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# PMN J0525-3343: soft X–ray spectral flattening in a blazar at z=4.4

## 1 Introduction

Active Galactic Nuclei (AGN) at high redshift are powerful tools with which to study the evolution of massive black holes and of their young galaxy hosts. A particularly interesting class is formed by several high redshift ($`z>4`$), X-ray bright, radio–loud quasars (Fabian et al 1997, 1998; Moran & Helfand 1997; Zickgraf et al 1997; Hook & McMahon 1998) which present characteristics typical of blazars. One such source, GB 1428+4217, is variable in both the X-ray and radio bands and has a spectral energy distribution which peaks at hard X-ray energies (Fabian et al 1998). Recently this object (Boller et al 2000) and RXJ1028.6-0844 (Yuan et al 2000) have been found to show spectral flattening which is interpreted as due to X-ray absorption, implying an absorbing column density of $`1.5\times 10^{22}`$cm-2and $`2.1\times 10^{23}`$cm-2, respectively, if intrinsic. We report here on the discovery and study of a similar object, PMN J0525-3443 at $`z=4.4`$, which shows similar spectral flattening.

Fiore et al (1998) have earlier found from ROSAT data an apparent systematic decrease with redshift of the spectral slope of the soft X–ray emission of radio-loud quasars from local to $`z3.9`$ objects. The change in spectra with redshift might be associated with an increase with redshift in the amount of absorbing (intrinsic or external) gas. Cappi et al (1997) find evidence for absorption using ASCA data for a small sample of high-redshift ($`1.2<z<3.4`$) radio-loud quasars. Confirmation of a systematic spectral flattening has been also reported by Reeves & Turner (2000) for a significant number of radio–loud sources observed by ASCA up to $`z`$=4.2. Understanding the nature and evolution of this spectral change will be of great importance for our knowledge of gaseous environments of powerful quasars, their intrinsic properties as well as their cosmological evolution and the radio–loud quasar/galaxy connection.

The object under study here, PMN J0525-3343, was identified by McMahon and Hook as part of their program to identify high redshift radio–loud quasars (Hook & McMahon 1998). The quasar was selected as a flat spectrum (i.e. $`\alpha <`$ 0.5; $`F_\nu \nu ^\alpha `$) radio source using the 4850 MHz Parkes-MIT-NRAO (PMN) survey (Wright et al 1996) and 1.4 GHz NRAO VLA Sky Survey (NVSS, Condon et al 1998). The 5.0GHz and 20cm fluxes are 210$`\pm `$18 and 188.7$`\pm `$5.7 mJy, respectively, giving a spectral index $`\alpha _{1.495.0GHz}=0.1`$. The radio sources were matched against the APM UKST catalogue using the NVSS radio position and it was identified as a red stellar object with R=18.5 and colour B–R=2.80. Subsequent optical spectroscopy identified the radio source as a quasar with z=4.4. It was confirmed to be an X–ray source with the ROSAT HRI and we have since observed it with ASCA and $`Beppo`$SAX. We present here X-ray fluxes and spectra, together with measurements of its radio and optical spectra. PMN J0525-3443 is the second most distant object in the X–ray bright, radio–loud class of quasars.

The optical, radio and X–ray data analysis procedure and results are reported in Sections 2, 3 and 4, respectively, while discussion and conclusions are presented in Sections 5 and 6. $`H_0`$=50 km s-1 Mpc-1 and $`q_0`$=0.5 have been used throughout the paper.

## 2 Identification and Optical data

An X–ray image of the quasar was obtained with the ROSAT HRI on 1998 March 4–6 for 8222 s. Contours of X-ray emission are overlaid on the POSS optical image in Fig. 1, demonstrating that the X–ray identification is secure (the approximately 4 arcsec offset is within the ROSAT positional uncertainties).

An optical spectrum covering the spectral range 4000-9000Å was obtained on 1998 October 15 with the R-C spectrograph on the CTIO 4m telescope. It is shown in Fig. 2 (reproduced from Peroux et al 2000, in prep). The spectrum is characterized by emission lines at $``$6600Å from the Lyman-$`\alpha `$(1216Å)+NV(1240Å) blend and CIV(1549) at $``$8300Å. The Lyman-$`\alpha `$ line has a peak at 6587$`\pm `$10Å corresponding to a redshift of 4.418. The observed equivalent width of the Ly-$`\alpha `$/NV blend is 191Å (EW(rest)=35Å). This is relatively small compared with radio–quiet $`z>`$4 quasars, but similar to that of the other strongly X-ray emitting radio–loud quasars (see Figure 4 in Hook & McMahon 1998). The peak of the CIV emission line is at 8340$`\pm `$10Å corresponding to a redshift of 4.384. The observed and rest frame equivalent widths are 131Å and 30Å, respectively. The CIV line is asymmetric with a strong CIV absorption doublet (observed EW=13.5Å) at $`z=4.4325\pm `$0.0005 i.e. redshifted with respect to the peak of the CIV emission line by 2700 km s-1. This absorption system also displays absorption from SiIV(1394,1403) and NV and Lyman-$`\alpha `$ where the observed EW of Lyman-$`\alpha `$ is 7.9 (rest=1.45) Å.

There is no evidence for an optically thick Lyman-limit system at the redshift of the quasar and we set a conservative upper limit of the $`N(HI)`$ column density at $`<3\times 10^{17}`$ cm-2 i.e. $`\tau `$$`<`$1. To be consistent with the above Lyman-$`\alpha `$ absorption line strength and the constraint on $`N(HI)`$, the doppler parameter $`b>`$40 km s-1.

The emission line redshift difference of 1800 km s-1 is smaller than the CIV line width (FWHM) of 11,500 km s-1 and is within the range observed in other $`z>`$4 quasars (1100$`\pm `$1790 km s-1; Storrie-Lombardi et al 1996) and in lower redshift quasars (Tytler & Fan 1992). We take the redshift of the quasar to be the mean of these two lines at $`z=4.401\pm `$0.006. CIV absorption within $`\pm `$5000 km s-1 of the CIV emission line redshift is quite common in radio–loud quasars, though its origin is debatable (Anderson et al 1987).

The continuum flux at a rest frame wavelength of 1450Å is 5.8$`\times `$ 10-17 erg s-1 cm-2 Å-1, while the spectral index is difficult to measure due to the presence of broad weaker emission lines that lie between NV and CIV.

## 3 Radio data

PMN J0525-3343 was observed for two hours on 1998 December 30 with the Very Large Array in the C (3 km) configuration, and for 2 hr on 1999 February 26 in the D (1 km) configuration. The radio source was observed at 8.4 GHz, 22 GHz, and 43 GHz. The spatial resolutions for the 3 km array observations were: $`7.9^{\prime \prime }`$x$`2.4^{\prime \prime }`$, $`2.5^{\prime \prime }`$x$`0.86^{\prime \prime }`$, and $`1.2^{\prime \prime }`$x$`0.4^{\prime \prime }`$, respectively (FWHM of major and minor axes of the Gaussian restoring beam, with major axis position angle oriented north-south at all frequencies). The absolute flux scale was set by observing 3C 286. The radio source position was found to be: 05 25 06.18$`\pm `$0.16, -33 43 05.55 $`\pm `$ $`0.05^{\prime \prime }`$ (J2000). Its flux density on 1998 December 30 was 41.0 $`\pm `$ 0.8 mJy at 8 GHz, 12.1 $`\pm `$ 0.5 mJy at 22 GHz, and 5.5 $`\pm `$ 0.6 mJy at 43 GHz. On 1999 February 26 it was 39.9 $`\pm `$ 0.8 at 8 GHz, 11.1 $`\pm `$ 0.7 at 22 GHz, and 6.5 $`\pm `$ 0.9 at 43 GHz. Thus no significant variability has been detected on a time scale of two months, with limits of $``$ 3 per cent at 8 GHz, 7 per cent at 22 GHz, and 18 per cent at 43 GHz. The source appeared spatially unresolved at all frequencies. The 43 GHz image constrains the size to be less than 0.4′′ in the east-west direction, and less than about 1′′ in the north-south direction.

The spectral index over the observed frequency range of 8 to 43 GHz is $`\alpha _r`$=1.2. The steep spectral index for this blazar may be due to the high rest frame frequency range of 44 GHz to 240 GHz. Steep spectrum cores at observed frequencies $``$ 8 GHz have been seen in many $`z>`$ 2 radio–loud quasars and radio galaxies (Lonsdale, Barthel & Miley 1993, Carilli et al 1997). Lonsdale et al (1993) present models in which the dominant component in the core-jet may not be synchrotron self-absorbed at these high frequencies, thereby setting a lower limit of about 1 mas to the typical size of the dominant core radio component.

Our present observations do not constrain the sub-arcsec radio structure of the object; very long baseline interferometry is in progress.

## 4 X–ray data

The ROSAT HRI count rate of the source on 1998 March 4–6 was $`0.012\pm 0.001`$ ct s-1. PMN J0525-3343 was next observed with ASCA on 1999 March 1-2. The data reduction was done using FTOOLS version 4.2 and the standard calibration provided by the ASCA Guest Observer Facility (ASCA GOF) at NASA/Goddard Space Flight Center. Good exposure times for each detector pair are 34 ks for the SIS and 31 ks for the GIS.

We consider the 0.8–10 keV data from both the SIS and GIS detectors, taking into account the possible systematic error discussed below. Although a significant deficiency in the SIS detector response curve below 1 keV has been reported for observations carried out after 1994 (ASCA GOF 1999), which could lead to an overestimate in measured absorption column densities, this effect should not be relevant here since the statistical error dominates over the systematic one in this faint X-ray source. In the energy range we use, the SIS and GIS data are indeed in good agreement and therefore an X-ray deficit in the low energy band, as reported below, is not an artifact of the calibration uncertainty. The SIS data in the 0.6–0.8 keV band are consistent with the trend found from the higher energy data. The result is also confirmed by the $`Beppo`$SAX/LECS data.

A fit with a simple power-law modified only by the Galactic absorption (a column density of $`2.2\times 10^{20}`$ cm-2; Elvis, Lockman & Fassnacht 1994) yields a photon index ($`\mathrm{\Gamma }=\alpha +1`$) of $`\mathrm{\Gamma }=1.38\pm 0.06`$ with $`\chi ^2=201.0`$ for 210 degrees of freedom (uncertainties on all spectral parameters are quoted at the 90 per cent confidence level). This fit is statistically acceptable, but leaves systematic, curved residuals across the fitted energy range. This spectral feature can be accounted for by introducing a flattening in the low energy part of the spectrum either due to excess absorption – local or intrinsic – or to an intrinsic change in the (power–law) slope. The inclusion of the low energy spectral flattening improves the quality of the fit by about 10 in $`\chi ^2`$ for both models (see Table 1; these improvements are significant at the 99.9 and 99 per cent confidence levels for the absorption and broken power-law models, respectively). We assume neutral absorption and solar abundances (solar or higher nuclear abundances appear to be present even at such high $`z`$, eg Shields & Hamann 1997).

$`Beppo`$SAX observed the source on 2000 February 27-28, with the three main detectors of the Narrow Field Instrument package. The exposure times for each detector are 24 ks, 60 ks and 29 ks for the LECS, MECS and PDS, respectively. The background subtracted PDS count rate is $`0.054\pm 0.024`$ cts s-1, which is just above the systematic error of the instrument ($`0.03`$ cts s-1, Guainazzi & Matteuzzi 1997). We therefore consider the PDS detection as not significant. The extrapolation of the best-fit model obtained from the LECS and MECS data is consistent with the PDS result (marginally significant detection would be achieved at the ASCA flux level). Spectral flattening is evident at low energies; $`\chi ^2`$ drops by 2 for intrinsic absorption and 7 for a broken power law.

As the fit to the $`Beppo`$SAX data is consistent with the ASCA one (no indication of spectral changes between the two observations can be found) we performed a joint fit of the two datasets, leaving the relative normalization free. The flattening is convincingly seen from both instruments (see Fig. 3) and both the (intrinsically) absorbed power-law model and the broken power–law give statistically good fits to the combined data (see Fig. 4, Table 1).

The observed flux is $`F(210\mathrm{keV})=1.2\times 10^{12}`$ erg cm-1 s-1 (ASCA). No statistically significant variations were found within the individual observations – weak variability is only hinted at in the second half of the ASCA observation, with an amplitude not exceeding 30 per cent (see Fig. 5). However the flux change between the ASCA and $`Beppo`$SAX datasets corresponds to a variation of 60 per cent over $``$ 2 months in the source frame, i.e. the flux ratio ASCA/$`Beppo`$SAX is 1.6$`\pm `$0.2. Note that the agreement in flux calibration between $`Beppo`$SAX (MECS) and ASCA is better than 3 per cent, according to the results of the (quasi-) simultaneous observations of 3C273 (see Yaqoob & ASCA Team 2000). Although this intercalibration might depend on the spectral shape of a source, the spectra of 3C273 and PMN J0525-3343 are similarly hard and thus we expect that the agreement should be at the same level. Therefore systematic errors between the two instruments are much smaller than the statistical one.

Only marginal variability has been instead found between the ASCA and $`Beppo`$SAX observations and the ROSAT HRI one: the HRI count rate in the 0.1–2.4 keV band corresponds to a flux of $`4.20\times 10^{13}`$ erg cm-2 s-1, assuming Galactic absorption and the ASCA/$`Beppo`$SAX photon index of $`\mathrm{\Gamma }=0.9`$, to be compared to $`5.2(3.3)\times 10^{13}`$ erg cm-2 s-1 for the ASCA ($`Beppo`$SAX) observations, respectively.

The integrated hard X–ray luminosity, not corrected for absorption, is $`L(210\mathrm{keV},\mathrm{ASCA})=5.0\times 10^{46}`$ erg s-1 (rest frame range $``$ 11 – 54 keV).

Finally, we note that the observed X–ray variability, which sets limits on the emitting region size $`<3\times 10^{17}\delta _1`$ cm, $`\delta _1=\delta /10`$ being the Doppler factor, and the broad band spectral indices (i.e, $`\alpha _{ro}=0.81,\alpha _{rx}=1.03,\alpha _{ox}=1.22`$, where the optical radiation is assumed unbeamed) suggest that the emission properties of PMN J0525-3433 resemble those of blazars (see also Fabian et al 1999).

## 5 Discussion

PMN J0525-3433 (here), GB 1428+4217 (Boller et al 2000) and RXJ 1028.6-0844 (Yuan et al 2000) are the most distant objects for which it has been possible to determine X-ray spectral features, i.e. a flattening of the lower energy X–ray spectrum. Intriguingly, the inferred soft energy (observer frame) spectral slope of PMN J0525-3433 follows the trend found by Fiore et al (1998) and Reeves & Turner (2000) for sources up to $`z`$ 4.2. As it is not yet clear whether this is due to external or intrinsic absorption, or to the shape of the emitting particle or soft photon spectra we will discuss all possibilities in turn.

### 5.1 Absorption

The first issue concerns whether absorbing material is located along the line of sight or is intrinsically associated with the system. The hypothesis in which the spectral flattening is due to changes in the source, either evolutionary or cosmological changes, is favoured by the fact i) that the flattening seems to be associated mostly with higher redshift radio–loud quasars (although the data are sparse, the only two $`z>1`$ radio-quiet quasars showing a flattening in the Reeves & Turner sample seem to be atypical sources); ii) that as well as PMN J0525-3433 the other three $`z>4`$ quasars show this feature: it therefore appears unlikely that an (unusually thick) absorber is located along the lines of sight to all of them.

It is therefore interesting to explore viable origins of the putative intrinsic absorbing gas. Note that the results on PMN J0525-3343 seem to definitely exclude that the trend in flattening is due to a shift of a soft X–ray excess component out of the observational band in the higher redshift objects: since the soft X-ray spectrum is flatter than, and not similar to, the hard X–ray one. 111Note also that the ROSAT PSPC (data used by Fiore et al) would not have enabled a flattening in PMN J0525-3343 (and thus in all lower redshift objects) to be seen, as the break energy would have been close to the upper extreme of its spectral coverage.

It is possible that the gas occupies a large scale, although this requires high values of the mass of the absorber. It might, for example, be associated with a galactic outflow, perhaps following the formation and initial activity of the central black hole, which expels gas from the host–galaxy (Silk & Rees 1998, Fabian 1999), with inferred mass outflows of the order of $`\dot{M}`$ few$`\times 10^3M_{}`$ yr-1.

On the other hand, Elvis et al (1998) have pointed out that in the ‘flattening’ sources the presence of absorbing line systems at high velocities (up to 10,000 km s-1) and/or reddening, are unusually common. Thus a nuclear origin is favoured, at least for the highest line velocity systems.

#### 5.1.1 X-ray vs optical-UV absorption

We stress however that serious problems arise, independently of the location or nature of the absorbing material. The column densities inferred from the X–ray spectrum imply, for a standard gas-to-dust ratio and composition, an extinction in the optical–UV band far in excess of that allowed from the detected optical fluxes. The UV reddening constraints indicate that the column density in neutral hydrogen is less than $`3\times 10^{17}`$cm-2 to the nucleus whereas the X-ray spectrum requires a column corresponding to $`2\times 10^{23}`$cm-2(equivalent to $`A_V100`$).

High metal enrichment or the presence of large dust grains (presumably not yet fragmented at high redshift) are possibilities which can account for the qualitatively similar discrepancy between the inferred $`N_H`$ and $`A_V`$ in both local radio–quiet sources (e.g. Salvati & Maiolino 2000) and in radio–galaxies (e.g. Cen A). Nevertheless, such possibilities do not seem sufficient to account for the large discrepancy found in PMN J0525-3343.

A possibility is that the optical photons are scattered along the line of sight. Strong (if unbeamed) emission and a high covering factor for the scattering medium are required. Note that the optical component cannot be totally dominated by beamed emission, although the intrinsic EW of the lines appear rather low compared to those of unbeamed objects. Although possible for one object it would be very unlikely if this geometry applied to all three objects yet studied above $`z>4`$.

One alternative solution to the millionfold discrepancy is that the absorbing gas is highly ionized and dust destroyed, because of the nuclear source itself or high temperature, so that the absorber is, say, OVII (most absorption will be due to oxygen at the observed energies). The absorber therefore resembles a warm absorber such as is common in Seyfert galaxies (Reynolds 1997). Indeed, the presence of absorption features associated with CIV (and Lyman-$`\alpha `$ \+ NV), which are seen in almost all luminous quasars with X–ray absorption column densities comparable to that inferred from PMN J0525-3343 (e.g. Brandt, Laor & Wills 2000), supports this hypothesis. (The CIV and X-ray absorbers in low $`z`$ objects are not due to exactly the same material, but are clearly associated in some way.)

In order to verify the viability of the warm absorber hypothesis, we have performed X–ray spectral fits using the results from the photoionization code CLOUDY, allowing the column density and ionization parameter $`\xi =L/nR^2`$ to vary. $`L,n`$ and $`R`$ are the luminosity of the ionizing source, the density of the absorber and its distance from the source, respectively. The intrinsic spectral index of the ionizing radiation is fixed at the value $`\mathrm{\Gamma }=1.75`$ obtained from the fitting of the highest X-ray energy spectrum. The results are shown as confidence contours of $`\xi `$ vs $`N_H`$ in Fig. 6, and are well consistent with a moderate ionization parameter of $`\xi 10`$ and a high column $`N_H3\times 10^{23}`$ cm-2. The attenuation of the optical–UV spectrum obtained is consistent with observations, provided that $`\xi >10`$ (so that the HI photoelectric edge remains small; i.e. $`\tau <1`$).

### 5.2 Intrinsic spectral properties

An alternative view might invoke evolution with redshift of the spectral characteristics of either the emitting particle distribution and/or an external photon field. The most accepted scenario for blazar emission attributes the production of the high energy component to inverse Compton scattering of soft photons on relativistic electrons. For the powerful sources an intense quasi–isotropic radiation field, peaked at frequency $`\nu _{\mathrm{ext}}`$, is believed to be produced in the nuclear regions. This dominates over the synchrotron photon energy density emitted locally inside the jet, and provides the seed photons for scattering (Sikora, Begelman & Rees 1994). This scenario has been quite convincingly tested by fitting the spectral energy distributions of tens of local ($`z<2`$) blazars (e.g. Ghisellini et al 1998) and at least two at the largest redshifts: GB 1428+4217 at $`z=4.72`$ (Fabian et al 1998) and in Fig. 7 we show the specific modeling for PMN J0525-3343 (see the figure caption for the parameters involved in the fit). Note in particular that there is an apparent tendency for the high redshift sources to require more extreme values of the intensity of the external soft photon field compared with lower redshift objects, in turn leading to larger cooling through scattering on external photons.

Note that the spectral break observed here is significantly different from that already found in some blazars, where both convex and concave (e.g. Wolter et al 1998) X–ray spectra are observed. The former ones are interpreted as due to the contribution of both the steep synchrotron and flat inverse Compton emission, at lower and higher frequencies, respectively, while the latter ones are well reproduced as the tail of the synchrotron component: there however the higher energy part of the spectrum is extremely steep, at odds with the flat high energy component detected in PMN J0525-3343.

#### 5.2.1 A cutoff in the particle distribution

A flattening of the spectrum could indeed be expected if there is a low energy cutoff in the emitting particle distribution. In fact, within the above picture, a low energy cutoff in the relativistic particle distribution at $`\gamma _{\mathrm{min}}`$ would produce a flattening in the scattered spectrum below $`\gamma _{\mathrm{min}}^2\mathrm{\Gamma }^2\nu _{\mathrm{ext}}`$, where $`\mathrm{\Gamma }`$ is the bulk Lorentz factor. The flattest slope which could in principle be obtained corresponds to the energy distribution produced by the scattering of a single electron on an isotropic field, i.e. $`\alpha =1`$. Therefore the results on PMN J0525-3433 are fully consistent with such a hypothesis 222Note that also the findings on RXJ1028.6-0844 (Yuan et al 2000) are consistent with a flattening of the spectrum rather than excess absorption.. In particular if $`\nu _{\mathrm{ext}}10^{15}`$ Hz (rest frame), the break observed in the X–ray spectrum of this source would imply a cutoff in the particle distribution at a Lorentz factor $`\gamma _{\mathrm{min}}`$ a few.

The importance of such a finding would be two-fold. On one side $`\gamma _{\mathrm{min}}`$ constitutes a crucial parameter to determine the nature of the power and matter flowing in the jet, as it determines the total density of (relativistic) particles present in the flow (Celotti & Fabian 1993; Sikora & Madejski 2000). On the other side, a cutoff in the particle distribution implies, as the cooling timescales are extremely short, that an highly efficient re–acceleration process is operating at the same rate.

Problems arise also with this interpretation (see also Fiore et al 1998), as there is no evidence of intrinsic breaks in the X–ray spectra of nearby radio–loud quasars which would be well detectable if located at the corresponding intrinsic energy $``$ 8 keV. Indeed one might expect that in less powerful (nearby) objects, the density in the external radiation field would be lower and the cooling less dramatic and thus under these conditions the cooling break in the particle distribution would be located at even higher energies.

#### 5.2.2 Sharply peaked soft photon distribution

An alternative scenario occurs if the seed photon distribution is peaked, or at least rapidly decreases below $`\nu _{\mathrm{ext}}`$. If so, the distribution of the scattered photons (by the lowest energy electrons) would reproduce such a slope (e.g. Ghisellini 1996). As the scattering electrons are moving with Lorentz factor $`\mathrm{\Gamma }`$, in the observed frame the scattered radiation will appear boosted in frequency by a factor $`\mathrm{\Gamma }^2`$. Thus below $`\mathrm{\Gamma }^2\nu _{\mathrm{ext}}`$ a spectral decline will be observable. The sharpness of such a spectral break could be accounted for by the strong anisotropy of the scattered radiation (we see only photons within a small angle).

Clearly such a possibility is highly speculative given the lack of information on the nuclear soft photon field distribution. Note however, that if the electron distribution extends down to low energies, the location of the X-ray spectral break in PMN J0525-3343 would indicate the beaming Lorentz factor of the emitting plasma, which then must be $`40`$, if $`\nu _{\mathrm{ext}}10^{15}`$ Hz.

The main difficulty arising with scenarios attributing the flattening to intrinsic properties of the electron/soft seed photon distributions, is to convincingly account for the intriguing trend with $`z`$ of the soft X–ray spectrum of radio–loud objects which systematically flatten with redshift (Fiore et al 1998). An interesting possibility, within the external Compton scenario, is that by increasing the redshift (and luminosity) of the source, the ratio of external Compton (EC) to synchrotron self–Compton (SSC) increases. If so, in high power sources the EC strongly dominates the emission, and leads to the depression (extreme flattening of soft X–rays) in the spectrum, while in increasingly lower redshift (weaker) sources the SSC contributes to the soft-medium X–ray emissions, filling the spectral depression (e.g. Sikora et al 1994). Clearly such an increase in the external photon energy density could be associated both with the source power and with the nuclear conditions of quasars at higher $`z`$.

## 6 Conclusions

We have studied the X-ray spectral properties of the high redshift radio–loud quasar PMN J0525-3343, by means of ROSAT, ASCA and $`Beppo`$SAX observations. We have found that the spectrum flattens at the lowest energies, indicating either a spectral flattening or a significant absorption in excess of the Galactic one. This finding is consistent with and extends the range in redshift of the systematic trend of increasing flattening with increasing redshift found previously for radio–loud sources. Several possibilities have been discussed.

The most plausible hypotheses include either an intrinsic flattening of the soft X–ray spectrum, originating from the shape of the energy distribution of particles and/or seed photons involved in the production of the Compton component, or the presence of warm absorbing gas in the nuclear region. If this is similar to the absorber found in local (Seyfert) objects, its distance from the central source would be of order $`10^{16}`$ cm. Evidence for CIV absorption in the spectrum supports the warm absorber hypothesis. The equivalent width of the absorption and value of $`\alpha _{\mathrm{ox}}`$ for PMN J0525-3343 fall on the correlation of Brandt et al (2000; Figure 4). Indeed the objects neighbouring PMN J0525-3343 in that correlation are observed to have X-ray warm absorbers. The velocity difference between the CIV absorption and emission are unlikely, in an object at $`z=4.4,`$ to be due to an intervening galaxy in a massive cluster of galaxies, since such clusters would not have then formed. Possibly the absorption line redshift is that of the quasar nucleus, and the broad emission line profiles have been altered by further, unresolved, absorption into peaking at a lower redshift.

In the former case, the column-redshift dependence could be accounted for by the decreasing contribution of synchrotron self–Compton emission at the softest energies due to an increasingly intense external photon field. In the latter, one might envisage an increase in the amount of nuclear gas and/or of ionizing radiation with $`z`$. Interestingly, it has been suggested (e.g. Reeves & Turner 2000 and references therein) from the observed characteristics of the spectra of radio–quiet sources, that the key parameter regulating their spectral properties is the mass accretion rate in Eddington units: high luminosity sources would thus be characterized by an increasing ionization state of the reflecting disc and possibly of any nuclear absorber. A similar trend might be at the origin of the increasing photon density required by the above scenario in radio–loud objects.

Future observations with Chandra and XMM-Newton, and in the optical, will enable us to discriminate between the models for these sources.

Clearly, this issue needs more investigation, since it represents a potential means for understanding the conditions and evolution of the nuclear/galactic environment and the galaxy–quasar connection. In particular future X–ray observations with wide energy coverage and good spectral resolution as provided by a significant number of high redshift radio–loud objects, will allow us to a) establish the origin of the spectral flattening, determining the abundance and ionization state of any absorber and – if variability or clear features are detected – its spatial location and redshift/velocity and b) assess its evolutionary properties. Information from the optical–UV spectrum are also of prime importance, as the amount of (or limit on) the extinction can be directly compared to the X–ray one and any line absorption feature would determine the absorbing gas velocity, although photometry alone might not be sufficient to distinguish between the steep non–thermal continuum typical of blazars and a reddened quasar spectrum.

## Acknowledgments

The VLA is operated by the National Radio Astronomy Observatory, which is a facility of the National Science Foundation operated under cooperative agreement by Associated Universities, Inc. CLC would like to thank G. Taylor for useful discussions. The Royal Society (ACF), the Italian MURST (AC) and the NASA LTSA grant NAG 5-8107 (WNB) are acknowledged for financial support.


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# Constraints on the tensor mode from large scale structure observations

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# UWThPh-2000-45 November 2000 Elastic 𝜈𝑒⁻ scattering of solar neutrinos with electromagnetic moments

## Abstract

We consider the azimuthal asymmetry of the recoil electrons in elastic $`\nu e^{}`$ scattering of solar neutrinos, which can arise if neutrinos have electromagnetic moments and there is a large solar magnetic field. We show that using this effect it is not possible to distinguish between magnetic and electric dipole moments in the 1-Dirac and 2-Majorana neutrino cases and that averaging over neutrino energy is important and suppresses the azimuthal asymmetry in the 2-Majorana neutrino case.

111Talk given by T.S. at EuroConference on Frontiers in Particle Astrophysics and Cosmology, San Feliu de Guixols, Spain, 30 Sept. - 5 Oct. 2000

Neutrinos produced in the sun provide an interesting possibility to investigate neutrino properties. Beside the well-established neutrino oscillation search using solar neutrinos it is also well-known that they can be used to look for a magnetic moment (MM) or an electric dipole moment (EDM) of the neutrinos . If there exists a large magnetic field inside the sun the so-called Resonant Spin-Flavour Precession scenario provides an appealing sollution to the solar neutrino problem . Here we consider elastic scattering of solar neutrinos with MMs and EDMs off electrons. If the neutrinos acquire a transverse polarization because of the solar magnetic field there can be an azimuthal asymmetry in the recoil electron momentum . Such an effect could be observed in a $`\nu e^{}`$ scattering experiment sensitiv to low energy solar neutrinos with good angular resolution like the proposed experiment HELLAZ . Details of our considerations and further references can be found in Ref..

The electromagnetic Hamiltonian. To describe the interaction of Dirac neutrinos with a MM and an EDM with the electromagnetic field we use the Hamiltonian

$$_{\mathrm{em}}^D=\frac{1}{2}\overline{\nu }_R\lambda \sigma ^{\alpha \beta }\nu _LF_{\alpha \beta }+\mathrm{h}.\mathrm{c}.$$
(1)
Here $`\nu _{L(R)}^T=(\nu _e,\nu _\mu ,\nu _\tau ,\nu _s,\mathrm{})_{L(R)}`$ is the vector of the left-handed (right-handed) flavour eigenfields including an arbitrary number of sterile neutrinos. The hermitian matrices $`\mu `$ of MMs and $`d`$ of EDMs are condensed in the non-hermitian matrix

$$\lambda =\mu id\text{with}\mu =\frac{\lambda +\lambda ^{}}{2},d=\frac{i(\lambda \lambda ^{})}{2}.$$
(2)
If the basis of the neutrino fields is changed by unitary rotations $`\nu _L=S_L\nu _L^{}`$ and $`\nu _R=S_R\nu _R^{}`$ the matrix (2) in the new basis is obtained by the simple relation $`\lambda ^{}=S_R^{}\lambda S_L`$, whereas $`\mu `$ and $`d`$ obey rather complicated transformation laws .

Similarly, for Majorana neutrinos we have the Hamiltonian

$$_{\mathrm{em}}^M=\frac{1}{4}\nu _L^TC^1\lambda \sigma ^{\alpha \beta }\nu _LF_{\alpha \beta }+\mathrm{h}.\mathrm{c}.,$$
(3)
where $`C`$ is the charge conjugation matrix. Now the matrix $`\lambda `$, defined as in Eq.(2), is antisymmetric and the MM and EDM matrices are antisymmetric and hermitian.

The cross section. In addition to the electromagnetic interaction there is also the weak interaction of neutrinos with electrons, which is described by the Hamiltonian

$$_\mathrm{w}=\frac{G_F}{\sqrt{2}}\underset{\alpha }{}\overline{\nu }_\alpha \gamma _\lambda (1\gamma _5)\nu _\alpha \overline{e}\gamma ^\lambda (g_V^\alpha g_A^\alpha \gamma _5)e,$$
(4)
where $`G_F`$ is the Fermi constant and $`g_V^\alpha =2\mathrm{sin}^2\mathrm{\Theta }_W+d^\alpha ,g_A^\alpha =d^\alpha ,g_{V,A}^s=0`$, with the weak mixing angle $`\mathrm{\Theta }_W`$ and $`d^e=1/2,d^{\mu ,\tau }=1/2`$.

In the general case of an arbitrary neutrino polarization the cross section for elastic $`\nu e^{}`$ scattering consists of three terms

$$\frac{d^2\sigma }{dTd\varphi }=\frac{d^2\sigma _\mathrm{w}}{dTd\varphi }+\frac{d^2\sigma _{\mathrm{em}}}{dTd\varphi }+\frac{d^2\sigma _{\mathrm{int}}}{dTd\varphi },$$
(5)
where $`\varphi `$ is the azimuthal angle which is measured in the plane orthogonal to the momentum of the initial neutrino and $`T`$ is the recoil energy of the scattered electron. The first and the second term are the pure weak and electromagnetic terms, respectively, and the third term is the interference term between the weak and the electromagnetic amplitude which is proportional to the transverse neutrino polarization and gives rise to the azimuthal asymmetry.

For the initial neutrino state in (5) we use an arbitrary superposition of flavour and helicity states:

$$|\nu _{\mathrm{in}}=\underset{\alpha =e,\mu ,\tau ,s,\mathrm{}}{}\left(a_{}^\alpha |\nu _\alpha ^{()}+a_+^\alpha |\nu _\alpha ^{(+)}\right).$$
(6)
In the massless limit the negative helicity states are left-handed neutrinos whereas the positive helicity states are sterile right-handed neutrinos in the Dirac case and right-handed antineutrinos in the Majorana case.

The weak cross section for Majorana neutrinos is given by

$$\frac{d^2\sigma _\mathrm{w}^M}{dTd\varphi }=\underset{\alpha }{}\left(|a_{}^\alpha |^2\frac{d^2\sigma _{\nu _\alpha e}}{dTd\varphi }+|a_+^\alpha |^2\frac{d^2\sigma _{\overline{\nu }_\alpha e}}{dTd\varphi }\right),$$
(7)
where $`\sigma _{\nu _\alpha e(\overline{\nu }_\alpha e)}`$ is the cross section for elastic scattering of neutrinos (antineutrinos) of flavour $`\alpha `$ off electrons given e.g. in . For Dirac neutrinos the second term in Eq.(7) is absent.

The electromagnetic cross section has the same form for Dirac and Majorana neutrinos:

$$\frac{d^2\sigma _{\mathrm{em}}}{dTd\varphi }=c\left(\frac{1}{T}\frac{1}{\omega }\right)\left(a_{}^{}\lambda ^{}\lambda a_{}+a_+^{}\lambda \lambda ^{}a_+\right),$$
(8)
where $`c=\alpha ^2/2m_e^2\mu _B^2`$, $`\omega `$ denotes the neutrino energy and $`a_{}^T=(a_{}^e,a_{}^\mu ,\mathrm{})`$.

The interference cross section is given by

$$\frac{d^2\sigma _{\mathrm{int}}}{dTd\varphi }=f\text{Re}\left[a_+^{}(\lambda g+\overline{g}\lambda )a_{}(p_x^{}ip_y^{})\right].$$
(9)
Here we have defined $`f=G_F\alpha /2\sqrt{2}\pi m_eT\mu _B`$ and $`g=\text{diag}\left[g_V^\alpha (2T/\omega )+g_A^\alpha T/\omega \right]`$. For Majorana neutrinos $`\overline{g}=\text{diag}\left[g_V^\alpha (2T/\omega )g_A^\alpha T/\omega \right]`$ whereas $`\overline{g}=0`$ in the Dirac case. For the direction of the initial neutrino we choose the $`z`$-axis and the transversal components of the recoil electron momentum are related to the azimuthal angle via $`p_x^{}=p_{}^{}\mathrm{cos}\varphi ,p_y^{}=p_{}^{}\mathrm{sin}\varphi `$ with $`p_{}^{}{}_{}{}^{2}=p_{x}^{}{}_{}{}^{2}+p_{y}^{}{}_{}{}^{2}`$. Therefore we find from Eq.(9)

$$\frac{d^2\sigma _{\mathrm{int}}}{dTd\varphi }\mathrm{cos}(\varphi \gamma ).$$
(10)
The measurement of the azimuthal asymmetry in an experiment would allow to determine the angle $`\gamma `$ which is defined as $`\gamma \text{Arg}[a_+^{}(\lambda g+\overline{g}\lambda )a_{}]`$.

In the following we will consider the question: Is it possible to obtain information on complex phases in the electromagnetic moment matrix $`\lambda `$ or in the neutrino mixing matrix via a measurement of $`\gamma `$?

Neutrino evolution in the sun. The evolution of the neutrino state produced in the core of the sun under the influence of the solar magnetic field and matter effects is governed by the Schrödinger-like equation

$`i{\displaystyle \frac{d}{dz}}\left(\begin{array}{c}\phi _{}\\ \phi _+\end{array}\right)=H_{\mathrm{eff}}\left(\begin{array}{c}\phi _{}\\ \phi _+\end{array}\right)\text{with}`$ (15)
$`H_{\mathrm{eff}}\left(\begin{array}{cc}V_L+U_L\frac{\widehat{m}^2}{2\omega }U_L^{}& B_+\lambda ^{}\\ B_{}\lambda & V_R+U_R\frac{\widehat{m}^2}{2\omega }U_R^{}\end{array}\right).`$ (18)
In this equation, $`\phi _{}`$ and $`\phi _+`$ denote the vectors of neutrino flavour wave functions corresponding to negative and positive helicity, respectively. $`V_L=\sqrt{2}G_F\text{diag}(n_en_n/2,n_n/2,n_n/2,0,\mathrm{})`$ is the matter potential where $`n_e(n_n)`$ is the electron (neutron) density in the sun and $`V_R=0(V_L)`$ for Dirac (Majorana) neutrinos. The diagonal matrix of neutrino masses is denoted by $`\widehat{m}`$ and $`U_L`$ is the unitary mixing matrix connecting left-handed flavour and mass eigenfields. $`U_R`$ is an arbitrary unitary matrix for Dirac neutrinos and $`U_R=U_L^{}`$ in the Majorana case. Finally, $`B_\pm =B_x\pm iB_y`$ where $`B_x`$ and $`B_y`$ are the components of the solar magnetic field orthogonal to the neutrino momentum.

Neutrinos are produced as electron neutrinos in the sun at the coordinate $`z_0`$ and are detected on earth at $`z_1`$. Hence we express the initial condition as $`\phi _{}^T(z_0)=(1,0,\mathrm{}),\phi _+^T(z_0)=(0,\mathrm{})`$ and for the neutrino state at the detector, Eq.(6), we have $`a_{}\phi _{}(z_1)`$. For a given magnetic field along the neutrino path in the sun, the neutrino state described by the vectors $`a_{}`$ can in principle be obtained by solving Eq.(15), as a function of neutrino MMs, EDMs, masses and mixing parameters. These flavour vectors $`a_{}`$ have to be used in the cross section for elastic $`\nu e^{}`$ scattering of solar neutrinos.

Phase counting. Let us first consider a single Dirac neutrino. In this simplest case there is only one complex phase in the problem, which is the phase $`\delta `$ defined through $`\mu +id=\sqrt{\mu ^2+d^2}e^{i\delta }`$ where $`\mu `$ and $`d`$ are real numbers in this case. Now, the evolution Eq.(15) leads to $`a_+^{}=e^{i\delta }a_+`$ such that $`a_{}`$ and $`a_+^{}`$ as well as the angle $`\gamma `$ in the interference cross section (10) depend only on $`\sqrt{\mu ^2+d^2}`$. Hence, the phase $`\delta `$ disappears from the problem. This means that it is not possible to distinguish between a Dirac MM and EDM via a measurement of $`\gamma `$. A nonzero $`d`$ leads to CP violation at the level of the Lagrangian. However, the above consideration implies that no CP violating effects can be observed in elastic $`\nu e^{}`$ scattering of solar neutrinos.

In the second simple case of two Majorana neutrinos there are two phases in the problem: one in the transition moment $`\mu id`$ in the matrix $`\lambda `$ ($`\mu `$ and $`d`$ imaginary) and one phase in the mixing matrix (Majorana phase). One can show with arguments similar to the one Dirac case that both phases can be absorbed through redefinitions. Again it is not possible to distinguish between a MM and an EDM and no CP violating effects show up.

Now we come to the general case of $`n`$ neutrino flavours. In the first two lines of Table 1 we give the numbers of complex phases in the mixing matrix and in $`\lambda `$ at the level of the Lagrangian, in a phase convention where as much phases as possible are removed from the mixing matrix. However, not all of these phases show up in elastic $`\nu e^{}`$ scattering of solar neutrinos because of the relevant physical approximations: neutrino masses enter in the evolution equation (15) only via the terms $`U_L\widehat{m}^2U_L^{},U_R\widehat{m}^2U_R^{}`$ and are neglected in the cross section. Therefore, in the physical situation under consideration there is more phase freedom which can be used to reduce the number of phases in the problem. Moreover, complex phases can be shifted from the mixing matrix to $`\lambda `$ and vice versa . In the last line of Table 1 we show the total number of physical phases relevant for the azimuthal asymmetry in elastic $`\nu e^{}`$ scattering of solar neutrinos.

Decoherence effects. Here we consider the effect of neutrino oscillations and averaging over the neutrino energy on the solar neutrino state arriving at the earth.

The neutrino state undergoes vacuum oscillations between the sun and the earth. Therefore, denoting the values of $`\phi _{}`$ (15) at the edge of the sun by $`b_{}`$, we have $`a_{}=U_L\mathrm{exp}\left(i\widehat{m}^2L/2\omega \right)U_L^{}b_{}`$ and $`a_+=U_R\mathrm{exp}\left(i\widehat{m}^2L/2\omega \right)U_R^{}b_+`$. Here $`L1.5\times 10^{11}`$ m is the distance between the sun and the earth. Now the crucial point is that, according to the quadratic appearance of $`a_{}`$ in the cross section, the phase factors $`e^{\pm i\phi _{jk}}`$ are important with $`\phi _{jk}=2\pi L/\mathrm{}_{jk}`$ where $`\mathrm{}_{jk}=4\pi \omega /\mathrm{\Delta }m_{jk}^2`$ is an oscillation length with $`\mathrm{\Delta }m_{jk}^2=m_j^2m_k^2>0`$. The phases vary with energy as

$$\delta \phi _{jk}=\frac{\mathrm{\Delta }m_{jk}^2L}{2\omega }\frac{\delta \omega }{\omega }=2\pi \frac{L}{\mathrm{}_{jk}}\frac{\delta \omega }{\omega }.$$
(19)
Hence, integration over energy intervals such $`\delta \omega \omega \mathrm{}_{jk}/L`$ $`j,k`$ leads to an averaging of the oscillations, which can formally be expressed as $`e^{\pm i\phi _{jk}}=\delta _{jk}`$, where $`\delta _{jk}`$ is the Kronecker delta. Numerically, we have

$$\frac{\mathrm{}_{jk}}{L}1.7\times 10^{11}\frac{\omega (\text{MeV})}{\mathrm{\Delta }m_{jk}^2(\text{eV}^2)}.$$
(20)
If we consider, for example, $`\mathrm{\Delta }m^210^8`$ eV2 allowed by the RSFP scenario  and $`\omega 0.27`$ MeV, the average energy of the $`pp`$ neutrinos, we find $`\mathrm{}/L5\times 10^4`$, where $`\mathrm{}`$ is the oscillation length corresponding to $`\mathrm{\Delta }m^2`$. Therefore, to avoid the averaging one would have to measure the neutrino energy with an accuracy better than $`\delta \omega /\omega 10^4`$, which seems rather impossible. The energy averaging of the vacuum oscillations is equivalent to consider the neutrino state arriving at the earth as an incoherent mixture of mass eigenstates.

The expressions for the general energy averaged cross sections are given in Ref.. Here we want to discuss the effect of decoherence for the 2-Majorana neutrino case. For total incoherence the interference cross section is proportional to

$$\frac{d^2\sigma _{\mathrm{int}}^M}{dTd\varphi }f\frac{T}{\omega }\mathrm{sin}2\theta \mathrm{cos}(\varphi \gamma )$$
(21)
where $`f`$ is given after Eq.(9). Again all complex phases disappear, especially $`\gamma `$ does not depend on the phase of $`\mu id`$. There are two important implications of relation (21): (i) The dependence on the electron recoil energy of this expression is very different from the corresponding term in the case of full coherence and the Dirac terms with and without coherence, because the recoil energy $`T`$ drops out of the product $`fT`$. (This is also true for an arbitrary number of Majorana neutrinos.) (ii) Expression (21) is proportional to the mixing angle $`\mathrm{sin}2\theta `$. Large values for $`\mathrm{sin}2\theta `$ are disfavoured in the RSFP scenario  and by the non-observation of electron antineutrinos in Super-Kamiokande  and hence the asymmetry is suppressed.

These arguments suggest that a significant asymmetry measured in an experiment is unlikely to result from a 2-Majorana neutrino scenario, except for very small mass-squared differences ($`\mathrm{\Delta }m^2<10^{11}`$ eV2). Of course, it could result from Dirac diagonal moments. In this case the states of negative and positive helicity belong to the same mass eigenvalue and no averaging due to oscillations is possible.

Conclusions. We have considered the possibility to investigate neutrino properties using the azimuthal asymmetry in elastic $`\nu e^{}`$ scattering of solar neutrinos. We have shown that it is not possible to distinguish MMs and EDMs for 1-Dirac and 2-Majorana neutrinos and no CP violation will show up in these cases. For $`n`$ neutrino flavours there is a phase freedom because of the physically motivated approximations. This allows to eliminate complex phases in the mixing matrix and the MM/EDM matrix. Furthermore we have shown that energy averaging is important and leads to a suppression of the azimuthal asymmetry in the 2-Majorana case.


text:
# Self-organized stable pacemakers near the onset of birhythmicity

## Abstract

General amplitude equations for reaction-diffusion systems near to the soft onset of birhythmicity described by a supercritical pitchfork-Hopf bifurcation are derived. Using these equations and applying singular perturbation theory, we show that stable autonomous pacemakers represent a generic kind of spatiotemporal patterns in such systems. This is verified by numerical simulations, which also show the existence of breathing and swinging pacemaker solutions. The drift of self-organized pacemakers in media with spatial parameter gradients is analytically and numerically investigated.

Oscillatory reaction-diffusion systems, such as the Belousov-Zhabotinsky (BZ) chemical reaction, exhibit a rich variety of nonlinear wave patterns. The first complex pattern discovered in this reaction was the target pattern, where concentric waves were emitted by a pacemaker representing a periodic wave source . Subsequently, similar target structures have been observed in many other chemical, physical, and biological systems . A simple theoretical explanation of target patterns in oscillatory chemical systems is that their pacemakers are created by impurities which increase the local oscillation frequency in the medium . Most of the target patterns seen in the BZ reaction are indeed caused by small local inhomogeneities, such as dust particles. A general question is whether self-organized target patterns, representing an intrinsic dynamical property, are also possible in reaction-diffusion systems. Examples of stable autonomous pacemakers with localized or extended wave patterns are indeed known for several reaction-diffusion models .

The aim of the present Letter is to show that stable autonomous pacemakers with extended wave patterns represent a generic pattern-forming object in oscillatory reaction-diffusion systems near the onset of birhythmicity. Birhythmicity, the coexistence of two stable limit cycles corresponding to uniform oscillations with different frequencies, is possible in various systems , including glycolytic oscillations  and the photosensitive BZ reaction . Here, we derive two coupled amplitude equations yielding the normal form of such a dynamical system near a supercritical pitchfork-Hopf bifurcation which leads to birhythmicity. Using singular perturbation theory, an analytical solution for autonomous pacemakers is then constructed and its stability is numerically confirmed. In addition, target patterns with breathing or swinging pacemakers are observed. Finally, we show that autonomous pacemakers can drift under the influence of a parameter gradient and determine the drift velocity.

The derivation of normal forms for various kinds of reaction-diffusion systems has recently been discussed by one of the authors . Here, we focus our attention on systems near to a supercritical pitchfork-Hopf bifurcation, where a real uniform eigenmode and a pair of complex conjugate uniform eigenmodes start to grow simultaneously. This implies that either a stable small-amplitude limit cycle becomes unstable and gives rise to two stable limit cycles or a pair of stable and unstable limit cycles of small amplitude emerges near to a stable limit cycle. At least three species are needed to realize this bifurcation.

Using the approach described in , we have derived the normal form of this bifurcation for a general reaction-diffusion system . The normal form is given by

$`_tA`$ $`=A(1+\mathrm{i}\alpha )|A|^2A+(1+\mathrm{i}\beta )^2A+(1\mathrm{i}ϵ)Az,`$ (1a)
$`\tau _tz`$ $`=\sigma \gamma |A|^2+z\nu z^3+\lambda ^2^2z,`$ (1b)
The system (1) represents a complex Ginzburg-Landau equation (CGLE) for a supercritical Hopf bifurcation (1a) which is coupled to an equation describing an imperfect pitchfork bifurcation (1b). Here $`A`$ is the complex oscillation amplitude and $`z`$ is the amplitude of the slow real mode. The coefficients $`\tau `$ and $`\lambda `$, respectively, are the ratios of the characteristic time and length scales of the real and the oscillatory mode. The parameter $`ϵ`$ specifies the frequency shift of the oscillatory mode due to coupling to the real mode, $`\gamma `$ characterizes the strength of the feedback from the oscillatory to the real mode, and $`\nu `$ determines the nonlinear saturation of the real mode. When $`\sigma =0`$, Eq. (1b) describes a supercritical pitchfork bifurcation, whereas $`\sigma 0`$ corresponds to an imperfect pitchfork (or “cusp” ) bifurcation. Only positive parameters $`\gamma ,\nu `$, and $`\sigma `$ will be considered in this Letter. We assume that uniform oscillations are modulationally stable in this system, i.e. the Benjamin-Feir-Newell condition $`1+\alpha \beta >0`$ is satisfied, and that the waves have positive dispersion, i.e. $`\beta \alpha >0`$.

It can be seen that Eqs. (1) have solutions corresponding to two uniform stable limit-cycle oscillations with frequencies $`\mathrm{\Omega }_1`$ and $`\mathrm{\Omega }_3`$ and to an unstable limit cycle with frequency $`\mathrm{\Omega }_2`$. The frequencies are given by $`\mathrm{\Omega }_{1,2,3}=\alpha +\left(\alpha +ϵ\right)z_{1,2,3}`$ where $`z_{1,2,3}`$ are the real roots of the equation $`\nu z^3(1\gamma )z+\gamma =\sigma `$. When $`\alpha +ϵ<0`$ (which is the case that we chose in the simulations), the smallest root $`z_1`$ corresponds to the most rapid oscillations, i.e. $`\mathrm{\Omega }_3<\mathrm{\Omega }_2<\mathrm{\Omega }_1`$.

In addition to these uniform oscillations, the system described by Eqs. (1) may have stable nonuniform solutions representing self-organized pacemakers. To create a pacemaker, a sufficiently strong local perturbation should be applied to the state comprised of uniform oscillations with the lower frequency $`\mathrm{\Omega }_3`$, so that a small core region is formed where oscillations have a higher frequency. Inside this region, the variable $`z`$ is close to $`z_1`$, whereas outside, it is near to $`z_3`$. The core starts to send out waves and hence a pacemaker is created. The core expands ($`\gamma >\sigma `$ is a necessary condition for this, otherwise it will contract) and the frequency and the wavenumber of the emitted waves slowly increase at the same time. In turn, this leads to a decrease of the oscillation amplitude of emitted waves. This amplitude controls the propagation velocity of the front, representing the boundary of the expanding core. When a critical wavenumber is reached, the front velocity becomes zero and a stationary pacemaker is formed.

We have constructed an analytical solution for stationary pacemakers in the one-dimensional system (1). The phase $`\varphi `$ and amplitude $`\rho `$ are introduced by $`A=\rho \mathrm{exp}[\text{i}(\mathrm{\Omega }_3t+\varphi )]`$. Then $`\rho `$ is adiabatically eliminated using $`\rho ^21+z(\varphi )^2+\beta ^2\varphi `$. The phase equation approximation  is valid for smooth phase perturbations and $`\nu 1\gamma `$. Assuming that the characteristic length scale of the real mode, determining the front width, is much shorter than the characteristic length scale of the oscillatory subsystem (i.e. that $`\lambda 1`$), we apply singular perturbation theory to this problem. The derivation will be published separately  and only selected results are reported in this Letter.

The velocity of the front $`V`$ (of the expanding core) depends on the wavenumber $`k`$ and is given by

$$V(k)=3\frac{\lambda }{\tau }\sqrt{\frac{\nu }{2}}\stackrel{~}{z}_2(k),$$
(2)
where $`\stackrel{~}{z}_2(k)`$ is the middle root of the cubic equation $`\nu z^3\left(1\gamma +\gamma a\right)z+\gamma (1+az_3k^2)=\sigma `$, with $`a=\beta (\alpha +ϵ)/(1+\alpha \beta )`$. On the other hand, if the core radius $`R`$ is known, the wavenumber $`k`$ of emitted waves can be analytically found if the condition $`\lambda k1`$ is satisfied (cf. ). The inverted dependence $`R(k)`$ and the velocity $`V(k)`$ are displayed in Fig. 1(a).

For stationary pacemakers, the front velocity $`V`$ vanishes. This determines the wavenumber $`k_0`$ of a stationary pacemaker and thus allows us to find its core radius $`R_0`$. Analytical solutions for these key properties have been constructed. We find that

$`k_0`$ $`=`$ $`\sqrt{1\sigma /\gamma +az_3},`$ (3)
$`R_0`$ $`=`$ $`{\displaystyle \frac{1+\alpha \beta }{(\beta \alpha )\sqrt{k_{\mathrm{max}}^2k_0^2}}}\mathrm{tan}^1\left({\displaystyle \frac{k_0}{\sqrt{k_{\mathrm{max}}^2k_0^2}}}\right),`$ (4)
where $`k_{\mathrm{max}}^2=(\alpha +ϵ)(z_1z_3)/(\beta \alpha )`$. The frequency $`\mathrm{\Omega }_0`$ of a stationary pacemaker is $`\mathrm{\Omega }_0=\mathrm{\Omega }_3+(\beta \alpha )k_0^2`$. The wavenumber $`k_0`$ and the radius $`R_0`$ of a stationary pacemaker are shown as functions of the coupling coefficient $`\gamma `$ in Fig. 1(b).

Examining the constructed solutions, we note that generally $`\mathrm{\Omega }_3<\mathrm{\Omega }_0<\mathrm{\Omega }_1`$. The frequency $`\mathrm{\Omega }_0`$ of a stationary pacemaker approaches the frequency $`\mathrm{\Omega }_1`$ of rapid uniform oscillations, when the core radius $`R_0\mathrm{}`$ (and $`k_0k_{\mathrm{max}}`$). On the other hand, when the core is small, $`k_0`$ is small and the frequency $`\mathrm{\Omega }_0`$ is close to $`\mathrm{\Omega }_3`$. Stationary pacemakers exist inside an interval of the coupling intensity $`\gamma `$ \[see Fig. 1(b)\]. Our approximate analysis based on singular perturbation theory is only valid when the core is not too small, i.e. $`R_0\lambda `$.

Some conclusions about the stability of stationary pacemakers can already be drawn from Fig. 1(a). Suppose the radius $`R`$ has increased above the stationary radius $`R_0`$. This leads to an increase of the wavenumber $`k`$ of emitted waves which, in turn, will make the front velocity $`V`$ negative. Therefore the front will retreat, decreasing the radius $`R`$ back to its stationary value. This argument is, however, only applicable when the characteristic time scale of the core evolution is much longer than the time needed for the wave pattern to adjust to its changes, i.e. when $`\tau 1`$. Generally, the stability of stationary pacemakers should be numerically investigated.

The system described by Eqs. (1) was integrated with an explicit Euler scheme where the Laplacian operator was discretized with a nearest-neighbor approximation. No-flux boundary conditions were used. Figure 2(a) displays the evolution of a stationary pacemaker from a small initial perturbation of the real mode $`z`$. In the first stage, the core grows with approximately constant speed. Later, the growth is terminated and a stationary object is formed. Figure 2(b) displays the creation and emission of waves in the oscillatory subsystem. The profile of the asymptotic stable stationary pacemaker is shown in Fig. 2(c).

Pacemakers are stable for sufficiently large $`\tau `$. When $`\tau `$ is decreased, numerical integrations show that stationary pacemakers become unstable. Close to the instability boundary, stable breathing and swinging pacemakers were found \[Figs. 3(a)–3(b)\]. For a breathing pacemaker, the center remains stationary whereas the radius oscillates. For swinging pacemakers, the radius stays approximately constant while the position of the pacemaker oscillates. Further lowering of $`\tau `$ leads to the disappearance of any stable pacemaker solutions.

Similar to plane waves in the CGLE , the waves emitted by a pacemaker may become unstable when their wavenumber $`k_0`$ exceeds the Eckhaus wavenumber given by $`k_{\mathrm{EH}}\sqrt{(1+z_3)(1+\alpha \beta )(3+\alpha \beta +2\alpha ^2)^1}`$. Among other effects, this may lead to the destabilization of a stationary pacemaker, as illustrated by Figs. 3(c)–3(d). Phase singularities and thus oscillation amplitude defects are periodically generated at the core boundary, giving rise to a short-wavelength regime in the core and to a long-wavelength regime in the periphery. The core gradually grows and eventually the whole medium is occupied by rapid uniform oscillations.

In contrast to pacemakers which are created by local heterogeneities, autonomous pacemakers are not pinned and their location is determined only by the initial conditions. Moreover, such self-organized structures are able to move through the medium when spatial parameter gradients are present. Suppose, for example, that the parameter $`\gamma `$ varies with a constant gradient $`\kappa `$, i.e. $`\gamma (x)=\gamma _0+\kappa (xx_0)`$, where $`\gamma _0`$ is the value of $`\gamma `$ in the center of the pacemaker. For sufficiently small gradients ($`\kappa R_0\gamma _0`$), linear perturbation theory can be used. Its application (see ) allows us to determine analytically the drift velocity $`V_\mathrm{D}`$ as $`V_\mathrm{D}=\kappa R_0_\gamma V(\gamma _0,k_0)`$ where $`V(\gamma ,k)`$ is the front velocity given by Eq. (2).

The simulation displayed in Fig. 4(a) was initiated with a stable stationary pacemaker. After a constant gradient in the parameter $`\gamma `$ was introduced, the pacemaker drifted through the medium in the direction of increasing $`\gamma `$. When the gradient was removed, the drift of the pacemaker terminated and a spatially shifted stationary pacemaker was recovered. The emission and propagation of waves persisted during the drift \[Fig. 4(b)\]. In addition, the Doppler effect led to a small increase of $`k`$ in the direction of motion.

In this Letter, we have analytically constructed self-organized pacemaker solutions in the vicinity of a pitchfork-Hopf bifurcation. Our numerical investigations have shown that such self-organized patterns are stable for a wide range of parameters. To create autonomous pacemakers, a sufficiently strong local perturbation should be applied to the state corresponding to stable uniform oscillations. This is in contrast to , where autonomous target patterns were found near a Hopf bifurcation with a finite wavenumber and thus uniform oscillations of the medium were absolutely unstable. Our approach is also different from the model  that was constructed to explain target pattern formation in electrohydrodynamic convection and which is based on a Hopf bifurcation of a cellular spatial structure. On the other hand, Ohta et al.  have investigated a two-component activator-inhibitor model with coexistence of excitable kinetics and stable uniform oscillations, and reported several different kinds of autonomous wave sources. The subsequent numerical studies  have, however, shown that while localized target patterns are stable, target patterns which extend over the whole medium are unstable in the model and slowly evolve into uniform oscillations. Stable localized target patterns are also found in the quintic CGLE .

Since our analysis is based on general amplitude equations, the results presented here are valid for any reaction-diffusion system near a soft onset of birhythmicity with small-amplitude limit cycles. In a separate publication , this analysis will be applied to a particular chemical model system. As in the case of a Turing-Hopf bifurcation, the results of our analysis based on the amplitude equations may remain (qualitatively) applicable even at significant separation from the bifurcation point. Finally, we note that the physical mechanism responsible for the stabilization of pacemakers in the considered system involves a long-range negative feedback, similar to the one necessary for the formation of stable localized spots in reaction-diffusion models with fast inhibitor diffusion. Here, however, an infinite-range inhibition is caused not by diffusion, but by non-damped propagation of waves emitted from the core region. The effect of pacemaker drift in systems with spatial parameter gradients provides a convenient experimental method to identify self-organized pacemakers and distinguish them from other target patterns caused by local heterogeneities in the medium.

The authors thank T. Ohta for an interesting discussion and H. Engel for bringing Ref.  to our attention. Financial support of the Humboldt Foundation (Germany) is gratefully acknowledged.


text:
# Coherent control of enrichment and conversion of molecular spin isomers

## I Introduction

It is well known that many symmetrical molecules exist in Nature only in the form of nuclear spin isomers . Spin isomers are important for fundamental science and have various applications. They can serve as spin labels, influence chemical reactions , or tremendously enhance NMR signals . Progress in the spin isomers study depends heavily on available methods for isomer enrichment. Although this field has been significantly advanced recently (see the review in ), one needs more efficient enrichment methods.

Recently two enrichment methods based on optically induced change of molecular level populations have been proposed . The purpose of the present paper is to investigate the isomer enrichment caused by optically induced coherences in the molecule.

## II Quantum relaxation

Nuclear spin isomers of molecules were discovered in the late 1920s. The most known example is the isomers of H2. These isomers have different total spin of the two hydrogen nuclei, $`I=1`$ for ortho molecules and $`I=0`$ for para molecules. Symmetrical polyatomic molecules have nuclear spin isomers too. For example, CH3F can be in ortho, or in para state depending on the total spin of three hydrogen nuclei equal 3/2, or 1/2, respectively (see, e.g., ). Different spin isomers are often distinguished also by their rotational quantum numbers. Consequently, all rotational states of the molecule are separated into nondegenerate subspaces of different spin states. Schematically, these subspaces for the case of two spin states, ortho and para, are presented in Fig. 1. (For a moment, an optical excitation shown in the ortho space has to be omitted.)

Nuclear spin conversion can be produced by collisions with magnetic particles. This is a well-known mechanism for the conversion of hydrogen imbedded in paramagnetic oxygen . If a molecule is surrounded by nonmagnetic particles, collisions alone cannot change the molecular spin state. In this case the spin conversion is governed by quantum relaxation which can be qualitatively described as follows. Let us split the molecular Hamiltonian into two parts,

$$\widehat{H}=\widehat{H}_0+\mathrm{}\widehat{V},$$
(1)
where $`\widehat{H}_0`$ is the main term which has the ortho and para states as the eigen states (states in Fig. 1); $`\widehat{V}`$ is a small intramolecular perturbation able to mix the ortho and para states. Suppose that the test molecule was placed initially in the ortho subspace. Due to collisions the molecule starts undergo fast rotational relaxation inside the ortho subspace. This running up and down along the ortho ladder proceeds until the molecule reaches the ortho state $`m`$ which is mixed with the para state $`k`$ by the intramolecular perturbation $`\widehat{V}`$. Then, during the free flight just after this collision, the perturbation $`\widehat{V}`$ mixes the para state $`k`$ with the ortho state $`m`$. Consequently, the next collision can move the molecule to other para states and thus localize it inside the para subspace. Such mechanism of spin conversion was proposed in the theoretical paper  (see also ).

Relevance of the described mechanism to actual spin conversion in molecules is not at all obvious. The problem is that the intramolecular perturbations, $`\widehat{V}`$, able to mix ortho and para states are very weak. They have the order of $`10100`$ kHz (hyperfine interactions) which should be compared with other much stronger interactions in molecules, or with gas collisions. Nevertheless, the experimental and theoretical proves have been obtained that spin conversion in molecules is indeed governed by quantum relaxation . Although, only three molecules (CH3F, H2CO and C2H4) have been studied in this context so far, it is very probable that spin conversion in other polyatomic molecules of similar complexity is governed by quantum relaxation too. It is useful for the following to give a few examples of spin conversion rates. Most studied is the spin conversion in 13CH3F which has the rate,

$$\gamma _{13}/P=(12.2\pm 0.6)10^3\text{s}^1/\text{Torr},$$
(2)
in case of pure CH3F gas . Spin conversion in another isotope modification, 12CH3F, is by almost two orders of magnitude slower . Similar slow conversion was observed in ethylene, 13CCH4, ,

$$\gamma _{eth}/P=(5.2\pm 0.8)10^4\text{s}^1/\text{Torr}.$$
(3)
These data show that spin conversion by quantum relaxation is on $`911`$ orders of magnitude slower than the rotational relaxation, $`\nu 10^610^7`$ s-1/Torr.

## III Optical excitation

In this section we will analyze the spin conversion by quantum relaxation in the presence of a resonant electromagnetic radiation. The level scheme is shown in Fig. 1. In order to reveal the main features of the phenomenon we will consider the process in a simplest arrangement. First of all, we assume that molecular states are nondegenerate and that only one ortho-para level pair, $`mk`$, is mixed by the intramolecular perturbation, $`\widehat{V}`$. Monochromatic radiation is chosen to be in resonance with the rotational transition $`mn`$. In this arrangement the molecular Hamiltonian reads,

$$\widehat{H}=\widehat{H}_0+\mathrm{}\widehat{G}+\mathrm{}\widehat{V}.$$
(4)
New term, $`\widehat{G}`$, describes the molecular interaction with the radiation,

$$\widehat{G}=(𝐄_0\widehat{𝐝}/\mathrm{})\mathrm{cos}\omega _Lt,$$
(5)
where $`𝐄_0`$ and $`\omega _L`$ are the amplitude and frequency of the electromagnetic wave; $`\widehat{𝐝}`$ is the operator of the molecular electric dipole moment. We have neglected molecular motion in the operator $`\widehat{G}`$ because homogeneous linewidth of pure rotational transition is usually larger than the Doppler width.

Kinetic equation for the density matrix, $`\widehat{\rho }`$, in the representation of the eigen states of the operator $`\widehat{H}_0`$ has standard form,

$$d\widehat{\rho }/dt=\widehat{S}i[\widehat{G}+\widehat{V},\widehat{\rho }],$$
(6)
where $`\widehat{S}`$ is the collision integral.

Molecules in states ($`m,n,k`$) interacting with the perturbations $`\widehat{G}`$ and $`\widehat{V}`$ constitute only small fraction of the total concentration of the test molecules. Thus, one can neglect collisions between molecules in these states in comparison with collision with molecules in other states. The latter molecules remain almost at equilibrium. Consequently, the collision integral, $`\widehat{S}`$, depends linearly on the density matrix for the disturbed states $`m`$, $`n`$, and $`k`$ even in one component gas. Further, we will assume model of strong collisions for the collision integral. The off-diagonal elements of $`\widehat{S}`$ are

$$S_{jj^{}}=\mathrm{\Gamma }\rho _{jj^{}};j,j^{}m,n,k;jj^{}.$$
(7)
Here, $`j`$ and $`j^{}`$ indicate rotational states of the molecule. The decoherence rates, $`\mathrm{\Gamma }`$, were taken equal for all off-diagonal elements of $`\widehat{S}`$.

Collisions cannot alter molecular spin state in our model. It implies that the diagonal elements of $`\widehat{S}`$ have to be determined separately for ortho molecules,

$$S_{jj}=\nu \rho _o(j)+\nu w_o(j)\rho _o;\rho _o=\underset{j}{}\rho _o(j);j\text{ortho},$$
(8)
and for para molecules,

$$S_{jj}=\nu \rho _p(j)+\nu w_p(j)\rho _p;\rho _p=\underset{j}{}\rho _p(j);j\text{para}.$$
(9)
Here $`\rho _o`$, $`\rho _p`$ and $`w_o(j)`$, $`w_p(j)`$ are the total concentrations and Boltzmann distributions of ortho and para molecules. The rotational relaxation rate, $`\nu `$, was taken equal for ortho and para molecules, because kinetic properties of different spin species are almost identical.

One can obtain from Eq. (6) an equation of change of the total concentration in each spin space . For example, for ortho molecules one has,

$$d\rho _o/dt=2Re(i\rho _{mk}V_{km}).$$
(10)
In fact, this result is valid for any model of collision integral as long as collisions do not change the total concentration of molecules in each subspace, i.e., $`_jS_{jj}=0`$ if $`j`$ ortho, or $`j`$ para.

Let us approximate the density matrix by the sum of zero and first order terms over perturbation $`\widehat{V}`$,

$$\widehat{\rho }=\widehat{\rho }^{(0)}+\widehat{\rho }^{(1)}.$$
(11)
In zero order perturbation theory the ortho and para subspaces are independent, i.e., $`\rho _{mk}^{(0)}=0`$. Consequently, equation of change (10) is reduced to,

$$d\rho _o/dt=2Re(i\rho _{mk}^{(1)}V_{km}).$$
(12)
Note that the spin conversion appears in the second order of $`\widehat{V}`$.

Kinetic equations for zero and first order terms of the density matrix are given as,

$$d\widehat{\rho }^{(0)}/dt=\widehat{S}^{(0)}i[\widehat{G},\widehat{\rho }^{(0)}].$$
(13)
$$d\widehat{\rho }^{(1)}/dt=\widehat{S}^{(1)}i[\widehat{G},\widehat{\rho }^{(1)}]i[\widehat{V},\widehat{\rho }^{(0)}].$$
(14)
We start with zero order perturbation theory. In this approximation, the para subspace remain at equilibrium,

$$\rho _p^{(0)}(j)=\rho _p^{(0)}w_p(j);j\text{para}.$$
(15)
Here $`\rho _p^{(0)}`$ is the total concentration of para molecules.

Density matrix for ortho molecules can be determined from the two equations which follows from Eqs. (7),(8),(13):

$`d\rho _o^{(0)}(j)/dt`$ $`=`$ $`\nu \rho _o^{(0)}(j)+\nu w_o(j)\rho _o^{(0)}+2Re(i\rho _o^{(0)}(m|n)G_{nm})[\delta _{jm}\delta _{jn}];`$ (16)
$`d\rho _o^{(0)}(m|n)/dt`$ $`=`$ $`\mathrm{\Gamma }\rho _o^{(0)}(m|n)iG_{mn}[\rho _o^{(0)}(n)\rho _o^{(0)}(m)].`$ (17)
We will assume further the rotational wave approximation,

$$G_{mn}=Ge^{i\mathrm{\Omega }t};GE_0\overline{d}_{mn}/2\mathrm{};\mathrm{\Omega }=\omega _L\omega _{mn},$$
(18)
where the line over symbol indicate a time-independent factor. Rabi frequency, $`G`$, is assumed to be real. Rotational relaxation, $`\nu `$, and decoherence, $`\mathrm{\Gamma }`$, are on many orders of magnitude faster than the spin conversion. It allows to assume stationary regime for ortho molecules, thus having, $`d\rho _o^{(0)}(j)/dt=0`$. The substitution, $`\rho _o^{(0)}(m|n)=\overline{\rho }_o^{(0)}(m|n)\mathrm{exp}(i\mathrm{\Omega }t)`$, transforms Eqs. (17) to algebraic equations which can easily be solved. Thus one has,

$`\rho _o^{(0)}(j)`$ $`=`$ $`\rho _o^{(0)}\left[w_o(j)+{\displaystyle \frac{2\mathrm{\Gamma }}{\nu }}{\displaystyle \frac{G^2\mathrm{\Delta }w}{\mathrm{\Gamma }_B^2+\mathrm{\Omega }^2}}(\delta _{jm}\delta _{jn})\right];`$ (19)
$`\overline{\rho }_o^{(0)}(m|n)`$ $`=`$ $`\rho _o^{(0)}iG\mathrm{\Delta }w{\displaystyle \frac{\mathrm{\Gamma }+i\mathrm{\Omega }}{\mathrm{\Gamma }_B^2+\mathrm{\Omega }^2}};`$ (20)
$`\mathrm{\Gamma }_B^2`$ $`=`$ $`\mathrm{\Gamma }^2+4\mathrm{\Gamma }G^2/\nu ;\mathrm{\Delta }ww_o(n)w_o(m).`$ (21)
We turn now to the calculation of the first order term, $`\rho _{mk}^{(1)}`$, which has to be substituted into the equation of change (12). The density matrix element, $`\rho _{mk}^{(1)}`$, can be found from the two equations which are derived from Eqs. (7),(14),

$`d\rho _{mk}^{(1)}/dt+\mathrm{\Gamma }\rho _{mk}^{(1)}+iG_{mn}\rho _{nk}^{(1)}`$ $`=`$ $`iV_{mk}[\rho _o^{(0)}(k)\rho _o^{(0)}(m)];`$ (22)
$`d\rho _{nk}^{(1)}/dt+\mathrm{\Gamma }\rho _{nk}^{(1)}+iG_{nm}\rho _{mk}^{(1)}`$ $`=`$ $`iV_{mk}\rho _o^{(0)}(n|m).`$ (23)
Substitution,

$$V_{mk}=\overline{V}e^{i\omega t},(\omega \omega _{mk});\rho _{mk}^{(1)}=\overline{\rho }_{mk}^{(1)}e^{i\omega t};\rho _{nk}^{(1)}=\overline{\rho }_{nk}^{(1)}e^{i(\omega \omega _{kn})t},$$
(24)
transforms Eq. (23) to algebraic equations from which one finds $`\rho _{mk}^{(1)}`$. Then, Eq. (12) gives the following equation for the total concentration of ortho molecules,

$`{\displaystyle \frac{d\rho _o}{dt}}=2|\overline{V}|^2`$ $`Re`$ $`{\displaystyle \frac{[\mathrm{\Gamma }+i(\mathrm{\Omega }+\omega )][\rho _p^{(0)}(k)\rho _o^{(0)}(m)]iG\overline{\rho }_o^{(0)}(n|m)}{F(\mathrm{\Omega })}};`$ (25)
$`F(\mathrm{\Omega })`$ $``$ $`(\mathrm{\Gamma }+i\omega )[\mathrm{\Gamma }+i(\mathrm{\Omega }+\omega )]+G^2.`$ (26)
After an appropriate change of notations, the right hand side of Eq. (26), coincides formally with the solution  for the work of weak optical field in the presence of strong optical field. Strong field splits the upper state $`m`$ on two, which appears as two roots of the denominator of Eq. (26) being the second order polynomial on $`\omega `$. It results in two ortho-para level pairs mixed by the perturbation $`\widehat{V}`$ instead of one pair in the absence of an external field. In analogy with the optical case, one can distinguish the isomer conversion caused by population effects (terms proportional to the level populations $`\rho _p^{(0)}(k)`$ and $`\rho _o^{(0)}(m)`$) and by coherences (term proportional to the off-diagonal density matrix element, $`\overline{\rho }_o^{(0)}(n|m)`$).

Eq. (26) describes time dependence of the concentration of ortho molecules, $`\rho _o`$, in the second order of $`\widehat{V}`$. One can neglect at this approximation small difference between $`\rho _o`$ and $`\rho _o^{(0)}`$. The density of para molecules can be expressed through the density of ortho molecules as, $`\rho _p^{(0)}=n\rho _o^{(0)}`$, where $`n`$ is the total concentration of the test molecules. Using these points and zero order solution given by Eqs. (15),(21), one can obtain final equation of change for ortho molecules,

$$d\rho _o/dt=n\gamma _{op}\rho _o\gamma ;\gamma \gamma _{op}+\gamma _{po}+\gamma _n+\gamma _{coh},$$
(27)
where partial conversion rates were introduced,

$`\gamma _{op}`$ $`=`$ $`2|\overline{V}|^2w_p(k)f(\mathrm{\Omega });f(\mathrm{\Omega })Re{\displaystyle \frac{\mathrm{\Gamma }+i(\mathrm{\Omega }+\omega )}{F(\mathrm{\Omega })}};`$ (28)
$`\gamma _{po}`$ $`=`$ $`2|\overline{V}|^2w_o(m)f(\mathrm{\Omega });`$ (29)
$`\gamma _n`$ $`=`$ $`2|\overline{V}|^2{\displaystyle \frac{G^2\mathrm{\Delta }w}{\mathrm{\Gamma }_B^2+\mathrm{\Omega }^2}}{\displaystyle \frac{2\mathrm{\Gamma }}{\nu }}f(\mathrm{\Omega });`$ (30)
$`\gamma _{coh}`$ $`=`$ $`2|\overline{V}|^2{\displaystyle \frac{G^2\mathrm{\Delta }w}{\mathrm{\Gamma }_B^2+\mathrm{\Omega }^2}}Re{\displaystyle \frac{\mathrm{\Gamma }i\mathrm{\Omega }}{F(\mathrm{\Omega })}}.`$ (31)
Here the rates $`\gamma _{op}`$, $`\gamma _{po}`$, and $`\gamma _n`$ are due to molecular level populations and the rate $`\gamma _{coh}`$ is due to coherences. The terms $`\gamma _{op}`$ and $`\gamma _{po}`$ are the only ones which remain in the absence of an external field. In the radiation free case ($`G=0`$) the result (31) becomes identical with the solution given in .

## IV Enrichment

Solution to Eq. (27) can be presented as, $`\rho _o=\overline{\rho }_o+\delta \rho _o\mathrm{exp}(\gamma t)`$, where time-independent part is given by

$$\overline{\rho }_o=n\frac{\gamma _{op}}{\gamma }.$$
(32)
Without an external radiation (at the instant $`t=0`$), the equilibrium concentration of para molecules is equal to,

$$\rho _p(0)=n\rho _o(0)=n\frac{w_o(m)}{w_p(k)+w_o(m)}=\frac{n}{2}.$$
(33)
For simplicity, the Boltzmann factors in Eq. (33) were assumed to be equal, $`w_p(k)=w_o(m)w`$, which implies, $`\gamma _{op}=\gamma _{po}`$. External field produces a stationary enrichment of para molecules. One can derive from Eqs. (32),(33),

$$\beta \frac{\overline{\rho }_p}{\rho _p(0)}1=12\frac{\gamma _{op}}{\gamma }.$$
(34)
An enrichment coefficient, $`\beta `$, is defined here in such a way that $`\beta =0`$ if there is no external electromagnetic field. Enrichment of ortho molecules is equal to $`\beta `$. Note, that the enrichment, $`\beta `$, does not depend on the magnitude of intramolecular perturbation $`\widehat{V}`$. It is the consequence of the assumption that only one ortho-para level pair is mixed. Enrichment, $`\beta `$, depends on the ratio of Boltzmann factors, $`w_o(n)/w_o(m)`$, but does not depend on the magnitude of $`w_o(n)`$ itself. In further numerical examples relative difference of the Boltzmann factors will be chosen as $`w_o(n)=1.2w`$.

One needs to specify a few other parameters in order to investigate properties of the optically induced enrichment. We will use, where it is possible, parameters relevant to the spin conversion in 13CH3F. Thus the decoherence rate, $`\mathrm{\Gamma }`$, will be chosen equal 6 MHz, which corresponds to the gas pressure of pure CH3F equal 0.2 Torr . Rotational relaxation, $`\nu `$, will be chosen by one order of magnitude slower than the decoherence rate, $`\nu =0.1\mathrm{\Gamma }`$.

Expressions for the enrichment, $`\beta `$, are given in the Appendix. If ortho-para mixing is performed for a degenerate pair of states $`mk`$ ($`\omega =0`$), the enrichment of para states, $`\beta `$, has one peak at $`\mathrm{\Omega }=0`$. This peak is determined mainly by population effects.

More interesting is the case of nondegenerate states ($`\omega 0`$). In this case one has two peaks, at $`\mathrm{\Omega }=\omega `$ and at $`\mathrm{\Omega }=0`$ (Fig. 2). Peak 1 ($`\mathrm{\Omega }=\omega `$) is due to the coherent effects determined by $`\gamma _{coh}`$. Peak 2 ($`\mathrm{\Omega }=0`$) is mainly due to the optically induced level population changes determined by $`\gamma _n`$. In the case of well-separated peaks ($`\mathrm{\Gamma }_B\omega `$), the amplitudes of the peak 1 and peak 2 read,

$`A_1`$ $`=`$ $`{\displaystyle \frac{\mathrm{\Delta }w}{w}}{\displaystyle \frac{G^2}{\mathrm{\Gamma }^2+G^2}}\left[{\displaystyle \frac{1}{4}}+{\displaystyle \frac{D}{\mathrm{\Gamma }_B^2+\omega ^2}}\right];D\mathrm{\Gamma }^2+5G^2/4\mathrm{\Gamma }G^2/\nu +\omega ^2/4;`$ (35)
$`A_2`$ $`=`$ $`{\displaystyle \frac{\mathrm{\Delta }w}{w}}{\displaystyle \frac{G^2}{\mathrm{\Gamma }_B^2}}\left[{\displaystyle \frac{\mathrm{\Gamma }}{\nu }}{\displaystyle \frac{3}{4}}+{\displaystyle \frac{D}{\mathrm{\Gamma }_B^2+G^2+\omega ^2}}\right].`$ (36)
Amplitude of the peak 2 grows rapidly with $`G`$ up to $`\beta 4.5\%`$. Amplitude of the peak 1 grows with $`G`$ to even bigger value $`\beta 5.5\%`$. These data are shown in Fig. 3 (upper panel) where points are obtained by fitting an exact expression (34) by two Lorentzians and solid curves are given by Eqs. (36). $`\omega `$ was chosen equal 130 MHz which corresponds to the ortho-para level gap in 13CH3F . Note, that there is no optically induced enrichment if $`\mathrm{\Delta }w=0`$.

Widths of the enrichment peaks are given by the expressions,

$$W_1=2\sqrt{\mathrm{\Gamma }^2+G^2};W_2=2\mathrm{\Gamma }_B.$$
(37)
The two enrichment peaks experience completely different power broadening which are shown in Fig. 3 (low panel). Peak 1 has the width much smaller than the Peak 2. Solid curves in Fig. 3 (low panel) are given by Eqs. (37). Points are obtained by fitting the exact expression for enrichment, $`\beta `$, by two Lorentzians.

## V Conversion

Conversion rate in the presence of an external electromagnetic field has complicated dependence on radiation frequency detuning, $`\mathrm{\Omega }`$, and Rabi frequency, $`G`$. It is convenient to characterize the conversion rate in relative units,

$$\gamma _{rel}=\frac{\gamma }{\gamma _{free}}1,$$
(38)
where $`\gamma _{free}`$ is the field free conversion rate. Similar to the enrichment, $`\beta `$, this parameter does not depend on magnitude of the perturbation $`\widehat{V}`$ and on absolute values of the Boltzmann factors.

Expressions for the conversion rate, $`\gamma _{rel}`$, are given in the Appendix. In the case of degenerate ortho-para level pair $`mk`$ ($`\omega =0`$), $`\gamma _{rel}`$ has narrow negative structure at $`\mathrm{\Omega }=0`$ (Fig. 4). Amplitude of this dip grows rapidly with increasing $`G`$. If $`G\mathrm{\Gamma }\nu `$, and all Boltzmann factors have the same order of magnitude, the conversion rate at $`\mathrm{\Omega }=0`$ is given by

$$\gamma _{rel}\frac{\mathrm{\Gamma }^2}{G^2}1.$$
(39)
If $`G`$ is large, the relative conversion rate, $`\gamma _{rel}1`$, which corresponds to $`\gamma 0`$. Thus the spin conversion can be inhibited by radiation having large $`G`$ and $`\mathrm{\Omega }=0`$.

In the nondegenerate case ($`\omega 0`$) conversion rate, $`\gamma _{rel}`$, has two peaks (Fig. 5). If these peaks are well resolved, $`\mathrm{\Gamma }_B\omega ^{}`$, conversion rate is given by,

$$\gamma _{rel}=\frac{\mathrm{\Gamma }^{}\mathrm{\Gamma }^1G^2}{\mathrm{\Gamma }^2+(\mathrm{\Omega }+\omega ^{})^2}+\frac{\mathrm{\Delta }w}{w}\frac{G^2}{\mathrm{\Gamma }_B^2+\mathrm{\Omega }^2}\left(\frac{\mathrm{\Gamma }}{\nu }\frac{1}{2}\right),$$
(40)
where new parameters are determined as,

$$\mathrm{\Gamma }^{}\mathrm{\Gamma }\left(1+\frac{G^2}{\mathrm{\Gamma }^2+\omega ^2}\right);\omega ^{}\omega \left(1\frac{G^2}{\mathrm{\Gamma }^2+\omega ^2}\right).$$
(41)
The two peaks in the conversion have Lorentzian profiles and amplitudes determined by the expressions,

$$A_3=\frac{G^2}{\mathrm{\Gamma }^{}\mathrm{\Gamma }};A_4=\frac{\mathrm{\Delta }w}{w}\frac{G^2}{\mathrm{\Gamma }_B^2}\left(\frac{\mathrm{\Gamma }}{\nu }\frac{1}{2}\right).$$
(42)
These amplitudes are shown in Fig. 6 (upper panel) by solid curves. Points are obtained by fitting the exact solution by two Lorentzians. In this examples, $`\omega `$ was chosen equal 130 MHz. Peak 4 at $`\mathrm{\Omega }=0`$ is proportional to the ratio of Boltzmann factors. This peak does not grow significantly with $`G`$. The peak 3 at $`\mathrm{\Omega }=\omega ^{}`$ almost does not depend on Boltzmann factors and at large $`G`$ grows up to $`\gamma _{rel}=(\omega /\mathrm{\Gamma })^2`$. Thus strong electromagnetic field can speed up the conversion significantly, viz., by two orders of magnitude in our numerical example.

Widths of the two peaks in the conversion rate are determined by the equations,

$$W_3=2\mathrm{\Gamma }^{};W_4=2\mathrm{\Gamma }_B,$$
(43)
and have very different field dependences. In fact, the peak 4 at $`\mathrm{\Omega }=0`$ is broadened even faster than $`2\mathrm{\Gamma }_B`$. Peak 3 at $`\mathrm{\Omega }=\omega `$ has almost no power broadening, if $`G\omega `$ (Fig. 6, low panel). Solid curves in Fig. 6, low panel, corresponds to the Eqs. (43). Points are obtained by fitting the exact solution by two Lorentzians.

## VI Conclusions

We have shown that an external resonant radiation can influence spin isomer conversion in two ways, through level populations and through optically induced coherences. The coherences introduce in the process new and interesting features. In many cases, the coherences play more important role than the level populations. This analysis have been performed in a simplest arrangement in order to reveal the main features of the phenomenon.

Optically induced coherences introduce extra resonances both in enrichment and in conversion frequency dependences. These new resonances are important for future experimental realizations of the optical control of isomer conversion. First, they give convenient opportunity to find coincidences between molecular transitions and available sources of powerful radiation. Second, an observation of the phenomenon will be easier also because electromagnetic radiation can significantly speed up the conversion. Thus steady state enrichment can be achieved much faster than without field. It allows to work at low gas pressures where described above effects can be achieved at smaller radiation intensity.

Another advantage is that one can use resonance at which there is no large radiation absorption and, consequently, no significant level population change by radiation. It should decrease some spurious effects, like molecular resonance exchange. The latter effect can cause serious problems in realization of the optically induced enrichment by population effects .

## VII Appendix

Here we give expressions for the enrichment, $`\beta `$, and conversion rate, $`\gamma _{rel}`$. Enrichment of para molecules is given by Eq. (34). For equal Boltzmann factors, $`w_o(m)=w_p(k)w`$, one has

$$\beta =1\left(1+\frac{\gamma _n+\gamma _{coh}}{2\gamma _{op}}\right)^1,$$
(44)
and an approximate expression in case of small enrichment,

$$\beta \frac{\gamma _n+\gamma _{coh}}{2\gamma _{op}}.$$
(45)
Using Eqs. (31), this expression can be reduced to,

$`\beta `$ $`{\displaystyle \frac{\mathrm{\Delta }w}{w}}`$ $`\left[{\displaystyle \frac{1/4}{\mathrm{\Gamma }^2+G^2+(\mathrm{\Omega }+\omega )^2}}+{\displaystyle \frac{\mathrm{\Gamma }/\nu 3/4}{\mathrm{\Gamma }_B^2+\mathrm{\Omega }^2}}+{\displaystyle \frac{D}{(\mathrm{\Gamma }_B^2+\mathrm{\Omega }^2)[\mathrm{\Gamma }^2+G^2+(\mathrm{\Omega }+\omega )^2]}}\right];`$ (46)
$`D`$ $``$ $`\mathrm{\Gamma }^2+5G^2/4\mathrm{\Gamma }G^2/\nu +\omega ^2/4.`$ (47)
There are two peaks in enrichment, at $`\mathrm{\Omega }=\omega `$ and at $`\mathrm{\Omega }=0`$. These peaks have Lorentzian shape if $`\omega \mathrm{\Gamma }_B`$. In the degenerate case ($`\omega =0`$) there is one peak of complicated form at $`\mathrm{\Omega }=0`$.

The spin conversion rate, $`\gamma _{rel}`$, is defined as,

$$\gamma _{rel}=\frac{\gamma }{\gamma _{free}}1.$$
(48)
Using Eqs. (31) one can obtain after straightforward calculations the following expression,

$`\gamma _{rel}=`$ $`g{\displaystyle \frac{(1+g)(\omega ^2\mathrm{\Gamma }^2)+2\omega (\mathrm{\Omega }+\omega ^{})}{\mathrm{\Gamma }^2+(\mathrm{\Omega }+\omega ^{})^2}}+`$ (52)
$`{\displaystyle \frac{\mathrm{\Delta }w}{w}}{\displaystyle \frac{G^2}{\mathrm{\Gamma }_B^2+\mathrm{\Omega }^2}}\left({\displaystyle \frac{\mathrm{\Gamma }}{\nu }}{\displaystyle \frac{1}{2}}\right)\left[1+g{\displaystyle \frac{(1+g)(\omega ^2\mathrm{\Gamma }^2)+2\omega (\mathrm{\Omega }+\omega ^{})}{\mathrm{\Gamma }^2+(\mathrm{\Omega }+\omega ^{})^2}}\right]+`$
$`{\displaystyle \frac{\mathrm{\Delta }w}{2w}}{\displaystyle \frac{G^2}{\mathrm{\Gamma }_B^2+\mathrm{\Omega }^2}}{\displaystyle \frac{(1+g)(2\mathrm{\Gamma }^2+\omega ^2)\omega (\mathrm{\Omega }+\omega ^{})}{\mathrm{\Gamma }^2+(\mathrm{\Omega }+\omega ^{})^2}};`$
$`g{\displaystyle \frac{G^2}{\mathrm{\Gamma }^2+\omega ^2}};\mathrm{\Gamma }^{}\mathrm{\Gamma }(1+g);\omega ^{}\omega (1g).`$
Thus the conversion rate has two peaks situated at $`\mathrm{\Omega }=\omega ^{}`$ and at $`\mathrm{\Omega }=0`$. Position of the peak at $`\mathrm{\Omega }=\omega ^{}`$ depends on the field intensity.

In the case of degenerate ortho-para level pair ($`\omega =0`$), frequency dependence of $`\gamma _{rel}`$ has complicated shape with a dip in the center at $`\mathrm{\Omega }=0`$ (Fig. (4)). The whole structure is described by the expression,

$$\gamma _{rel}=\frac{(1+g)G^2}{\mathrm{\Gamma }^2+\mathrm{\Omega }^2}+\frac{\mathrm{\Delta }w}{w}\frac{G^2}{\mathrm{\Gamma }_B^2+\mathrm{\Omega }^2}\left[\left(\frac{\mathrm{\Gamma }}{\nu }\frac{1}{2}\right)\left(1\frac{(1+g)G^2}{\mathrm{\Gamma }^2+\mathrm{\Omega }^2}\right)+\frac{\mathrm{\Gamma }^{}\mathrm{\Gamma }}{\mathrm{\Gamma }^2+\mathrm{\Omega }^2}\right].$$
(53)
## Acknowledgments

This work was made possible by financial support from the Russian Foundation for Basic Research (RFBR), grant No. 98-03-33124a