystal-field (CEF) considerations with discrete, in the meV energy scale, energy spectrum  did not yield final convincing solution for the magnetism, the electronic structure and thermodynamics for LaCoO3. A short comparative discussion of different modern theoretical approaches to LaCoO3 one can find in Ref. .

Recently Noguchi et al.  have succeeded in the Electron Spin Resonance (ESR) measurements for an excited triplet, behavior of which under external magnetic field applied along different crystallographic directions of single-crystalline LaCoO3 is very well described by an effective spin-Hamiltonian, Eq. 3.1 of Ref. , with the effective spin S=1 and with fitted values $`g_{}`$=3.35, $`g_{}`$=3.55 and $`D`$= +4.90 cm-1 (=7.056 K=0.6 meV). This excited triplet has been discussed in connection to the intermediate-spin state in the standard description of LaCoO3 in terms of low-spin (LS), intermediate-spin (IS) and high-spin (HS) states .

The aim of this paper is to provide the proof that the triplet state revealed in the recent ESR experiment of Noguchi et al. is the state originating from the atomic-like term $`{}_{}{}^{5}D`$ of the 3$`d^6`$ electron system existing in the Co3+ ion. This 25-fold degenerate $`{}_{}{}^{5}D`$ term (in the $`|LSL_\text{z}S_\text{z}`$ space) and its 15-fold degenerate $`{}_{}{}^{5}T_{2g}^{}`$ octahedral subterm we have studied in great details as we have considered its singlet as the ground state in our up-to-now description of LaCoO3, see Fig. 1c of Ref.  and Fig. 2c of .

2. Theoretical outline

For the description of the excited triplet we apply exactly the same Hamiltonian as has been used by us in Refs  namely Eq. 1 of Ref. and of Ref. for the term $`{}_{}{}^{5}D`$ with $`S`$=2 and $`L`$=2:

$$H_d=H_{cub}(L,L_z)+\lambda LS+B_2^0O_2^0(L,L_z)+\mu _B(L+g_sS)B$$
(1)
where $`H_{cub}=B_4(O_4^0+5O_4^4)`$ for $`z`$ axis along the cube edge and $`O_m^n`$ are the Stevens operators collected in, e.g. , table 16, p. 863. The cubic CEF Hamiltonian takes, for the $`z`$ axis along the cube diagonal, the form $`H_{cub}=`$ $`\frac{2}{3}B_4(O_4^020\sqrt{2}O_4^3)`$. This later form is useful for LaCoO3 due to the experimentally observed rhombohedral (trigonal) distortion that can be then described by the parameter B$`{}_{}{}^{0}{}_{2}{}^{}`$. For the 3$`d^6`$ system in the oxygen octahedron B4$`>`$0 , p. 374. The last term in Eq. (1) allows studies of the influence of the magnetic field B, in the present case used for computer ESR experiments. The energy states, calculated for the dominant octahedral crystal field, weaker intra-atomic spin-orbit interactions and the weakest trigonal distortion, are shown in Fig. 1d and Fig. 2c of Ref. and in Fig. 1d of Ref. . According to us the observed triplet is the one shown as the lowest triplet in these figures.

3. Results and discussion

The splitting of the triplet, into the singlet and doublet, results from the trigonal distortion. This splitting, denoted as $`D`$ in Ref., is roughly proportional to the trigonal distortion B$`{}_{}{}^{0}{}_{2}{}^{}`$ parameter, Fig. 1. The magnetic moment, equal to the $`g`$ factor in case of the triplet, of the doublet decreases with the increasing distortion from a value of 3.53 $`\mu _B`$ found for the purely octahedral crystal field in the presence of the spin-orbit coupling, Fig. 1c of Ref. . Fig. 2 shows variation of the magnetic moment vs the splitting $`D`$ for different values of the spin-orbit coupling in the presence of the octahedral crystal field described by the octahedral parameter B4=+200 K. The experimentally observed values $`D`$=+4.90 cm-1 (for $`D>0`$ the singlet is lower) and $`g`$ = 3.35 are obtained for $`\lambda `$ = -185 K and B$`{}_{}{}^{0}{}_{2}{}^{}`$=+7.2 K. Practically the same curves are obtained for larger values of B4 \- it is related to the fact that B4 determines the splitting of the $`{}_{}{}^{5}D`$ term and the 2-3 eV energy scale.

The calculated dependence of the triplet states under the action of the external magnetic field applied along different crystallographic directions, denoted in Fig. 1 of Ref. , is shown on Figs 3, 4 and 5 together with the ESR transitions fo, f1 and f2 for selected frequencies. For clarity, we have performed calculations of all 25 states in the $`|LSL_\text{z}S_\text{z}`$ space , but only the three lowest states are shown in Figs 3-5. The energy structure of the 15 lowest states, originating from the $`{}_{}{}^{5}T_{2g}^{}`$ subterm, is shown in Fig. 6. It is predominantly determined by the spin-orbit interactions that define the 0.1 eV energy scale. The comparison of our Fig. 3 with Fig. 4 of Ref. , Fig. 4 with Fig. 5a of Ref.  and Fig. 5 with Fig. 5b of Ref.  reveals a perfect reproduction of the experimental ESR results. In particular, we would like to put attention to the reproduction of the behavior for the cubic-edge direction (Fig. 4) and for the direction perpendicular to the cube diagonal (Fig. 5). For the cubic direction the resonance fields f1 and f2 are the same what is not the case for the perpendicular direction. For the  direction, the cube diagonal, the resonance fields are shifted by 6 T, Fig. 3, in agreement with the experimental observation, shown in Fig. 4 of Ref. .

It is worth to point out that for the shown description we use only 3 parameters: B4 (not so sensitive provided that it is positive and it is in the range 50-300 K), $`\lambda `$ and B$`{}_{}{}^{0}{}_{2}{}^{}`$, that have been selected as shown in Figs 1 and 2. All of them have clear physical meaning. In fact, the most important is the choice of the atomic term, the term $`{}_{}{}^{5}D`$ with $`S`$=2 and $`L`$=2 in the present case. In this choice we have been oriented by our assumption of the fulfilling of two Hund’s rules also in case of solids. The spin-orbit coupling parameter is by 12% smaller than the free-ion value, what is reasonable. But in fact, the most important ”unwritten” assumption is an assumption about the significant surviving of the atomic states of the 3$`d^6`$ system - it corresponds to the very strong correlations among 3$`d`$ electrons. Thanks these strong intra-atomic correlations the atomic-like terms of the Co3+ ion survive also in the solid when this cation becomes the full part of a solid.

4. Conclusions and remarks

We proved that the excited triplet, revealed in the ESR experiment by Noguchi et al. , originates from the $`{}_{}{}^{5}D`$ term, more exactly from the lowest triplet of its $`{}_{}{}^{5}T_{2g}^{}`$ subterm. The zero-field $`g`$-factor and the singlet-doublet splitting as well as the ESR excitations for different crystallographic directions have been very well described by taking into account the octahedral CEF interactions, the intra-atomic spin-orbit coupling and a relatively weak trigonal distortion. So good and very consistent description with so limited number of parameters provides significantly large confidence to the found physical origin of the excited triplet. It is worth to add that the same approach we have used for FeBr2 and the term $`{}_{}{}^{5}D`$ has been found to be the ground term of the Fe2+ ion . In FeBr2 the value of $`D`$ was derived to be -33 K and also has resulted from the trigonal distortion B$`{}_{}{}^{0}{}_{2}{}^{}`$ of -30 K. The splitting $`D`$ in both compounds is of the same size in the absolute value. However, in LaCoO3 the $`{}_{}{}^{5}D`$ term is the excited term as thanks the activated character of the ESR spectra we became sure that there is an extra singlet at $`\mathrm{\Delta }_{st}`$ =140 K below - as is shown in Fig. 6c. This singlet it is a state $`{}_{}{}^{1}A_{1}^{}`$. It originates from the $`{}_{}{}^{1}I`$ term, that in the free Co3+ (CoIV) ion lies 4.43 eV above the ground term . The 13-fold degenerate term $`{}_{}{}^{1}I`$ splits under the action of the octahedral crystal field into 6 states and the singlet $`{}_{}{}^{1}A_{1}^{}`$ state is strongly pushed down due to its very large value of the orbital quantum number $`L`$=6. The situation with the $`{}_{}{}^{1}A_{1}^{}`$ subterm being slightly lower than the $`{}_{}{}^{5}T_{2g}^{}`$ subterm occurs for $`Dq`$/$`B`$=2.025 on the Tanabe-Sugano diagrams presented on p. 388 of Ref. . Assuming the Racah parameter $`B`$ of 1065 cm-1 one gets $`Dq`$=2156 cm-1 and consequently B4=+260 K. This value is only slightly larger, by 30%, than we used previously  and in the calculations of ESR dependences on Figs 3-5. Thus, the crystal field interactions are strong in LaCoO3 but not so strong to destroy the atomic discrete electronic structure of the 3$`d`$-electron states as is postulated by the Quantum Atomistic Solid-State theory (QUASST) . The inferred electronic structure, in the 4 eV scale, of cubic subterms of the Co3+ ion in the octahedral crystal field, relevant to LaCoO3, is shown in Fig. 7. Surely, our long-lasting studies as well as growing number of more and more sophisticated experiments indicate that it is the highest time to ”unquench” the orbital moment in the solid-state physics for description of the magnetism and the electronic structure of 3$`d`$-atom containing compounds .

Acknowledgement. The authors are grateful to M. Kocor and A.J. Baran for the assistance in the computer preparation of this paper.

Fig. 1. Calculated dependence of the splitting $`D`$ of the lowest triplet, into a singlet and excited doublet, of the $`{}_{}{}^{5}T_{2g}^{}`$ subterm on the distortion trigonal parameter B$`{}_{}{}^{0}{}_{2}{}^{}`$ in the presence of the octahedral crystal field B4=+200 K and the spin-orbit coupling $`\lambda `$=-185 K.

Fig. 2. Calculated dependence of the magnetic moment of the excited doublet on the splitting $`D`$ for different values of the spin-orbit coupling $`\lambda `$ in the presence of the octahedral crystal field B4=+200 K. Values of $`g_{}`$=3.35 and $`D`$= +4.90 cm-1 (=7.056 K=0.6 meV) are reproduced by $`\lambda `$=-185 K and the trigonal distortion parameter B$`{}_{}{}^{0}{}_{2}{}^{}`$=+7.2 K. Curves for a larger value of B4=+260 K are only slightly above (less than 1%).

Fig. 3. Calculated field dependence of the three lowest states, the quasi triplet, of the 25-fold degenerate $`{}_{}{}^{5}D`$ term for the octahedral crystal-field parameter B4=+200 K, the spin-orbit coupling $`\lambda `$=-185 K and the distortion trigonal parameter B$`{}_{}{}^{0}{}_{2}{}^{}`$=+7.2 K for external magnetic fields applied along the diagonal of the cube of the perovskite structure of LaCoO3. The ESR transitions f1 and f2 for the frequency of 1000 GHz (=48 K) are shown. The zero energy is at the level of the unsplit $`{}_{}{}^{5}D`$ term.

Fig. 4. Calculated field dependence of the three lowest states of the $`{}_{}{}^{5}D`$ term for the octahedral crystal field B4=+200 K, the spin-orbit coupling $`\lambda `$=-185 K and the distortion trigonal parameter B$`{}_{}{}^{0}{}_{2}{}^{}`$=+7.2 K for external magnetic fields applied along the edge of the cube of the perovskite structure of LaCoO3. The ESR transitions fo, f1 and f2 for the frequency of 760 GHz (=36.5 K) are shown. The ESR transitions f1 and f2 occur practically at the same magnetic field, what is a characteristic feature for the cubic direction.

Fig. 5. Calculated field dependence of the three lowest states of the $`{}_{}{}^{5}D`$ term for the octahedral crystal field B4=+200 K, the spin-orbit coupling $`\lambda `$=-185 K and the distortion trigonal parameter B$`{}_{}{}^{0}{}_{2}{}^{}`$=+7.2 K for external magnetic fields applied along the  direction, i.e. perpendicular to the diagonal of the cube of the perovskite structure of LaCoO3. The ESR transitions fo, f1 and f2 for the frequency of 429 GHz (=20.6 K) are shown.

Fig. 6. Calculated low-energy electronic structure of the Co3+ ion in LaCoO3 originating from the $`{}_{}{}^{5}T_{2g}^{}`$ cubic subterm with the $`{}_{}{}^{1}A_{1}^{}`$ singlet ground subterm put 140 K below the lowest $`{}_{}{}^{5}T_{2g}^{}`$ state. Such the structure is produced by the dominant octahedral crystal-field interactions and the intra-atomic spin-orbit coupling (b). c) shows the splitting produced by the trigonal distortion. The states are labelled by the degeneracy, the magnetic moment and the energy with respect to the lowest state of the $`{}_{}{}^{5}D`$ term.

Fig. 7. Electronic structure of cubic subterms of the Co3+ ion in the octahedral crystal field inferred from the Tanabe-Sugano diagram for $`Dq`$/$`B`$ =2.025 relevant to LaCoO3. The arrow indicates the strength of the octahedral crystal field considered by us in the previous studies. The crystal field is slightly stronger but still not so strong to destroy the atomic-like discrete structure of the $`d`$-electron states as is postulated by the Quantum Atomistic Solid-State theory.


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# Acceleration of chemical reaction by chaotic mixing

(January 10, 2003)

## Abstract

Theory of fast binary chemical reaction, $`𝒜+𝒞`$, in a statistically stationary chaotic flow at large Schmidt number Sc and large Damköhler number Da is developed. For stoichiometric condition we identify subsequent stages of the chemical reaction. The first stage corresponds to the exponential decay, $`\mathrm{exp}(\lambda t)`$ (where $`\lambda `$ is the Lyapunov exponent of the flow), of the chemicals in the bulk part of the flow. The second and the third stages are related to the chemicals remaining in the boundary region. During the second stage the amounts of $`𝒜`$ and $``$ decay $`1/\sqrt{t}`$, whereas the decay law during the third stage is exponential, $`\mathrm{exp}(\gamma t)`$, where $`\gamma \lambda /\sqrt{Sc}`$.

A common expectation is that random advection should essentially accelerate chemical reactions in fluid phase, since it should lead to homogenization of the reaction mixtures. Then dynamics is determined by an interplay of three factors: diffusion, advection and chemical reaction rate. Typical situation realizing in chemical reactors is that chemical reaction itself is much faster than mixing and diffusion, i.e. the Damköhler number, Da, which is defined as the ratio of the mixing time to the characteristic time of the reaction 36Dam , is large. For the binary reaction this separation of temporal scales results in formation of lamellar structure, build of stripes, populated solely by one chemical. The stripes of different chemicals are separated from each other by an interface of complicated shape, and the chemicals co-exist only in the narrow interface domain where the chemical reaction occurs. The reaction is limited by diffusion in the sense that diffusion controls fluxes of the chemicals into the interfacial reaction zone 63FK ; 76Hil ; 84CO . The physical picture of the acceleration due to the random advection is that it stretches domains populated by one chemical into thin sheets, so that the chemical reaction driven by diffusion proceeds more efficiently because of an essential increase of the interface area. In this letter we explain how this general physical picture, formulated initially for unbounded flows applies to chaotic flows confined to a finite geometry.

We consider a binary chemical reaction, $`𝒜+𝒞`$, in a dilute solution of two chemicals. We study decay problem, with an initial distribution of the chemicals $`𝒜`$ and $``$, created by injecting solution of one chemical, say of $`𝒜`$, into solution of the other chemical, $``$. It is assumed that the inverse reaction $`𝒞𝒜+`$ is negligible, i.e. there is no back influence of $`𝒞`$ on the distribution of $`𝒜`$ and $``$. Then molecular concentrations of the chemicals, $`n_a`$ and $`n_b`$, vary according to the following non-linear governing equations (see, e.g., Landau )

$`_tn_{a,b}+(𝒗)n_{a,b}=\kappa _{a,b}^2n_{a,b}Rn_an_b,`$ (1)
where $`R`$ is the reaction rate coefficient, $`𝒗`$ is the velocity of the flow, which is assumed to be incompressible ($`𝒗=0`$), $`\kappa _{a,b}`$ are the diffusion coefficients of the chemicals. Here, we assume that the fluid dynamics is independent of the chemical reaction, that is the velocity field does not sense changes in the chemical concentrations nor heat is released in the result of the chemical reaction. Our approach is also applicable to the case, realized in tubular chemical reactors, when the solution of the chemicals, prepared at the entrance, is then pushed through a pipe. In this case the position along the pipe plays the role of time in the decay problem.

The major question addressed in the letter is: how do the total amounts of chemicals, $`N_{a,b}=\text{d}𝒓n_{a,b}(t,𝒓)`$, decay as time $`t`$ advances? We focus primarily on the stoichiometric case $`N_a=N_b`$. This case is of major interest for applications, as it allows to get pure product $`𝒞`$ (not mixed with the reagents), by the time reaction is completed. (An effect of a mismatch between $`N_a`$ and $`N_b`$ is briefly discussed later in this text.) We identify major stages of the chemical reaction and relate them to the chemicals decay in different parts of the flow. An essential part of the evolution is related to the boundary region.

We discuss mainly the case of $`\kappa _a=\kappa _b=\kappa `$. (It is argued later in the text that $`\kappa _a\kappa _b`$ does not lead to significant changes in the theory.) Then one obtains a closed equation for the difference field, $`n=n_an_b`$,

$`_tn+(𝒗)n=\kappa ^2n,`$ (2)
from Eq. (1), i.e. one finds that $`n(t,𝒓)`$ is a passive scalar field. Note, that $`n`$ has no definite sign, and that $`\text{d}𝒓n=0`$ in the case of perfect matching, $`N_a=N_b`$.

We assume that the chaotic statistically steady velocity field $`𝒗(t,𝒓)`$ contains only few harmonics of the reservoir size, i.e. the flow is smooth. This regime can be realized in chemical reactors with mechanically rotating mixers or externally driven magnets stirring the fluid in the perfect mixing devices and also in the tubular reactors at moderate Reynolds numbers. (See 99BB  for a discussion of the chemical engineering principles behind various reactor designs.) Complementary to its practical significance, passive scalar advection in a smooth chaotic flow is also a well studied (by both theoretical 59Bat ; 67Kra ; 94SS ; 95CFKLa ; 99BF  and experimental 97WMG ; 00JCT ; 01GSb  means) subfield of statistical hydrodynamics. (See also reviews 00SS ; 01FGV .) The passive scalar decay theory, developed in 99Son ; 99BF  for an unbounded flow, was recently modified for bounded flows, i.e. for chaotic flows with suitable (no slip) conditions on the boundary 02CLa . Smoothness of the flow allows one to approximate the velocity difference between close points by a linear, although fluctuating in time, profile. In the bulk region, the linear profile approximation is valid for separations smaller than the system size $`L`$. In the periphery, i.e. close to the solid boundary (wall), the linear profile approximation is valid for velocity fluctuations on a scale smaller than distance to the boundary. An important consequence of the linear velocity profile approximation is that close Lagrangian trajectories diverge exponentially in time. The mean logarithmic rate of the nearby Lagrangian trajectories divergence defines the Lyapunov exponent of the flow, $`\lambda `$. Notice, that in the peripheral domain advection is essentially anisotropic, and the stretching rate along the boundary is estimated by $`\lambda `$, while the stretching rate in the direction normal to the boundary is significantly smaller.

We now discuss characteristic spatial scales in the problem. The size of the system, $`L`$, which is also the chaotic flow typical eddy scale, is the largest scale in the problem. A comparison of the advection and diffusion terms in Eq. (1) sets the dissipative scale of the flow, which in the bulk region is $`r_d=\sqrt{\kappa /\lambda }`$. We assume that the Schmidt number, $`\text{Sc}(L/r_d)^2`$, is large, i.e. in the asymptotically wide range of scales, $`Lrr_d`$, advection dominates diffusion. The width of the diffusive boundary layer is estimated by $`r_{bl}\text{Sc}^{1/4}r_d`$, i.e. $`r_{bl}>r_d`$. Yet another important scale, associated with the chemical reaction itself, is the size of the reaction zone, $`r_{ch}`$ (the width of the interfacial domain where the chemical reaction occurs). In the bulk region the scale is estimated by $`r_{ch}=r_d[\lambda /(Rn_m)]^{1/3}`$, where $`n_m`$ is a typical concentration of the chemicals inside the layers. (The estimate for the width of the reaction zone should be modified near the boundary, where it appears to be larger than in the bulk.) Initially, $`r_{ch}`$ is much smaller than $`r_d`$ (and, consequently, than $`L`$); the inequality is a consequence of the $`\text{Da}1`$ assumption. (Indeed, in accordance with the definition, the Damköhler number can be estimated as $`\text{Da}Rn_0/\lambda `$, where $`n_0`$ is a typical value of the initial chemical concentration. Thus, at $`t=0`$, $`r_{ch}\text{Da}^{1/3}r_d`$.) However, $`r_{ch}`$ grows as $`n_m`$ decreases. Thus even though the separation of scales is perfect initially, it eventually breaks down at the latest stage of the chemical reaction. A cartoon illustration of the scale hierarchy is shown in Fig. 1. The magnified striped structure is shown on the chart in the upper right corner of the figure. Regions populated by one chemical are single-colored. To resolve the interface domain, even stronger magnification is needed. Dependence of the chemicals concentrations on the coordinate normal to the interface is shown schematically on the chart in the lower right corner of the figure.

The separation of scales, $`r_{ch}r_d,L`$, allows an important simplification in the description. Indeed, the chemical reaction takes place in the $`r_{ch}`$-narrow interface domain, where the values of $`n_a`$ and $`n_b`$ are comparable. Outside this narrow region, i.e. in the region dominated by one of the chemicals, the presence of the other chemical is negligible. Thus, in the limit $`r_{ch}0`$, i.e. when the reaction zone becomes infinitesimally thin, one obtains $`n_a=n,n_b=0`$ for $`n>0`$ and $`n_a=0,n_b=n`$ for $`n<0`$. These relations imply a remarkable conclusion 63FK ; 84CO : the fast chemical reaction can be described in terms of the linear setting (2) which does not contain the chemical reaction rate coefficient $`R`$. The reaction rate is determined by the diffusion fluxes of $`𝒜`$ and $``$ to the $`n=0`$ surface. These fluxes are equal to each other and opposite in sign, which is translated, at $`r_{ch}0`$, into a continuity condition for $`n`$ at the interface. This observation also means that, while $`r_{ch}`$ is much smaller than all other relevant scales, our problem is reduced to the problem of scalar decay in chaotic bounded flow.

Furthermore, from Eq. (2), it is straightforward to derive equations for correlation functions of $`n`$ (the derivation procedure is similar to the one described in 95CFKLa ; 99BF ). The equation for the mean value of $`n`$, $`n`$, derived by averaging over times larger than the correlation time of the flow $`\tau _0`$, is

$`_tn=_\alpha (D_{\alpha \beta }_\beta n)+\kappa ^2n.`$ (3)
In the case of a short-correlated (in time) flow, $`\lambda \tau _01`$, the turbulent diffusion tensor $`D`$ is expressed through the velocity pair correlation function: $`D_{\alpha \beta }(𝒓)=_0^{\mathrm{}}\text{d}tv_\alpha (t,𝒓)v_\beta (0,𝒓)`$. Eq. (3) remains valid in the general, not necessarily short-correlated limit. However, the relation between the eddy-diffusivity tensor and the velocity correlations becomes more complicated. $`D(𝒓)`$ tends to zero when $`𝒓`$ approaches the boundary, since the flow velocity tends to zero there. (The longitudinal component $`D_{}`$ of the tensor $`D`$ behaves as $`D_{}q^2`$, whereas its transverse component $`D_{}`$ behaves as $`D_{}q^4`$, where $`q`$ is the distance to the boundary.) Our description of the chemical reaction problem is based on the solutions of Eq. (3) in different spatio-temporal domains. Knowing $`n`$, one can establish the temporal behavior of $`N_{a,b}`$. The brief style of this letter does not allow us to present the complete analysis here. Therefore, below we report final results, omitting details of the derivation. To clarify the results, we also pay special attention to presenting a physical picture of the phenomenon.

We find that the chemical reaction (which starts at $`t=0`$) undergoes the following four stages:

I. Formation of stripes in the bulk. Advection creates from an initially smooth distribution a striped structure of alternating domains of $`𝒜`$ and $``$ 84CO . The stripes become dynamically thinner, i.e. inhomogeneities of smaller and smaller scales are produced. Once the width of the stripe decreases down to the diffusive scale, $`r_d`$, the stripe collapses (wiped out by the diffusion-limited chemical reaction) in a time $`\lambda ^1`$. Since the stretching (contraction) process leading to creation of the stripes is exponential in time 59Bat ; 67Kra ; 94SS ; 95CFKLa ; 00SS ; 01FGV , the initial stage (when the $`r_d`$-stripes are formed) lasts for $`\tau _1\mathrm{ln}(\text{Sc})/\lambda `$, i.e. just the time required for the cascade of passive scalar to run from $`L`$ down scale to $`r_d`$. Even though the interfacial area increases exponentially during the first stage, $`N_{a,b}`$ do not vary significantly. By the end of this stage the bulk parts of $`N_{a,b}`$ begin to decay rapidly (exponentially), with a decrement of the order of $`\lambda `$, according to the law of the passive scalar decay in an unbounded spatially smooth flow 99Son ; 99BF . Thus, after the first stage the chemicals remain mainly in the peripheral region.

Notice also, that after the first stage, stripes of different widths, distributed between $`r_d`$ and $`L`$, are present in the bulk. (This multi-scale structure is also seen in the passive scalar decay experiment 00JCT ; 01GSb , and in binary-reaction numerics 96ML .) When the $`r_d`$-wide stripe, say, of the chemical $`𝒜`$ collapses, then two nearby stripes of the chemical $``$ form one wider stripe. Thus, collapse of $`r_d`$-narrow stripes is accompanied by creation of wider stripes, which are shrunk by the flow in turn, and so on and so forth.

II. Peripheral-region-dominated dynamics. The same process of layered structure formation takes place in the peripheral domain as well. However, advection, which is statistically isotropic in the bulk, is strongly anisotropic in the peripheral domain, where advection is more efficient in the direction along the boundary than in the normal direction. This anisotropy causes the layers in the peripheral domain to stretch mainly along the boundary. The stripes closer to the boundary shrink slower than the remote ones, since the normal to the boundary component of the stretching rate decreases as one approaches the boundary. Therefore the developed layered structure (i.e. the one which contains stripes of the diffusive scale width) occupies a part of the peripheral region where the amounts of $`𝒜`$ and $``$ become negligible. Thus, the empty of chemicals region, formed in the bulk by the end of the first stage, starts to expand towards the boundary. As a result, the chemicals are arranged mainly within a $`\delta `$-vicinity of the boundary (wall), $`\delta L/\sqrt{\lambda t}`$, where the concentrations of the chemicals remain practically unchanged. Outside this layer, at $`Lq\delta `$ (where $`q`$ is the separation from the boundary), the concentration of chemicals decreases algebraically $`n_{a,b}t^{3/2}q^3`$. During this stage the overall amounts of chemicals decrease as $`\delta (t)`$, that is $`1/\sqrt{t}`$. The spatio-temporal picture explained above follows from the universal form of the velocity field profile in the proximity of the boundary. This stage lasts for $`\tau _2\sqrt{Sc}/\lambda `$, i.e. until $`\delta `$ shrinks to the width of the boundary layer, $`r_{bl}`$.

III. Boundary-layer-dominated dynamics. Chemicals remain mainly within the $`r_{bl}`$-thin (not varying with time) vicinity of the boundary. The boundary layer width, $`r_{bl}`$, is still much larger than the reaction zone size (defined for the boundary region), so that the passive scalar description applies. The interfacial area where the chemicals interact does not change significantly anymore. Thus, due to linear relation between flux of chemicals to the interface and their concentrations, the algebraic decay switches to an exponential one, i.e. $`n_{a,b}\mathrm{exp}(\gamma t)`$, for $`t\tau _2`$, where $`\gamma \lambda /\sqrt{Sc}L^1\sqrt{\lambda \kappa }`$. (Note, also, that the slow-exponential regime, derived in 02CLa  for the passive scalar, is consistent with the experimental observations of 01GSb .) Then, $`N_{a,b}(t)\mathrm{exp}(\gamma t)`$. Chemicals are mainly concentrated inside the diffusion boundary layer. Outside the boundary layer (at $`qr_{bl}`$) one of the chemicals prevails and its concentration decays algebraically, $`1/q^3`$. The passive scalar description in the vicinity of the boundary layer is broken when $`r_{ch}`$, which grows exponentially with time, becomes of the order of $`r_{bl}`$, i.e. when at the boundary $`n_{a,b}`$ becomes $`\lambda /(R\sqrt{\text{Sc}})`$. One concludes that the duration of the boundary-layer-dominated stage is $`\tau _3\gamma ^1\mathrm{ln}(Rn_0\sqrt{\text{Sc}}/\lambda )`$, where $`n_0`$ is the initial concentration of the chemicals.

IV. Nonlinear stage. By the end of the previous stage, advection and diffusion homogenize the remaining amounts of the chemicals, first, within the boundary layer and later over the entire reservoir. After that there are no inhomogeneities of $`n_{a,b}`$ left in the system. A purely homogeneous kinetic process takes over: $`\text{d}N_{a,b}/\text{d}t=RVN_aN_b`$ (where $`V`$ is the chemical reactor volume). Thus, $`N_{a,b}1/t`$, during the final stage.

If $`N_aN_b`$ then the proposed scheme is valid until $`N_{a,b}`$ become of the order of $`|N_aN_b|`$. Then $`N_a`$ saturates to a constant (if $`N_a>N_b`$) and $`N_b`$ disappears exponentially, $`\mathrm{exp}(RN_at/V)`$. (Note that the exponential decay starts after a short intermediate stage characterized by complete homogenization of $`𝒜`$ due to advection and diffusion.)

Let us now discuss the effect of unequal diffusion coefficients, still assuming that $`\sqrt{\kappa _{a,b}/\lambda }L`$. If $`\text{Da}1`$ then during the first stages, the chemical length $`r_{ch}`$ is (as above) much smaller than all other scales. This problem can also be reduced to a linear one considering the advection-diffusion equations in domains populated by different species, supplemented by the condition that fluxes of the two chemicals towards the interface are equal. During the first two stages, the evolution is controlled by the stripe formation process which is insensitive to the diffusion. During the latter, third and fourth, stages of the evolution in the uneven $`\kappa _a\kappa _b`$ case the chemicals evolve similarly to what was described above for the, $`\kappa _a=\kappa _b`$, case. Thus, the above description applies to the general, $`\kappa _a\kappa _b`$, case as well.

We conclude with some general remarks. A complicated spatio-temporal behavior for the binary chemical reaction in a chaotic flow is established. Evolution of the chemicals near the boundary (where mixing is slower than in the bulk) determines the intermediate stages of the reaction. Those boundary-dominated stages were not singled out in the previous publications on the subject simply because the stages are not observed in an infinite 84CO  or periodic 96ML  flow systems. In our setting the lamellar structure (which is statistically isotropic in bulk and strongly anisotropic near boundaries) is dynamically generated by advection. (This situation is essentially different from the one considered in 90MO , where the lamellar structure is created initially and no advection participates in subsequent evolution.) We focused here on large scale chaotic flows with the size of the box being of the order of the major scale of the flow. However, it is also of interest for applications to describe chemical reaction acceleration in turbulent flows, which are smooth only inside the viscous range of scales. In this case with a large value of the viscous to dissipative scales ratio, a consideration similar to those presented in the letter is applicable. We plan to examine the more complicated case in the future. Also, the approach developed in the paper is generalizable for other, more complicated, types of chemical reaction, e.g. competing chemical reactions. For completeness, let us also mention another case of interest which is realized at moderate Da, large Sc and if one of chemicals is present in abundance. The joint effect of advection and chemistry is different in this case (than in the problem discussed in this letter), even though rich multi-scale structure of spatial correlations is also revealed 98Che . A final remark concerns the validity of the hydrodynamic description of the chemical reaction dynamics. It is known that the character of spatial fluctuations in the initial distribution of chemicals may essentially influence the long-time behavior in diffusion-limited chemical systems 78OZ ; 83TW . In some cases (of low space dimensionality, $`d2`$) large scale renormalization of the concentration fields due to the small scale fluctuations could be important. (See, e.g., 95Cara .) In our case, however, this does not happen because the long-time correlations are completely destroyed by chaotic advection.

We thank J. Cardy, G. D. Doolen, A. Fouxon, A. Groisman, I. Kolokolov, V. Steinberg, P. Tabeling, and Z. Toroczkai for helpful discussions and comments.


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# X-ray diffraction measurements of the c-axis Debye-Waller factors of YBa2Cu3O7 and HgBa2CaCu2O6

## Abstract

We report the first application of x-rays to the measurement of the temperature dependent Bragg peak intensities to obtain Debye-Waller factors on high-temperature superconductors. Intensities of $`(0,0,l)`$ peaks of YBa2Cu3O7 and HgBa2CaCu2O6 thin films are measured to obtain the c-axis Debye-Waller factors. While lattice constant and some Debye-Waller factor measurements on high Tc superconductors show anomalies at the transition temperature, our measurements by x-ray diffraction show a smooth transition of the c-axis Debye-Waller factors through Tc. This suggests that the dynamic displacements of the heavy elements along the c-axis direction in these compounds do not have anomalies at Tc. This method in combination with measurements by other techniques will give more details concerning dynamics of the lattice.

The majority of efforts to understand the mechanism of the high Tc superconductivity (HTSC) have been in terms of pure electronic effects, primarily because of the conjecture that electron-phonon coupling alone cannot give such a high Tc. However, there have been persistent efforts to study the role of the lattice in HTSCNazarenko ; Sakai ; You ; Asahi ; Kadowaki ; Braden ; Pasler . In addition to the fact that the structural information provides important information about the materials, the lattice can still play an important role as it affects both the hopping ($`t`$) and magnetic exchange ($`J`$) energies of these materials, the two most important parameters in the physics of these correlated systems. Indeed, there have been theoretical efforts to study the role of lattice vibration in the cupratesNazarenko ; Sakai . Therefore, experimental investigation of the temperature dependent lattice vibration in these materials, especially the critical behavior around Tc, is essential and can provide vital information concerning the low energy degrees of freedom.

Experimental evidence that shows clear correlation between the critical behaviors in the electronic and crystal structures are anomalies in lattice constants at Tc. These have been observed in various HTSC materials by x-rayYou ; Asahi  and more accurately by capacitance dilatometry methodsKadowaki ; Braden ; Pasler . They have shown that the lattice constant generally decreases at a much faster rate at Tc than at other temperatures as the temperature decreases. Subsequently, the thermal expansion coefficient $`\alpha `$ shows an anomaly that is of similar shape to the heat capacity anomalies observed at Tc. This enhanced decrease in the lattice constant has been related to the specific heat capacity through the thermodynamic Ehrenfest relationsPasler . Yet the microscopic reason behind such a lattice anomaly is not well understood. One natural question is if it is related to the dynamic properties of phonons. It will therefore be interesting to measure the Debye-Waller factors (DWF) of HTSC materials.

In complex materials, the DWFs are usually measured by extended x-ray absorption fine structure (EXAFS). In the HTSCs there have been efforts to measure the temperature dependent mean-square displacement $`\sigma ^2(T)`$ (which is inversely related to the DWF) by EXAFSYang ; Bridges ; Lanzara , with essentially only Hg based samples showing anomalies at TcLanzara . EXAFS measures local coordinates at a certain atom and therefore has an important advantage of being element specific. It, however, measures only relative atomic motions (for example, O relative to Cu or optical phonons in the Cu-O plane) and is insensitive to collective motions of the atoms, for instance, the low frequency acoustic phonons. To see the effect in the phonon population, the necessary condition is to have ample phonons in the first place. This may be difficult for optical phonons as their energy scale is usually very high compared to the experimental temperature scales (which are set by $`T_c`$). This may be related to the fact that EXAFS results largely show no anomalies. In contrast, even though they have their own disadvantages which will be discussed later, diffraction techniques in principle measure the integrated phonon effectsKittel . Here we report novel application of x-ray diffraction that can in principle measure DWFs. This is to our knowledge the first application of this method by x-rays to complex materials like HTSCs. We have measured the temperature dependence of the Bragg peak intensities, a quantity that can be related to the dynamic lattice motion. The results are discussed along with various aspects of x-ray diffraction and possible future experiments.

The experiments were performed at beamline 2-1 of the Stanford Synchrotron Radiation Laboratory (SSRL) which is equipped with a 2-axis Huber diffractometer. The diffractometer has an open cycle He cryostat. $`h\nu =8.8`$ keV x-rays, just below the Cu K edge, were used to reduce the background from the fluorescent light. For the reasons explained below, intensities of the $`(0,0,l)`$ peaks of YBa2Cu3O7 (YBCO) and HgBa2CaCu2O6 (Hg1212) thin film samples grown on SrTiO3 substrates were taken. These materials were grown according to the procedures described elsewhereCole ; Wu . The YBCO film has Tc of 90.5K with the $`\mathrm{\Delta }`$Tc less than 1K. The Hg1212 sample has the $`\mathrm{\Delta }`$Tc less than 1K locally but shows distribution of Tc’s from 123K at the center to 118K at the edge.

In order to obtain highly reliable intensities, it is essential to reduce the errors from the beam and sample instabilities and detector non-uniformity. The beam drifts were monitored in the I0 section and corrected for before each measurement. The biggest effect came from the motion of the cryo-head during the temperature cycle. To reduce such effects, a special manipulator has been designed as shown in Figure 1. The sample holder is in weak thermal contact with the cryo-head and has its own temperature sensor and heater. The thermal contact is weak enough so that the temperature of the sample holder can be varied between 10 K and 200 K with the temperature of the cryo-head maintained at 10 K. This removed most of the sample motion and greatly improved the reproducibility of the data.

The special manipulator did not completely remove the sample motion with respect to the beam during temperature cycling. If the sample was completely homogeneous then the relative motion of the sample will have no effect on the measurement. In our experience, the only high Tc samples which are homogeneous to a highly collimated and monochromatic synchrotron beam are fine grain powders. However, in a powder sample the high index peaks, the peaks more sensitive to the DWF (as DWF $`l^2`$), were too weak to measure with sufficient statistical accuracy in a reasonable amount of time. Even though the intensities of the high index Bragg peaks were acceptable in a single crystal we discovered, after looking at high Tc single crystals from several different sources, that these samples were really a bundle of several low angle grain boundary crystallites. Even a small motion of such a sample with respect to the incident beam changed the fraction of the diffracting domain in the beam, which resulted in a significant change in the diffracted beam intensity. Thin films of sufficiently high quality and lateral homogeneity for synchrotron measurements were available but they were all $`(0,0,l)`$ orientationSide . Hence, as a compromise between high intensity and sufficiently homogeneous samples, we performed our measurements on the $`(0,0,l)`$ peaks of thin film samples.

In addition to the motion of the cryostat upon the temperature change, other factors such as detector non-uniformity contributed to the irreproducibility of the data. Since the effect we were looking for was very small, the accuracy/reproducibility of the measurements had to be better than 0.5$`\%`$. Therefore, care had to be taken to remove any factor that affects the data quality. The following somewhat unconventional procedure was performed to obtain reliable data. First, the detector slit was set wide enough ($`\mathrm{\Delta }2\theta `$ 4 degrees) to accept all the diffracted x-ray within a certain Bragg peak (Fig. 1). This is to minimize the detector non-uniformity effect as use of angle limiting devices such as Soller slits resulted in very unreliable data. However, some degree of non-uniformity still existed and it was necessary to make it sure that the same part of the detector is used for each scan. To ensure this, we scanned 2$`\theta `$ at each temperature to locate the detector so that the centroid of the diffraction peak is at the center of the detector. In this way, the detector is essentially tracking the temperature dependent motion (in 2$`\theta `$) of the diffraction peak. As the last step, the $`\theta `$ scans (rocking curves) were taken to measure the diffraction peak intensity. The above procedure produced the most reliable data.

Fig. 2 shows $`\theta `$ scans as well as temperature dependent intensity plots measured as described above. Panel (a) shows normalized $`\theta `$ scans of the (0,0,13) peak from YBCO. The peak position in $`\theta `$ decreases as temperature increases, implying the increase of the c-axis lattice constant as expected. In addition to the decrease in the $`\theta `$ position, we note that the Bragg peak intensity decreases as the temperature increases (increased constant background due to incoherent scattering was also observed but subtracted in the plot and analysis). No appreciable change in the diffraction line shape, that is, no $`q`$ dependence is observed and thus the role of thermal diffuse scattering is not considered in the following discussions. Since the detector slit was wide open (in $`2\theta `$) to accept all the x-rays of the peak, each point on the $`\theta `$ scan represents Bragg peak intensity i.e., integration of a $`2\theta `$ scan at the given $`\theta `$ value. Therefore, the integration of the area represents the sum of the intensities from all the grains of the sample. It is apparent from the figures that the peak intensity decreases as the temperature increases.

To quantify the temperature dependent peak intensities, the peaks shown in Fig. 2a are integrated over the whole angular range. The results are normalized to a common linear extrapolated T=0 value and plotted against the temperature in panel (b). For monatomic systems, the intensity of a (0,0,$`l`$) Bragg peak is expressed as $`I=I_0\mathrm{exp}(\frac{1}{2}z^2l^2)`$ where the exponent is the DWF and $`z^2`$ is the thermally averaged mean square motion of the atoms in z directionDWF . For a classical Harmonic oscillator, $`z^2T`$ and the intensity thus becomes $`I=I_0\mathrm{exp}(\lambda l^2T)I_0(1\lambda l^2T)`$ where $`\lambda `$ is a constant. Therefore, one would expect linear temperature dependence of the DWFs for T$`1/\lambda l^2`$. The intensities in the figure show linear temperature dependence and no anomaly is found within the experimental errorErrorBar . Also shown in the panel is the temperature dependent intensity of the (0,0,11) peak from YBCO. The ratio of the DWFs of the (0,0,13) and (0,0,11) peaks is $`1.28\pm 0.05`$ which is somewhat close to the expected value of $`13^2/11^2=1.4`$ for monatomic systems with pure thermal phonon effects. The measured temperature dependent intensities suggest normal behavior of the c-axis DWF without any anomaly. Panels (c) and (d) show data from Hg1212 samples. Other than the larger rocking width, the behavior is more or less the same with YBCO case, showing no sign of anomaly at $`T_c`$ within the experimental error. The deviation of (0,0,10) data from the linear behavior is related to the fact that, unlike other peaks, it was measured along with substrate peaks hence producing larger experimental errors, and is assumed to be extrinsic effect.

Interpretation of the above results, however, is not as easy as the case for monatomic systems such as Si. The expression of a Bragg peak intensity contains in general exponential functions of the displacement parameters of the atoms in the unit cell. For a monatomic case, it could be reduced to a single exponential function of the displacement parameter (assuming the displacement parameters for the atoms in the unit cell are the same) and the DWF can be interpreted with a relative ease. The form factors for polyatomic compounds however are different and the Bragg peak intensity is expressed by a combination of exponential functions. It is therefore very hard to extract the information on the dynamic displacements from DWFs. The other aspect is that the observed temperature dependence does not solely come from the dynamic displacements. Not only the phonons but also the changes in the static atomic positions within the unit cell affect the intensities.

In spite of the difficulties, we can still extract useful information from the results. Even though the Bragg peak intensity expression contains multiple exponential terms, it shows linear temperature dependence if the displacements are purely due to thermal vibrations. Therefore, the fact that experimental data show linear temperature dependence strongly suggests that the major contributor to the DWF is the dynamic displacements as there is no intrinsic reason for such temperature dependence from the static displacements. Indeed, detailed neutron diffraction experiments on YBCO show that the mean square displacements are mostly dynamicSchweiss . We also note that heavy elements contribute more to the diffraction intensities in our x-ray measurements due to their greater high Z sensitivity. To see the different contributions, we list in Table 1 calculated fractions of the planar oxygen and Cu-O planar contributions to the total diffraction peak intensities of YBCO and Hg1212 using the published structural informationJorgensen ; Morosin . Note that the fractions do not add up to make the total due to the interference but roughly show the insignificant Cu-O plane contribution to the total intensity. It is thus conceivable that the phonon anomalies in the Cu-O plane measured by EXAFSLanzara  may be buried under the contributions from the heavy elements. Based on these, it is reasonable to conclude that at least the heavy elements do not show anomaly at $`T_c`$ in their c-axis dynamic properties.

On the more fundamental side, the anomalies in the c-axis lattice constants are generally relatively small compared to those along a- or b-axesAsahi ; Braden ; Pasler . Therefore, it is possible that the c-axis phonon population anomaly may well be very small and undetectable. Looking at a- and b-axis Debye-Waller factors is therefore essential. This may explain the absence of the anomaly in the Hg1212 data while measurement by EXAFS on powder samples of similar compound HgBa2CuO4 shows anomaly in the mean square dispacementsLanzara . Use of Rietveld refinement with powder diffraction at a brighter x-ray source could give an answer to this. Better yet, considering all the factors discussed above, similar experiments by neutron diffraction may resolve most of the problems; the typical grain sizes of HTSC crystals and sample motion upon temperature change are insignificant compared to the neutron beamsize. This will allow us to investigate a- and b-axis DWFs by a diffraction technique. In addition, its sensitivity to low Z atoms will allow more accurate estimation of the oxygen contribution to the DWFs. There indeed is a strong indication that temperature dependent (1,2,12) neutron Bragg peak intensities of YBCO crystals have anomalies at the TcSchweiss .

In conclusion, temperature dependent c-axis DWFs of YBCO and Hg1212 thin films are obtained by measuring the temperature dependent $`(0,0,l)`$ x-ray Bragg peak intensities. The measured DWFs show linear temperature dependence within the experimental errors, showing no anomalous effects near Tc. Considering the fact that the x-ray diffraction intensity is much more sensitive to the heavy elements, the results suggest that there is no anomalous lattice dynamics of heavy elements along the c-axis. Further studies of a- and b-axis temperature dependent DWFs by neutron diffraction in combination with temperature dependent structural studies by EXAFS may shed more light on the temperature dependent lattice dynamics, i.e., role of the phonons in HTSCs.

We would like to thank F. Bridges and J. Arthur for helpful discussions, and H. Shin for statistical analysis. SSRL is operated by the DOE office of Basic Energy Research, Division of Chemical Sciences. The office’s division of Material Science provided support for this research. This work is supported (in part) by the Korean Science and Engineering Foundation (KOSEF) through Center for Strongly Correlated Materials Research (CSCMR) at Seoul National University.


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# Update on pion weak decay constants in nuclear matter

## I INTRODUCTION

The pion decay constant in nuclear matter is one important parameter to be determined in modern nuclear physics. As an order parameter of spontaneous chiral symmetry breaking, its reduction in the matter may indicate a partial restoration of chiral symmetry. In particular, recent measurements of deeply bound pionic atoms Gilg:1999qa ; Itahashi:1999qb ; Geissel:ur ; Suzuki:2002ae  give rise to an exciting discussion on pion-nucleus optical potential. The isovector parameter of the s-wave pion nucleus potential is directly related to the pion decay constant, and its observed enhancement in nuclear matter can be interpreted as a partial restoration of chiral symmetry Friedman:um ; Kaiser:2001bx ; Kolomeitsev:2002gc ; Weise:sg , namely by the decrease of the decay constant. This restoration causes the universal softening of $`\sigma `$ and $`\rho `$ in the matter Yokokawa:2002pw . Furthermore, the change in the decay constant is believed to scale the reduction of hadron masses in the medium Brown:kk . Also the decay constant is directly connected to the renormalization of the induced pseudoscalar coupling in the matter, which is believed to control muon captures in nuclei Kirchbach:1993ep ; Akhmedov:ms ; Kirchbach:1997rk ; Akhmedov:yj .

One interesting feature of the in-medium pion decay constant is its separation into the time ($`f_t`$) and space ($`f_s`$) components. For a model-independent prediction, it will be interesting to calculate the decay constants using QCD sum rules Shifman:bx ; Shifman:by . Indeed, one of present authors (H.K) recently performed a QCD sum rule calculation of the decay constants Kim:2001xu  using pseudoscalar-axial vector correlation function in the matter,

$`\mathrm{\Pi }^\mu =i{\displaystyle d^4xe^{ipx}\rho |T[\overline{d}(x)i\gamma _5u(x)\overline{u}(0)\gamma ^\mu \gamma _5d(0)]|\rho }.`$ (1)
This correlation function is useful because it can reproduce the Gell-Mann$``$Oakes$``$Renner (GOR) relation in vacuum as well as its in-medium version. Also one can clearly see the separation of $`f_t`$ and $`f_s`$ in QCD calculation. It was found that the splitting between $`f_t`$ and $`f_s`$ is mainly driven by the dimension 5 condensate in the nucleon, $`\overline{q}(iD_0)^2q_N+\frac{1}{8}\overline{q}g_s\sigma 𝒢q_N`$. But its positive value leads to a somewhat puzzling result of $`f_s/f_t1`$, which neither agrees with the result from in-medium chiral perturbation theory Kirchbach:1997rk ; Meissner:2001gz , $`f_s/f_t0.28`$ (or smaller), nor with the causal constraint from Ref. Pisarski:1996mt , $`f_s/f_t1`$.

However, before making a definite claim from QCD sum rules, one may need to re-examine the sum rule calculation in various respects. First, the argument leading to a positive value for the dimension 5 condensate is based on the Hermitian property of the operators involved but, as we will discuss below, it is not sufficient for determining the definite sign of the dimension 5 condensate. One needs an alternative way to constrain the value of the dimension 5 condensate. One possibility is to constrain it by requiring that the sum rules reproduce a reasonable in-medium pion mass. Another ingredient for this update is to check more carefully the quasi-pion dominance of the correlation function Eq.(1). In particular, we need to calculate the contributions from $`N`$ and $`\mathrm{\Delta }`$ intermediate states and estimate how large the change is from these intermediate states. In this work, we address these two aspects and improve the previous QCD sum rule calculation for $`f_t`$ and $`f_s`$.

This paper is organized as follows. In Sec. II, we briefly re-derive QCD sum rules for $`f_t`$ and $`f_s`$. The issue on the sign of the dimension 5 condensate is discussed in Sec.III. The contributions from $`N`$ and $`\mathrm{\Delta }`$ intermediate states are studied in Sec. IV and Sec. V. For the $`\mathrm{\Delta }`$ contribution, we propose a way to subtract it from our sum rules. In Sec. VI, we constrain the dimension 5 condensate by requiring it to reproduce an acceptable in-medium pion mass within our sum rule and use it to calculate $`f_t`$ and $`f_s`$. We then summarize in Sec. VII.

## II The QCD sum rule for $`f_t`$ and $`f_s`$.

In this section, we briefly go through the QCD sum rule derivation of the in-medium pion decay constants, $`f_t`$ and $`f_s`$, in Ref. Kim:2001xu . Ref. Kim:2001xu  considered the pseudoscalar-axial vector correlation function in nuclear matter, Eq.(1), and constructed the two sum rules in the following limit

$`\mathrm{\Pi }_t\underset{𝐩0}{lim}{\displaystyle \frac{\mathrm{\Pi }^0}{ip_0}};\mathrm{\Pi }_s\underset{𝐩0}{lim}{\displaystyle \frac{\mathrm{\Pi }^j}{ip^j}}.`$ (2)
Using the in-medium decay constants defined by

$`\rho |\overline{d}\gamma ^\mu \gamma _5u|\pi ^+(k)\rho =(if_tk_0,if_s𝐤),`$ (3)
and its derivative, we obtain the phenomenological sides

$`\mathrm{\Pi }_t^{phen}={\displaystyle \frac{m_{\pi }^{}{}_{}{}^{2}}{2m_q}}{\displaystyle \frac{f_{t}^{}{}_{}{}^{2}}{p_0^2m_{\pi }^{}{}_{}{}^{2}}};\mathrm{\Pi }_s^{phen}={\displaystyle \frac{m_{\pi }^{}{}_{}{}^{2}}{2m_q}}{\displaystyle \frac{f_tf_s}{p_0^2m_{\pi }^{}{}_{}{}^{2}}},`$ (4)
when a quasi-pion intermediates the correlation function. On the other hand, the operator product expansion (OPE) allows us to calculate the correlation function using QCD degrees of freedom. Up to dimension 5 in the expansion, the OPE side of the correlation function is given by Kim:2001xu ,

$`\mathrm{\Pi }_t^{ope}`$ $`=`$ $`{\displaystyle \frac{3}{4\pi ^2}}{\displaystyle _0^1}𝑑um_q\mathrm{ln}[u(1u)p_0^2+m_q^2]+{\displaystyle \frac{2\overline{q}q_\rho }{p_0^2m_q^2}}+{\displaystyle \frac{8m_qq^{}iD_0q_\rho 2m_q^2\overline{q}q_\rho }{(p_0^2m_q^2)^2}},`$ (5)
$`\mathrm{\Pi }_s^{ope}`$ $`=`$ $`{\displaystyle \frac{3}{4\pi ^2}}{\displaystyle _0^1}𝑑um_q\mathrm{ln}[u(1u)p_0^2+m_q^2]+{\displaystyle \frac{2\overline{q}q_\rho }{p_0^2m_q^2}}{\displaystyle \frac{8}{3}}{\displaystyle \frac{m_qq^{}iD_0q_\rho }{(p_0^2m_q^2)^2}}{\displaystyle \frac{2m_q^2\overline{q}q_\rho }{(p_0^2m_q^2)^2}}`$ (6)
$`+{\displaystyle \frac{32}{3}}\left[\overline{q}(iD_0)^2q_\rho +{\displaystyle \frac{1}{8}}\overline{q}g_s\sigma 𝒢q_\rho \right]{\displaystyle \frac{1}{(p_0^2m_q^2)^2}}.`$
Here the subscript “$`\rho `$” denotes the nuclear expectation value.

When Eqs.(4),(5) and (6) are put into the Borel weighted sum rules,

$`{\displaystyle _0^{S_0}}𝑑se^{s/M^2}{\displaystyle \frac{1}{\pi }}\mathrm{Im}[\mathrm{\Pi }_l^{phen}(s)\mathrm{\Pi }_l^{ope}(s)]=0(l=t,s),`$ (7)
we obtain the two sum rules,

$`{\displaystyle \frac{m_{\pi }^{}{}_{}{}^{2}}{2m_q}}f_{t}^{}{}_{}{}^{2}e^{m_{}^{}{}_{\pi }{}^{2}/M^2}`$ $`=`$ $`{\displaystyle \frac{3m_q}{4\pi ^2}}{\displaystyle _{4m_q^2}^{S_0}}𝑑se^{s/M^2}\sqrt{1{\displaystyle \frac{4m_q^2}{s}}}2\overline{q}q_\rho e^{m_q^2/M^2}`$ (8)
$`+`$ $`{\displaystyle \frac{8m_q}{M^2}}q^{}iD_0q_\rho e^{m_q^2/M^2}{\displaystyle \frac{2m_q^2}{M^2}}\overline{q}q_\rho e^{m_q^2/M^2},`$
$`{\displaystyle \frac{m_{\pi }^{}{}_{}{}^{2}}{2m_q}}f_tf_se^{m_{}^{}{}_{\pi }{}^{2}/M^2}`$ $`=`$ $`{\displaystyle \frac{3m_q}{4\pi ^2}}{\displaystyle _{4m_q^2}^{S_0}}𝑑se^{s/M^2}\sqrt{1{\displaystyle \frac{4m_q^2}{s}}}2\overline{q}q_\rho e^{m_q^2/M^2}`$ (9)
$``$ $`{\displaystyle \frac{8m_q}{3M^2}}q^{}iD_0q_\rho e^{m_q^2/M^2}{\displaystyle \frac{2m_q^2}{M^2}}\overline{q}q_\rho e^{m_q^2/M^2}`$
$`+`$ $`{\displaystyle \frac{32}{3M^2}}\left[\overline{q}(iD_0)^2q_\rho +{\displaystyle \frac{1}{8}}\overline{q}g_s\sigma 𝒢q_\rho \right]e^{m_q^2/M^2}.`$
Here $`S_0`$ is the continuum threshold and $`M`$ is the Borel mass. The various nuclear condensates appearing in the right-hand side are evaluated in the linear density approximation, which yields

$`q^{}iD_0q_\rho =\rho q^{}iD_0q_N+{\displaystyle \frac{m_q}{4}}\overline{q}q_\rho ,`$ (10)
$`\overline{q}(iD_0)^2q_\rho +{\displaystyle \frac{1}{8}}\overline{q}g_s\sigma 𝒢q_\rho =\rho \left[\overline{q}(iD_0)^2q_N+{\displaystyle \frac{1}{8}}\overline{q}g_s\sigma 𝒢q_N\right]+{\displaystyle \frac{m_q^2}{4}}\overline{q}q_\rho ,`$ (11)
$`\overline{q}q_\rho =\overline{q}q_0+\rho \overline{q}q_N.`$ (12)
Here the subscript “$`0`$” (“$`N`$”) denotes the vacuum (nucleon) expectation value. It is interesting to note that, when Eqs.(10) and (11) are put into our sum rules, the $`m_q^2\overline{q}q_\rho `$ terms are canceled away.

To leading order in quark mass, the ratio of the two sum rules gives

$`{\displaystyle \frac{f_s}{f_t}}1{\displaystyle \frac{16}{3M^2}}{\displaystyle \frac{\overline{q}(iD_0)^2q_\rho +\frac{1}{8}\overline{q}g_s\sigma 𝒢q_\rho }{\overline{q}q_\rho }}.`$ (13)
Thus, the main splitting between the two decay constants is driven by the nuclear dimension 5 condensate,

$`\overline{q}(iD_0)^2q_\rho +{\displaystyle \frac{1}{8}}\overline{q}g_s\sigma 𝒢q_\rho .`$ (14)
Note, in vacuum, this dimension 5 condensate is zero and both sum rules reproduce, up to leading order in quark mass, the well-known Gell-Mann$``$Oakes$``$Renner (GOR) relation (in vacuum, $`f_t=f_s=f_\pi =131`$ MeV),

$`m_\pi ^2f_\pi ^2=4m_q\overline{q}q_0.`$ (15)
Even including higher orders in quark mass, our sum rules reproduce the vacuum sum rule for the pseudoscalar decay constants Kim:2001ss . Moreover the $`\mathrm{\Pi }_t`$ sum rule, Eq.(8), satisfies the in-medium GOR relation

$`m_{\pi }^{}{}_{}{}^{2}f_t^2=4m_q\overline{q}q_\rho ,`$ (16)
to leading order in $`m_q`$.

## III The dimension 5 condensate

The dimension 5 condensate is crucial for splitting $`f_t`$ and $`f_s`$. Depending on its sign, we clearly have different prediction on the ratio $`f_s/f_t`$. The ratio becomes greater (smaller) than the unity if the dimension 5 condensate is positive (negative). Using $`\overline{q}g_s\sigma 𝒢q=2\overline{q}D^2q`$ in the chiral limit, the dimension 5 condensate in the linear density approximation can be rearranged into the form,

$`\overline{q}(iD_0)^2q_\rho +{\displaystyle \frac{1}{8}}\overline{q}g_s\sigma 𝒢q_\rho =\rho \left[{\displaystyle \frac{3}{4}}\overline{q}(iD_0)^2q_N+{\displaystyle \frac{1}{4}}\overline{q}(i𝐃)^2q_N\right].`$ (17)
Ref. Kim:2001xu  argued that, since $`iD_0`$ and $`i𝐃`$ are Hermitian operators, their square must be positive definite. Thus, the nucleon dimension 5 condensate, $`\frac{3}{4}\overline{q}(iD_0)^2q_N+\frac{1}{4}\overline{q}(i𝐃)^2q_N`$, is claimed to have the same sign with the positive quantity, $`\overline{q}q_N`$, which seems consistent with its rough estimate from the bag model Jin:1992id . This Hermitian argument however is not consistent with the vanishing dimension 5 condensate in vacuum 111 If the same Hermitian argument is applied to its vacuum expectation value, we should have $`\frac{3}{4}\overline{q}(iD_0)^2q_0+\frac{1}{4}\overline{q}(i𝐃)^2q_00`$ as $`\overline{q}q_0<0`$. Since the vacuum expectation value is zero, the Hermitian argument only leads to a trivial consequence in vacuum, $`\overline{q}(iD_0)^2q_0=\overline{q}(i𝐃)^2q_0=0`$. This however can not be correct because their difference is well-known to be nonzero, $`\overline{q}(D_0^2𝐃^2)q_0=\overline{q}D^2q_00`$..

A possible resolution for this inconsistency can be sought for by considering the condensate in the Euclidean space, $`x_0ix_4`$. In this space, the vacuum expectation value becomes $`\frac{3}{4}\overline{q}(iD_4)^2q_0+\frac{1}{4}\overline{q}(i𝐃)^2q_0`$ and, due to the $`O(4)`$ symmetry of vacuum, it is clear that the two terms are canceled to make their sum zero, agreeing with the expectation. Its nucleon expectation value, $`\frac{3}{4}\overline{q}(iD_4)^2q_N+\frac{1}{4}\overline{q}(i𝐃)^2q_N`$, however, is not necessarily zero because the $`O(4)`$ symmetry is broken by a preferred direction of the nucleon state. Now, because of the opposite sign, the Hermitian argument does not lead to a definite sign for the nucleon dimension 5 condensate.

We now comment on a rough estimate of the dimension 5 condensate using the bag model Jin:1992id . According to this, $`\overline{q}(iD_0)^2q_N`$ is zero and, depending on how one treats $`\overline{q}g_s\sigma 𝒢q_N`$, the dimension 5 condensate varies from $`0.08`$ GeV2 to $`0.3`$ GeV2. Though not precise, the bag model seems to suggest a positive value for the dimension 5 condensate. However, in the bag model estimate, the non-Abelian nature of gluon fields can not be implemented and the quark field equation is violated on the bag surface Jin:1992id . Because of this limitation, in the subsequent analysis of the in-medium nucleon sum rule Jin:1993up , the dimension 5 condensate is allowed to be negative, varying from $`0.5`$ GeV2 to 0.5 GeV2. Therefore, the positive value for the dimension 5 condensate as well as its magnitude is not firmly established. One needs an alternative method to constrain this condensate. In the following analysis, we look for this dimension 5 condensate within our sum rules using the in-medium pion mass as an input.

## IV The nucleon intermediate state

Another motivation for doing this update is to investigate more closely the hadronic content of the correlation function Eq.(1). In particular, the correlation function may pick up some contributions from $`N`$ and $`\mathrm{\Delta }`$ intermediate states and the quasi-pion dominance has to be checked further. The nuclear correlation function, Eq.(1), in the linear density approximation is separated into the vacuum and nucleon parts,

$`\mathrm{\Pi }^\mu =\mathrm{\Pi }_0^\mu +\rho \mathrm{\Pi }_N^\mu `$ (18)
where the nucleon correlation function is given by

$`\mathrm{\Pi }_N^\mu i{\displaystyle d^4xe^{ipx}N|T[\overline{d}(x)i\gamma _5u(x)\overline{u}(0)\gamma ^\mu \gamma _5d(0)]|N}.`$ (19)
The nucleon intermediate state can make a pole structure at $`p_0^2=0`$, which may affect the sum rules through Eq.(19) though its contribution is down by the nuclear density $`\rho `$.

To calculate the $`N`$ intermediate state contribution, we insertChristos:tu

$`{\displaystyle \frac{d^4q}{(2\pi )^4}\delta (q^2m_N^2)\theta (q_0)|N(𝐪)N(𝐪)|}`$ (20)
between the pseudoscalar and axial-vector currents in Eq.(19). The nucleon matrix elements of the axial-vector current and the pseudoscalar current are given respectively by Donoghue:1992dd

$`N(𝐪)|\overline{d}\gamma _\mu \gamma _5u|N(𝐤)`$ $`=`$ $`\overline{U}_N(𝐪)\left[g_A\gamma _\mu \gamma _5+(qk)_\mu \gamma _5g_p\right]U_N(𝐤)`$ (21)
$`N(𝐪)|\overline{d}i\gamma _5u|N(𝐤)`$ $`=`$ $`{\displaystyle \frac{f_\pi m_\pi ^2}{2m_q}}{\displaystyle \frac{g_{\pi NN}}{m_\pi ^2(qk)^2}}\overline{U}_N(𝐪)i\gamma _5U_N(𝐤)`$ (22)
where $`U_N`$ is the nucleon spinor, $`g_A`$ the nucleon axial charge and $`g_p`$ the induced pseudoscalar term. Inserting these into the nucleon correlation function, Eq.(19), we directly evaluate the $`N`$ intermediate state contribution. We find that this contribution is proportional to $`\sqrt{𝐩^2+m_N^2}m_N`$, which vanishes in the limit of Eq. (2). Therefore, the nucleon intermediate state does not contribute to the correlation functions, $`\mathrm{\Pi }_t`$ and $`\mathrm{\Pi }_s`$.

## V The $`\mathrm{\Delta }`$ intermediate state

We now consider the $`\mathrm{\Delta }`$ contribution in the nucleon correlation function, Eq.(19). A $`\mathrm{\Delta }`$ couples to $`\pi N`$ channel strongly and the correlation function may pick up a significant contribution from the $`\mathrm{\Delta }`$ intermediate state. The $`\mathrm{\Delta }`$ intermediate state in $`\mathrm{\Pi }_N^\mu `$ must have a pole at $`p_0^2=(m_\mathrm{\Delta }m_N)^20.09`$ GeV2. One can either treat this as a part of the continuum or directly calculate this contribution using an effective model. Unlike the nucleon intermediate case, however, the matrix elements involved, $`\mathrm{\Delta }|\overline{u}\gamma _\mu \gamma _5d|N`$ and $`\mathrm{\Delta }|\overline{d}i\gamma _5u|N`$, are not well-known. Even if one can establish a form of the $`\mathrm{\Delta }`$ contribution, the parameters involved highly depend on various models: the estimate of this contribution can not be precise.

Roughly, one may eliminate the $`\mathrm{\Delta }`$ contribution by considering the sum rules with an additional weight of $`s(m_\mathrm{\Delta }m_N)^2`$,

$`{\displaystyle _0^{S_0}}𝑑se^{s/M^2}[s(m_\mathrm{\Delta }m_N)^2]{\displaystyle \frac{1}{\pi }}\mathrm{Im}[\mathrm{\Pi }_l^{phen}(s)\mathrm{\Pi }_l^{ope}(s)]=0(l=t,s).`$ (23)
The new weight eliminates the pole at $`p_0^2=(m_\mathrm{\Delta }m_N)^2`$ and the sum rules are now free from the $`\mathrm{\Delta }`$ contribution. However, the new weight affects the vacuum part of the sum rules as well and, in the limit of $`\rho 0`$, the right-hand side of the GOR relation, Eq.(15), entails the factor

$`{\displaystyle \frac{m_q^2(m_\mathrm{\Delta }m_N)^2}{m_\pi ^2(m_\mathrm{\Delta }m_N)^2}}1.3`$ (24)
coming from the additional weight. Though this factor is the unity to leading order in the chiral expansion, its numerical value deviated from the unity affects the GOR relation. Thus, this way of eliminating the $`\mathrm{\Delta }`$ contribution is crude.

A more economical way is to apply the similar prescription only to the nucleon correlation function $`\mathrm{\Pi }_N^\mu `$ in Eq.(18). That is, we introduce $`\mathrm{\Pi }_{Nt}`$ and $`\mathrm{\Pi }_{Ns}`$ from $`\mathrm{\Pi }_N^\mu `$ similarly defined as $`\mathrm{\Pi }_t`$ and $`\mathrm{\Pi }_s`$ in Eq.(2) and construct

$`{\displaystyle _0^{S_0}}𝑑se^{s/M^2}[s(m_\mathrm{\Delta }m_N)^2]{\displaystyle \frac{1}{\pi }}\mathrm{Im}[\mathrm{\Pi }_{Nl}^{phen}(s)\mathrm{\Pi }_{Nl}^{ope}(s)]=0(l=t,s).`$ (25)
Obviously, this prescription does not suffer from the problem mentioned above: it does not affect the GOR relation in vacuum. To construct $`\mathrm{\Pi }_{Nt}^{phen}`$ and $`\mathrm{\Pi }_{Ns}^{phen}`$, we expand in terms of the density the in-medium parameters appearing in Eq.(4),

$`f_t=f_\pi +\rho \mathrm{\Delta }f_t;f_s=f_\pi +\rho \mathrm{\Delta }f_s;m_\pi ^{}=m_\pi +\rho \mathrm{\Delta }m_\pi .`$ (26)
The new phenomenological parameters, $`\mathrm{\Delta }f_t`$, $`\mathrm{\Delta }f_s`$ and $`\mathrm{\Delta }m_\pi `$, constitute $`\mathrm{\Pi }_{Nt}^{phen}`$ and $`\mathrm{\Pi }_{Ns}^{phen}`$. In the OPE side, using Eqs.(10),(11) and (12) for various nuclear condensates, we collect the terms proportional to $`\rho `$ corresponding to $`\mathrm{\Pi }_{Nt}^{ope}`$ and $`\mathrm{\Pi }_{Ns}^{ope}`$. We put them into Eq.(25) and obtain the $`\mathrm{\Delta }`$ subtracted sum rules for $`\mathrm{\Delta }f_t`$ and $`\mathrm{\Delta }f_s`$,

$`\mathrm{\Delta }f_t`$ $`=`$ $`{\displaystyle \frac{\mathrm{\Delta }m_\pi }{m_\pi }}f_\pi {\displaystyle \frac{2m_qr_\mathrm{\Delta }}{m_\pi ^2f_\pi }}\overline{q}q_Ne^{(m_\pi ^2m_q^2)/M^2}`$ (27)
$`+`$ $`{\displaystyle \frac{8m_q^2}{m_\pi ^2f_\pi }}q^{}iD_0q_N\left[{\displaystyle \frac{r_\mathrm{\Delta }}{M^2}}\pi _\mathrm{\Delta }\right]e^{(m_\pi ^2m_q^2)/M^2},`$
$`\mathrm{\Delta }f_t+\mathrm{\Delta }f_s`$ $`=`$ $`{\displaystyle \frac{2\mathrm{\Delta }m_\pi }{m_\pi }}f_\pi {\displaystyle \frac{4m_qr_\mathrm{\Delta }}{m_\pi ^2f_\pi }}\overline{q}q_Ne^{(m_\pi ^2m_q^2)/M^2}`$ (28)
$``$ $`{\displaystyle \frac{16m_q^2}{3m_\pi ^2f_\pi }}q^{}iD_0q_N\left[{\displaystyle \frac{r_\mathrm{\Delta }}{M^2}}\pi _\mathrm{\Delta }\right]e^{(m_\pi ^2m_q^2)/M^2}`$
$`+`$ $`{\displaystyle \frac{64m_q}{3m_\pi ^2f_\pi }}\left[\overline{q}(iD_0)^2q_N+{\displaystyle \frac{1}{8}}\overline{q}g_s\sigma 𝒢q_N\right]\left[{\displaystyle \frac{r_\mathrm{\Delta }}{M^2}}\pi _\mathrm{\Delta }\right]e^{(m_\pi ^2m_q^2)/M^2},`$
where we have defined

$`r_\mathrm{\Delta }={\displaystyle \frac{m_q^2(m_\mathrm{\Delta }m_N)^2}{m_\pi ^2(m_\mathrm{\Delta }m_N)^2}};\pi _\mathrm{\Delta }={\displaystyle \frac{1}{m_\pi ^2(m_\mathrm{\Delta }m_N)^2}}.`$ (29)
Note, the pion mass shift in the exponential, which is an order $`𝒪(m_\pi ^3)`$ or higher, has been neglected in deriving these sum rules. Once $`\mathrm{\Delta }m_\pi `$ is given, these sum rules yield $`\mathrm{\Delta }f_t`$ and $`\mathrm{\Delta }f_s`$, which then, through Eq.(26), lead to $`f_t`$ and $`f_s`$ with the $`\mathrm{\Delta }`$ contribution being subtracted. For the justification of this, we have checked that, without $`\mathrm{\Delta }`$ subtraction, this procedure gives $`f_t`$ and $`f_s`$ similar in magnitude with those obtained directly from Eqs.(8),(9).

One may worry about the $`\mathrm{\Delta }`$ decay width and argue that the $`\mathrm{\Delta }`$ contribution is not a pole. A $`\mathrm{\Delta }`$ in free space strongly decays to $`\pi N`$ with its width $`115`$ MeV. However, in nuclear matter, a $`\mathrm{\Delta }`$ at rest can not decay to $`\pi N`$ by the Pauli blocking 222 Note, the limit of Eq.(2) means that we are considering a $`\mathrm{\Delta }`$ at rest.. On the other hand, a $`\mathrm{\Delta }`$ in nuclear matter can have a “spreading width” through the mechanism $`\mathrm{\Delta }+NN+N`$. Its width at nuclear saturation density is between 57 to 75 MeV Kim:1996ad ; Jain:kf , reasonably small. The pole ansantz for a resonance with this small width is believed to be reasonable.

## VI Sum Rule Analysis

As we have discussed, the dimension 5 condensate is important for splitting $`f_s`$ and $`f_t`$ but its value is not well-known. An additional information is necessary to restrict the value of the dimension 5 condensate. Instead of relying on a model calculation, we look for its value directly from our sum rules using in-medium pion mass as an input. The in-medium pion mass has been studied extensively by chiral perturbation theory Meissner:2001gz ; Park:2001ht ; Delorme:1996cc ; Kaiser:2001bx . Experimentally, it is extracted from the local potential of the deeply bound pionic atom in 208Pb Yamazaki:1997na . A consensus from these studies is that the in-medium pion mass increases slightly up to 20 MeV. We therefore look for an optimal value of the dimension 5 condensate that leads to the in-medium pion mass within $`139159`$ MeV from the $`\mathrm{\Pi }_s`$ sum rule, Eq.(9). The $`\mathrm{\Pi }_t`$ sum rule, Eq.(8), can not be used for this purpose as it does not depend on the dimension 5 condensate.

To calculate the pion mass from our sum rules, we take the derivative of Eq.(9) with respect to $`1/M^2`$ and divide the resulting formula by Eq.(9). Namely, by defining the right-hand side of Eq.(9) by $`\mathrm{\Pi }_{Borel}(M^2)`$ and its derivative with respect to $`1/M^2`$ by $`\mathrm{\Pi }_{Borel}^{}(M^2)`$, the in-medium pion mass satisfies

$`m_{\pi }^{}{}_{}{}^{2}={\displaystyle \frac{\mathrm{\Pi }_{Borel}^{}(M^2)}{\mathrm{\Pi }_{Borel}(M^2)}}.`$ (30)
Using this formula, we plot $`m_{\pi }^{}{}_{}{}^{2}`$ versus the Borel mass $`M^2`$ in fig. 1 for various values of the nucleon dimension 5 condensate,

$`D_5\overline{q}(iD_0)^2q_N+{\displaystyle \frac{1}{8}}\overline{q}g_s\sigma 𝒢q_N.`$ (31)
The continuum threshold is set to be $`s_0=0.09`$ GeV2 corresponding to the $`\mathrm{\Delta }`$ intermediate state, i.e., $`(m_\mathrm{\Delta }m_N)^2`$ but the result is not sensitive to this choice. Other parameters used in our analysis are

$`m_q=0.007\mathrm{GeV};\overline{q}q_0=(0.225\mathrm{GeV})^3`$
$`\overline{q}q_N={\displaystyle \frac{0.045\mathrm{GeV}}{2m_q}};q^{}iD_0q_N=0.18\mathrm{GeV}.`$ (32)
As shown, we have quite different curves depending on the dimension 5 condensate, $`D_5`$. In particular, the positive value of $`D_5`$ leads to a tachyonic pion mass, $`m_{\pi }^{}{}_{}{}^{2}<0`$. As the positive value leads to $`f_s/f_t1`$ according to Eq.(13), the tachyonic pion mass for $`D_50`$ is consistent with the claim that $`f_s/f_t1`$ breaks the causality Pisarski:1996mt . When $`D_5`$ is fixed to be around $`0.02`$ GeV2, the pion effective mass is about 140 MeV and the stability is quite good over a wide range of the Borel masses. For the in-medium pion mass within $`139\mathrm{MeV}m_\pi ^{}159\mathrm{MeV}`$, $`D_5`$ is negative and its magnitude is within the range, $`0.019|D_5|0.025`$. We have also checked that this range of $`D_5`$ is stable under the rough subtraction of the $`\mathrm{\Delta }`$ contribution given in Eq.(23). Note, the $`\mathrm{\Delta }`$ subtraction procedure advocated in Eq.(25) is not applicable for obtaining the in-medium pion mass.

We now move to an analysis for the pion decay constants, $`f_t`$ and $`f_s`$. In fig.2, we plot $`f_t/f_\pi `$ using the sum rule Eq.(8) at the saturation density $`\rho =0.17`$ fm-3. When $`m_\pi ^{}=139`$ MeV, $`f_t/f_\pi =0.79`$ is obtained from the $`\mathrm{\Pi }_t`$ sum rule Eq.(8) at $`M^2=1`$ GeV2 but with $`\mathrm{\Delta }`$ subtracted according to Eqs.(26) and (27) the ratio becomes slightly smaller, 0.77. The Borel curves for these two cases are shown by the two upper curves in fig. 2. The solid curve is from Eq.(8) and the dashed curve is when the $`\mathrm{\Delta }`$ contribution is subtracted. The lower two curves are obtained when we use the larger pion mass, $`m_\pi ^{}=159`$ MeV. Increasing the pion mass makes $`f_t/f_\pi `$ smaller in both cases. Because the $`\mathrm{\Pi }_t`$ sum rule satisfies the in-medium GOR relation, Eq.(16), large $`m_\pi ^{}`$ is compensated by small $`f_t`$. Also at $`m_\pi ^{}=159`$ MeV, $`f_t`$ from the $`\mathrm{\Delta }`$ subtracted sum rule is 9 % smaller than the one without $`\mathrm{\Delta }`$ subtraction. Large $`m_\pi ^{}`$ may easily excite a $`\mathrm{\Delta }`$ so that the $`\mathrm{\Delta }`$ contribution becomes larger in the correlation function. It is interesting to note that $`f_t/f_\pi `$ at $`m_\pi ^{}=139`$ MeV, either with or without $`\mathrm{\Delta }`$ subtraction, is not far from the experimental value of 0.8 Suzuki:2002ae .

Fig. 3 shows the ratio $`f_s/f_\pi `$. To obtain this, we first calculate $`f_s/f_t`$ from the ratio of Eqs.(8) and (9), and multiply it by $`f_t/f_\pi `$ obtained from fig. 2. The results with $`\mathrm{\Delta }`$ subtraction from Eqs.(27) and (28) are shown by the dashed curves. Unlike to the $`f_t/f_\pi `$ case, a somewhat sizable suppression of $`f_s/f_\pi `$ is obtained when the $`\mathrm{\Delta }`$ contribution is subtracted. This shows that the $`\mathrm{\Pi }_s`$ sum rule depends heavily on the $`\mathrm{\Delta }`$ contribution. At $`m_\pi ^{}=139`$ MeV, the $`\mathrm{\Delta }`$ subtracted sum rule shifts $`f_s/f_\pi `$ from 0.78 to 0.57, 27% change, while at $`m_\pi ^{}=159`$ MeV, from 0.68 to 0.37, 45 % change. Such a large suppression of $`f_s`$ is similar to the results from the in-medium chiral perturbation theory Kirchbach:1997rk ; Meissner:2001gz . These results as well as the results for $`f_t`$ are summarized in Table 1.

Fig. 4 shows the density dependence of $`f_t/f_\pi `$. The solid curve is obtained from Eq.(8) with $`m_\pi ^{}=139`$ MeV and the dashed curve is when the $`\mathrm{\Delta }`$ contribution is subtracted according to Eqs.(26) and (27). The similar curves for $`f_s/f_\pi `$ are shown in Fig. 5. Again, we see that $`f_s/f_\pi `$ is strongly suppressed when the $`\mathrm{\Delta }`$ contribution is subtracted. It should be also noted that $`f_s/f_t`$ is less than the unity always, agreeing with the causal constraint derived from Ref. Pisarski:1996mt .

## VII Summary and outlook

We have updated the QCD sum rule calculation of the in-medium pion decay constants, $`f_t`$ and $`f_s`$, using pseudoscalar and axial vector correlation function. We have argued that the dimension 5 condensate, which is crucial for splitting between $`f_t`$ and $`f_s`$, is not necessarily restricted to be positive. In fact, the pion mass calculated from the $`f_t`$ sum rule takes a real value when the dimension 5 condensate is restricted to be negative. We have taken into account contributions from the $`N`$ and $`\mathrm{\Delta }`$ intermediate states in the correlation function. The $`N`$ intermediate state was found not to contribute to our sum rules. For the $`\mathrm{\Delta }`$ contribution, we have included either in the continuum or explicitly eliminated by putting an additional weight in the sum rules. The $`\mathrm{\Delta }`$ subtraction procedure was found to affect the extraction of $`f_t/f_\pi `$ slightly by $`39\%`$. For $`f_s/f_\pi `$, it affects strongly by $`2745\%`$. This strong suppression of $`f_s`$ is similar to the results from the in-medium chiral perturbation theory. In future, it will be interesting to apply our method for kaonic channel and investigate the in-medium $`f_K`$. As the strange quark mass is not small, the gluonic dimension 5 operator $`m_s𝒢^2`$, which is absent in this work, could be important.

###### Acknowledgements.

The work by Hungchong Kim was supported by the Korea Research Foundation Grant KRF-2002-015-CP0074.