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# Conversion of an Atomic Fermi Gas to a Long-Lived Molecular Bose Gas

(July 21, 2003)

## Abstract

We have converted an ultracold Fermi gas of 6Li atoms into an ultracold gas of 6Li2 molecules by adiabatic passage through a Feshbach resonance. Approximately $`1.5\times 10^5`$ molecules in the least-bound, $`v=38`$, vibrational level of the X$`{}_{}{}^{1}\mathrm{\Sigma }_{g}^{+}`$ singlet state are produced with an efficiency of 50%. The molecules remain confined in an optical trap for times of up to 1 s before we dissociate them by a reverse adiabatic sweep.

Feshbach resonances have emerged as a major tool for altering the strength and sign of interactions in ultracold atomic gases. A Feshbach resonance is a collisional resonance between pairs of free atoms and a bound state of the diatomic molecule, for which differences between the atomic and molecular magnetic moments enable the resonance to be magnetically tuned Stwalley (1976). Molecules can be formed near a Feshbach resonance and have recently been detected in ultracold gases for fields close to a resonance Donley et al. (2002). An adiabatic sweep of the magnetic field through the Feshbach resonance has been proposed as a highly-efficient method for converting ultracold atoms into ultracold molecules Timmermans et al. (1999); van Abeelen and Verhaar (1999); Mies et al. (2000); Yurovsky et al. (2000); Yurovsky and Ben-Reuven (2003); Mackie et al. (2002), as was recently demonstrated with a Fermi gas of 40K atoms Regal et al. (2003). This method might be used to create a Bose-Einstein condensation (BEC) of molecules. There is heightened interest in the case where the initial atoms are fermions Timmermans et al. (2001), since there are close connections between Cooper pairing in the BCS theory and BEC of molecules in the strong coupling limit Randeria (1995). However, molecules produced by this method are vibrationally excited, and thus far, the observed molecular lifetimes have been only $``$1 ms Wynar et al. (2000); Regal et al. (2003). This is likely to be shorter than the time needed for effective evaporative cooling, or for the thermal equilibration necessary for the molecules to Bose condense. In this paper, we report the efficient conversion of an atomic Fermi gas of 6Li atoms into a gas of molecules with an observed lifetime of $``$1 s.

Major components of the apparatus have been described previously Truscott et al. (2001); Strecker et al. (2002). After accumulating approximately 1010 bosons (7Li) and 109 fermions (6Li) in a magneto-optical trap, the atoms are optically pumped into the $`F=2,m_F=2`$ and $`F=3/2,m_F=3/2`$ states, respectively, and transferred to a magnetic trap. In contrast to our previous work, where only the 7Li atoms were evaporated and the 6Li were cooled sympathetically Truscott et al. (2001), we now evaporate both isotopes. This “dual evaporation” scheme is far more efficient, resulting in a 100-fold increase in the number of 6Li atoms to $`N=7\times 10^7`$ and a three-fold lowering of the relative temperature to $`T=0.1T_F`$, where $`T_F`$ is the Fermi temperature. This is the largest number of trapped fermions cooled to temperatures below $`T_F`$ reported thus far. The states of interest are not magnetically trappable, so we transfer them to an optical trap Strecker et al. (2002). The optical trapping potential is approximately harmonic radially, with a frequency of $``$800 Hz for 6Li and a depth of $``$10 $`\mu `$K. The potential is box-like axially with a length of 480 $`\mu `$m and a depth of $``$7 $`\mu `$K. The 7Li atoms are removed from the optical trap by a resonant laser pulse.

Feshbach resonances occur between the two lowest hyperfine levels, $`F=1/2,m_F=1/2`$ and $`F=1/2,m_F=1/2`$ in 6Li as was predicted in ref. Houbiers et al. (1998) and recently observed O’Hara et al. (2002). An adjustable uniform magnetic bias field of $``$549 G is applied to tune near a resonance. A frequency-swept microwave pulse transfers the 6Li atoms from the $`F=3/2,m_F=3/2`$ to the $`F=1/2,m_F=1/2`$ state with nearly 100% efficiency. The transition between the $`F=1/2,m_F=1/2`$ and $`F=1/2,m_F=1/2`$ states is driven by an RF pulse at $``$76 MHz. Symmetry requires that the two state mixture be incoherent, otherwise the atoms remain indistinguishable and do not interact. We observe a remarkable degree of coherence in this system, including Rabi oscillations that persist for several seconds without evidence of decoherence. In order to create an incoherent mixture of equal populations in each state, a small magnetic gradient is applied and the transition is driven for 1 s by a frequency-swept triangle wave that is swept back and forth across the resonance 50 times. Decoherence of this mixture is readily verified by observation of rapid loss from the shallow optical trap as the gas thermalizes. The mixture does not decohere without the field gradient. At the end of this process, we estimate the number of atoms in each spin state to be $`3\times 10^5`$, while the corresponding peak density of each state is $`3\times 10^{12}`$ cm-3, giving $`T_F1.4\mu `$K. Although accurate determinations of the temperature is limited by the flat axial density distribution in the optical trap, it is expected to be quite low due to rapid evaporative cooling. The radial profiles are consistent with temperatures below $`0.1T_F`$.

Although 6Li exhibits an extremely large Feshbach resonance at $``$850 G, we instead utilize the narrow resonance located at $``$543 G. We chose the narrow resonance for two reasons: first, it is technically simpler to sweep over a smaller range of magnetic field; and second, recent theoretical results indicate that one of the primary mechanisms for loss of atoms, the creation of pairs of hot atoms during the sweep, is minimized for a narrow resonance compared with a broad one van Abeelen and Verhaar (1999); Yurovsky and Ben-Reuven (2003). Figure 1 shows the results of a coupled-channels calculation of the scattering length for this resonance. The singlet and triplet potentials necessary for this calculation were constructed from spectroscopic data Abraham et al. (1997) and were further refined by the observation of the location of a Feshbach resonance in 7Li Strecker et al. (2002). The predicted location of the resonance, 543.8 G, deviates slightly from the measured location given by the data shown in the following figures. Figure 2 shows the lifetime of the trapped atoms for fixed fields near the resonance. The curve is asymmetric with a slower fall-off on the low-field side of the peak at 543.25 $`\pm `$ 0.05 G.

To convert atoms to molecules, the magnetic field is ramped from high field to low so that the molecular energy goes from above dissociation, to below. This creates molecules energetically stable against dissociation, and minimizes the creation of translationally hot atom pairs Timmermans et al. (1999); van Abeelen and Verhaar (1999); Mies et al. (2000); Yurovsky and Ben-Reuven (2003); Mackie et al. (2002). Although a Fermi gas contains a spread of atomic energies, the process can be approximated as an adiabatic passage through a two-level avoided crossing, where the two states are a pair of free atoms and a bound vibrational level of the diatomic molecule Mies et al. (2000). The Landau-Zener theory is applicable in this case, and predicts that the transition probability is proportional to $`1e^{\dot{B}^1}`$, where $`\dot{B}^1`$ is the inverse ramp rate Landau (1932). Experimentally, we start the ramp at a field far above the resonance (549 G) and end it far below ($``$350 G). The measured fraction of atoms remaining as a function of $`\dot{B}^1`$ is shown in Fig. 3, which exhibits the predicted exponential dependence. The Landau-Zener model also predicts that the conversion should be 100% if the ramp rate is sufficiently slow, while we observe a maximum efficiency of $``$50%. A similar maximum efficiency was reported in ref. Regal et al. (2003).

Figure 4 gives the fraction of atoms remaining when the field ramp begins at 549 G and is stopped at various final fields. The ramp rate is sufficiently slow to ensure maximum conversion efficiency. We fit the resulting data to the empirical equation $`1/2[1+1/(1+e^{(BB_o)/\mathrm{\Delta }B})]`$ and find that $`B_o=543.26\pm \mathrm{\hspace{0.17em}0.1}`$ G and $`\mathrm{\Delta }B=0.23`$ G. To within our resolution of 0.1 G, which is comparable to the width of the resonance itself, the peak of the loss (Fig. 2) and the center of the resonance, given by $`B_o`$, occur at the same field.

The results presented thus far indicate that atoms are lost while traversing the Feshbach resonance, but they do not distinguish between molecule conversion and other loss processes, such as inelastic collisions. To demonstrate that molecules are indeed produced, we show that the atom/molecule conversion process is reversible, as in ref. Regal et al. (2003), by first sweeping downward through the resonance, waiting for a fixed amount of time, then sweeping back to the original field. Molecules created by the downward ramp will be returned as atoms by the upward ramp, as long as the molecules themselves have not been lost during the time interval $`\tau `$ between their creation and subsequent dissociation back to atom pairs. It can be seen from Fig. 5 that close to 85% of the original atom population survives the double ramp, which demonstrates that no more than 15% of the original atom population is lost by inelastic processes. Furthermore, the data of Fig. 5 show that the molecules survive for an unexpectedly long time, of order 1 s.

The molecules produced by this method are vibrationally excited and can de-excite by inelastic collisions with atoms or other molecules. These vibrational quenching collisions impart kinetic energy to the participants in the collision equal to the energy difference between the initial and final vibrational levels. In the present case, the coupled-channels calculation indicates that the Feshbach resonance couples electronically spin-polarized pairs of atoms interacting via the molecular triplet potential with the least-bound ($`v=38`$) vibrational level of the X$`{}_{}{}^{1}\mathrm{\Sigma }_{g}^{+}`$ singlet state of 6Li2. We have calculated that the $`v=37`$ and $`v=38`$ levels are separated by over 50 GHz, so any vibrational quenching collision results in the release of over 2 K of energy, far exceeding the depth of the optical trap. Previous determinations of vibrational quenching of weakly bound vibrational levels of the bosons 87Rb Wynar et al. (2000) and Na Stenger et al. (1999); van Abeelen and Verhaar (1999); Yurovsky et al. (2000), and of the fermion 40K Regal et al. (2003), are consistent with lifetimes of $``$1 ms and rate constants of $``$10-10 cm$`{}_{}{}^{3}s_{}^{1}`$. Similarly, calculations for quenching of high-lying vibrational levels of H2 by H Balakrishnan et al. (1997) and of the $`v=1`$ level of Na2 by Na atoms Soldán et al. (2002) produce rate constants of approximately the same value. In contrast, we find an effective rate constant that is two to three orders of magnitude smaller. One might expect the quenching rate to be minimized by stopping the field ramp within the Feshbach resonance. In this case, the molecules are extremely weakly bound, and will have poor wavefunction overlap with lower-lying levels. However, this is not the origin of the rate reduction seen here, as the final field is well below the resonance, and the molecules are essentially pure singlet in character. Fermi statistics might cause a reduction in the rate of quenching if the size of the molecule is smaller than the size of the region over which the pair correlation is depleted.

The long molecular lifetime may enable the formation of a molecular BEC by allowing enough time for thermalization and evaporative cooling of the gas. Additionally, if the initial Fermi gas is already at $`T=0`$ and the conversion is slow with respect to the translational degrees of freedom, the conversion should proceed along the ground state of the system directly into a molecular BEC. For faster sweeps that are non-adiabatic with respect to the translational motion, but still adiabatic with respect to molecule formation, the molecular gas will have the same mean energy as the initial Fermi gas. In this case, the temperature is essentially equal to the BEC transition temperature of the molecules. If a molecular BEC can be formed, a completely adiabatic sweep back across the Feshbach resonance will maintain $`T=0`$, and allow the formation and investigation of Cooper pairs at any adjustable interaction strength Timmermans et al. (2001).

The authors gratefully acknowledge the contributions of Ying-Cheng Chen, and helpful conversations with Michael Jack and Andrew Truscott. This work was funded by grants from the NSF, ONR, NASA, and the Welch Foundation.


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# The Assessment and Calibration of Ensemble Seasonal Forecasts of Equatorial Pacific Ocean Temperature and the Predictability of Uncertainty

## 1 Introduction

One of the ways that users of seasonal forecasts can access forecast information is to monitor predictions of sea surface temperatures in the equatorial Pacific. The Niño3 and Niño3.4 regions in particular are good indicators of the state of ENSO, and numerous forecasts are available for these indices. These forecasts come from dynamical ensemble models such as those discussed in Stockdale et al. (1998) and Mason et al. (1999), from intermediate complexity models as described in Prigaud et al. (2000) and from pure statistical models such as that of Penland and Magorian (1993).

Users of any of these forecasts need to be able to answer a number of questions about a forecast before they can use it with confidence in an application. These questions include:

* Does the forecast need calibration?
* For how many months is the forecast of the mean temperature better than no forecast?
* What is the best way to derive a prediction of the uncertainty around the mean?
* Which is the best of the available forecasts?

These questions have been addressed by a number of authors. Methods used to answer the first question include assessments of bias and incorrect variance (Doblas-Reyes et al., 2003) and rank histograms and reliability diagrams (Wilks, 2000). The second question can be answered using the anomaly correlation between forecast and observations or the significance level of a regression coefficient between forecast and observations (Brankovic and Palmer, 2000). The third question is generally harder to answer and there do not seem to be any very satisfactory methods described in the literature. Finally, the fourth question can be answered using a combination of methods including anomaly correlation or mean squared error (MSE), which both address the skill of the mean of the forecast, or the relative operating characteristic (ROC) (Swets, 1988) and CRPS (continuous rank probability score) (Hersbach, 2000) which look at aspects of the distribution.

As part of a project to develop simple practical methods for use in industry, we will now show how it is possible to answer all four of these questions at once in a single consistent framework using the method described in Jewson et al. (2003) (henceforth JBZ). The values of the parameters from the JBZ method will give us clear answers to the first three questions, along with interesting insights into the predictability of uncertainty. We will answer the fourth question using a new skill measure that measures the ability of the forecast to predict the whole temperature distribution.

In section 2 we describe the observational and forecast data used for this study. In section 3 we will briefly describe the method we will apply and the interpretation of the resulting parameter values. In section 4 we show results from the analysis of our two time series of ensemble seasonal hindcasts, and in section 5 we discuss our results and draw some conclusions.

## 2 Data

All the analyses in this paper are based on sets of seasonal hindcasts from the European Centre for Medium Range Weather Forecasting (ECMWF) and Meteo France (MF) seasonal forecast models. These are both dynamical ocean-atmosphere models. The hindcasts were produced as part of the DEMETER project (Palmer et al., 2003) and consist of 6 month predictions of monthly mean Niño3 temperatures. Both sets of hindcasts cover the period 1958 to 2001 (44 years) and consist of ensembles of size nine. The forecasts start at four different times of year: February, May, August and November. These forecasts are compared with temperature observations for the Niño3 region obtained from the GISST2.3 and Reynolds 2D-Var SST data sets.

All values used in this study are deseasonalised in the mean and the standard deviation before any calculations are performed, and all equations given below apply to these deseasonalised values.

## 3 Method

We will address the four questions outlined in the introduction using the statistical model described in JBZ. This model consists of a simple calibration method in which the ensemble mean and the ensemble standard deviation are considered as inputs for a prediction for the mean temperature and the uncertainty around that temperature. The predictions of the mean and the uncertainty are derived from the ensemble mean and standard deviation using simple linear transformations. To be more specific, the model postulates that observed temperatures come from a normal distribution with estimated mean given by $`\widehat{\mu }_i=\alpha +\beta m_i`$ and estimated standard deviation given by $`\widehat{\sigma }_i=\gamma +\delta s_i`$, where $`m_i`$ is the ensemble mean and $`s_i`$ is the ensemble spread. We write this model as:

$$T_iN(\alpha +\beta m_i,\gamma +\delta s_i)=N(\widehat{\mu },\widehat{\sigma })$$
(1)
Although neither the mean temperature nor the standard deviation of temperature are actually observed, the parameters of this model can be fitted easily by maximizing a cost function which measures the goodness of fit of the normal distribution. There are a number of possible cost functions one could use, but we choose to use the likelihood, defined as the probability density of the observations given the calibrated forecast. Likelihood is the standard approach used for parameter estimation in statistics (see for example the statistics textbooks by Casella and Berger (2002) or Lehmann and Casella (1998)) and is one of the most natural methods for measuring the goodness of fit of a distribution. It also gives the most accurate possible parameter estimates for most statistical models.

Having determined the optimum values for the parameters $`\alpha ,\beta ,\gamma `$ and $`\delta `$ one can interpret them as follows:

* $`\alpha `$ identifies bias in the forecast. If $`\alpha `$ is significantly different from zero then the bias needs correcting.
* $`\beta `$ calibrates the variations of the ensemble mean to have the correct amplitude. If $`\beta `$ is significantly different from one then the forecast needs calibration. It is also used to assess whether the forecast contains any useful information: if $`\beta `$ is not significantly different from zero then the forecast is useless (at least in the context of this calibration model) and one should use climatological temperatures instead.
* $`\gamma `$ and $`\delta `$ calibrate the prediction of the uncertainty to have the correct size and variability. If there is very little information in the variability of the ensemble spread, then $`\delta `$ will be small and $`\gamma `$ will be larger to compensate. In the same way that $`\beta `$ can be used to assess whether the ensemble mean has any useful predictive information, $`\delta `$ can be used to assess the ensemble spread. If $`\delta `$ is not significantly different from zero then the ensemble spread contains no useful information (again, in the context of this model).

In the case in which $`\delta `$ is not significantly different from zero then, for that lead time, the hope that flow-dependent variations in uncertainty can be predicted has to be abandoned and one should re-fit using the alternative model:

$$T_iN(\alpha +\beta m_i,\widehat{\sigma }_0)$$
(2)
where $`\widehat{\sigma }_0`$ is constant in time for a given lead time. This model can also be fitted by maximizing the likelihood, which is equivalent to least squares linear regression in this case. Predictions of the uncertainty in this simplified model will come entirely from past forecast error statistics.

Even if $`\delta `$ is significantly different from zero and we conclude that the ensemble spread of a model does contain useful flow-dependent information about variations in the uncertainty, it is still not necessarily the case that the predicted variations in the uncertainty are material. In other words, they may be so small relative to the mean level of the uncertainty that they can as well be ignored. This can be for two reasons: either because the predicted variations in the uncertainty have a very low correlation with the actual variations in the uncertainty, or because the actual uncertainty itself simply does not vary very much. We will measure the materiality of the predictable variations in the uncertainty using the coefficient of variation of the spread (COVS), defined by the ratio of the standard deviation of the variations in the calibrated spread to the mean calibrated spread:

$$\text{COVS}=\frac{\delta \text{sd}(s)}{\gamma +\delta \overline{s}}$$
(3)
We arbitrarily choose a level of 0.05 to define the level below which we consider variations in the uncertainty to be immaterial. If uncertainty variations are immaterial then there is no need to use equation 1 to calibrate a forecast, and the simpler linear regression model (equation 2) can be used instead.

There are a number of ways to compare the resolution of forecasts from different models. To make a fair in-sample comparison, the same calibration methods must be used for all the models. Forecasts can then be compared using methods such as MSE, ROCs, or CRPS. However, to focus on the ability of a model to predict the probabilities across the whole distribution correctly we prefer to use the likelihood. Likelihood skill measures can be presented in a number of ways:

* The likelihood itself.
* The log-likelihood, which has a more compressed (and hence more convenient) range of values than the likelihood
* The square root of minus the log-likelihood (RMLL). This has the advantage that it is equivalent to use of the root-mean-square error in cases where the uncertainty is not flow-dependent.
* The log-likelihood skill-score (LLSS) defined as one minus the ratio of the log-likelihood to the climatological log-likelihood. This has the advantage that values range from zero for a useless forecast to one for a perfect forecast.

Likelihood skill measures can be presented for each lead time, or for all lead times together. We will present our comparison results in terms of the LLSS for each lead time.

## 4 Results

Figure 1 shows the optimum values for the parameters in equation 1 for the ECMWF hindcasts, based on forecasts made at all times of year. Each estimate also has an indication of the statistical or sampling uncertainty around the optimal parameter estimate. These uncertainties are calculated from the curvature of the log-likelihood in the standard way. 44 years of forecasts four times per year gives 176 past forecasts, and from the uncertainty estimates we see that this is enough to give reasonably accurate estimates of all the parameters.

The value of $`\beta `$ is significantly different from zero at all lead times up to six months. This shows that the ensemble mean contains useful information at all lead times. However, it certainly needs to be calibrated to give an optimum forecast, especially at the longer lead times. The value of $`\delta `$, however, is only significantly different from zero at leads one and two. This shows that the ensemble spread only contains useful information at these two lead times, and for longer leads does not contain useful information. For leads three to six one thus has to discard the results from the calibration model and refit the ensemble data using standard linear regression (equation 2). This will give optimal predictions of the mean and the uncertainty, but the uncertainty prediction will not be flow-dependent.

Figure 2 shows results for the same analysis for the MF model. The value of $`\beta `$ again shows that the ensemble mean contains useful information at all lead times. The values for $`\delta `$ are now significantly different from zero up to lead four. Only at leads five and six does the ensemble spread contain no useful information. Once again, at these lead times the results from the calibration model must be discarded and a linear regression model used instead.

We have seen that the ECMWF model can be used to make a flow dependent prediction of uncertainty at leads one and two, and the MF model can be used to make such a prediction for leads one to four. We now assess the size of these flow-dependent variations in uncertainty relative to the mean level of the uncertainty using the COVS. Values for the COVS for leads for which there is significant information about the spread are given in table 1. We see that the ECMWF model only gives material values of COVS at lead one. However at this lead the standard deviation of predictable variations in the uncertainty is nearly 14% of the total uncertainty. It would seem likely that this is a useful level of predictability of the variability of uncertainty for some users. The MF model gives material but rather low values for the COVS out to lead four.

We now address the question of whether the models show the same levels of predictability at different times of year by repeating the calibration analysis on each season separately. The seasonal parameters are fitted using only 44 past forecast values (one per year) and this means that the parameters cannot be estimated as accurately. This is balanced by the fact that we can hopefully pick up more detail in the structure of the predictability. For instance we might expect to see some signs of the well-known spring barrier (Webster and Yang, 1992).

The results for the ensemble mean (not shown) show that in all seasons both models contain useful predictive information out to six months. The results for the ensemble spread are more complex. Figure 3 shows the optimum values for the parameters in equation 1 for the MF forecasts started in May. In this case the ensemble spread contains detectable useful information from leads one to four, as with the annual data. Results for the uncertainty for all other seasons and for both models are summarized in table 2, which lists the months for which skillful flow dependent predictions of the variations in uncertainty can be made. We detect that the ECMWF model shows skill for the spread only in the first month, while the MF model shows skill for the spread for different numbers of months in each season. How is it that, when analyzed on annual data, the ECMWF model shows two months of significant spread, whereas when analyzed on seasonal data, it only shows one month? The answer is that the spread signal in the second month is very small, and reducing the number of data points from 176 to 44 means that it can no longer by detected. The MF model shows more seasonal variability in the predictability of spread than the ECMWF model. In particular, the model shows the least predictability of spread in February. This suggests that the spring predictability barrier may affect predictions of spread as well as predictions of the mean.

Finally we consider which of the two models produces better forecasts, taking into account the skill with which the model predicts the probabilities across the whole distribution by using a likelihood based skill measure. Figure 4 shows the LLSS for both models. We see that, by this measure, the ECMWF model is better at lead 1, but that the MF model is slightly better at all subsequent leads. The biggest fractional differences in the LLSS are at leads five and six. However, the differences are small and may be partly due to sampling variability.

## 5 Conclusions

We have described how the ensemble calibration model of JBZ can be used to assess and calibrate ensemble seasonal forecasts, and in particular how it can determine the limit of useful information in the ensemble mean and standard deviation of such forecasts. We have assessed time series of ensemble seasonal hindcasts from the ECMWF and MF models. The results are striking. For the ECMWF model although the ensemble mean contains useful predictive information out to the end of the forecast period at six months, the ensemble spread shows no useful predictive information beyond lead two. At lead times beyond the second (and beyond the first on a seasonal basis) it is more appropriate to calculate the uncertainty of the forecast from past forecast error statistics than it is to use the ensemble spread. Even at lead two, the size of the predictable component of the uncertainty could be considered immaterial relative to the total uncertainty. This finding contrasts with the results for *medium range* ensemble forecasts from ECMWF, for which both the mean and the spread contain useful information out to the end of the forecast at 10 days (see JBZ). For the MF model the ensemble mean also contains useful information to the end of the forecast, while the spread contains useful information up to month four. Only at months five and six does the spread not contain useful information about the variations in forecast uncertainty. When we consider the size of the variations in spread that are predictable from the MF model, we find that they are material relative to the total uncertainty, and are probably worth incorporating into a prediction of the uncertainty if accurate predictions of the uncertainty are important. They are, however, only a small fraction of the mean uncertainty and some users may decide to ignore them if less accuracy in the estimates of the uncertainty is required. When analyzed on a seasonal basis we see strong seasonal variability in the predictability of uncertainty consistent with there being a spring barrier for predictability of uncertainty as well as for predicting the mean.

We have demonstrated how long seasonal hindcasts are extremely useful both for defining accurate calibration parameters and for assessing the skill of forecast systems. A prudent user of forecasts would never use a forecast unless the skill can be identified statistically in hindcasts or past forecasts, and with seasonal forecasts skill can often only be identified with such long data sets.

Finally we have compared the ECMWF and MF hindcasts using a likelihood based skill measure which assesses the performance of the model in predicting the whole distribution of possible outcomes. We find that, according to this measure, the ECMWF model makes slightly better forecasts at lead one, while the MF model forecasts are slightly better for leads two to six.

There are a number of directions for future work arising from this study. It is important to assess results from calibration using the JBZ model in out-of-sample tests, and to compare the reliability of such results with those from other calibration methods. From a user-perspective it is important to extend this work to consider site-specific forecasts in addition to forecasts of the Pacific ocean temperature. Finally, the optimal predictions of the mean and variance that are produced by the calibration method described form a good basis for forming optimal multimodel forecasts, and it would interesting to compare the results from such multimodel forecasts with those derived using other methods.

## 6 Acknowledgements

We would like to thank ECMWF for providing us with the data on which this study was based, and D. Anderson, A. Brix, S. Mason and C. Ziehmann for helpful discussions. SJ funded his own research, while FDR and RH were funded by the DEMETER project (EVK2-1999-00197).


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# Sub-microsecond correlations in photoluminescence from InAs quantum dots

## I Introduction

A variety of memory effects have been reported in the optical emission of single semiconductor quantum dots. generaldot  Many of these effects occur on millisecond timescales, including blinking, diff\_efros ; diff\_pistol ; diff\_sugisaki  two-color blinking, diff\_bertram  and spectral diffusion. diff\_neuhauser ; diff\_robinson  Evidence suggests that millisecond blinking, seen only in a small minority of quantum dots, is caused by nearby defects. diff\_sugisaki  However, we have previously reported a much faster type of blinking that occurs in a majority of quantum dots subject to resonant optical excitation. sps\_santori  This blinking behavior appears as a positive correlation in two-photon coincidence measurements. Blinking has also been observed in diamond color centers, sps\_beveratos  semiconductor nanocrystals, nano\_kuno  and in molecules. blink\_molecules  In our case, the correlation timescale depends on the laser excitation power, but can vary from less than 10 ns to at least 800 ns.

This article presents a detailed study of these fast memory effects. In addition to presenting data on the blinking of quantum dots under resonant excitation, we report for the first time negative photon correlations with timescales greater than 100 ns for quantum dots under pulsed excitation with the laser tuned above the bandgap of the host semiconductor. From a physical viewpoint, studying these complimentary memory effects can provide valuable information about the states of a quantum dot, the transitions between them, and especially the nature of the optical excitation process. From a practical viewpoint, blinking effects reduce the efficiency of quantum-optical devices based on single dots, sps\_santori ; sps\_michler2 ; sps\_zwiller ; sps\_moreau ; sps\_pelton ; twop\_santori ; sps\_yuan ; sps\_vuckovic  and also bring into question whether quantum dots are stable enough for use in proposed quantum computation schemes that involve optical control. qcex\_imamoglu ; qcex\_troiani  Understanding the mechanisms responsible for these effects is a first step toward being able to suppress them.

Both negative and positive correlations over long timescales can be explained reasonably well through a simplified model presented later in this article. Memory effects imply multiple long-lived configurations of the quantum dot, and our analysis suggests that these are likely states with differing total charge. As explained below, negative correlations occur because above-band excitation injects electrons and holes into the dot separately, whereas positive correlation (blinking) occurs because resonant excitation injects electrons and holes together, in pairs.

## II Samples

Sample A, the principle sample used in this study, has been described in Refs. twop\_santori, ; sps\_vuckovic, . It contains self-assembled InAs quantum dots (about 25 $`\mu `$m-2) embedded in the middle of a GaAs spacer layer, and sandwiched between GaAs/AlAs distributed-Bragg-reflector (DBR) mirrors, grown by molecular-beam epitaxy. The quantum dots were grown at a relatively high temperature, which leads to intermixing between the InAs and surrounding GaAs, shortening the emission wavelength to approximately 900-950 nm. Pillars (Fig. 1a) with diameters ranging from 0.3 $`\mu `$m to 5 $`\mu `$m and heights of 5 $`\mu `$m were fabricated in a random distribution by chemically assisted ion beam etching (CAIBE) using sapphire dust particles as etch masks. The resulting microcavities, exhibiting three-dimensional photon confinement, cav\_gerard ; cav\_solomon  have quality factors of approximately 1000 and spontaneous-emission rate enhancement (Purcell) factors as high as 5. The purpose of the optical microcavity was to enhance the photon collection efficiency and to decrease the spontaneous emission lifetime through the Purcell effect. For this study, the enhanced collection efficiency was valuable, since the data collection rate in photon correlation measurements is proportional to the square of the efficiency.

Sample B, described in Ref. sps\_santori, , provided additional data for Figs. 5 and 7 below. This sample contained quantum dots (about 11 $`\mu `$m-2) embedded in simple mesa structures (0.2-0.4 $`\mu `$m diameter) without optical cavities. The emission wavelengths of these dots were shorter (860-900nm).

## III Experiment

The main features of the experimental setups used for acquiring photon correlation data are shown in Fig. 1. This type of setup, known as a Hanbury Brown and Twiss (HBT) setup, hbt\_old  has become a common tool for studying the dynamics of single quantum systems, including quantum dots. This measurement technique can be used to characterize the performance of single-photon devices sps\_santori ; sps\_michler2 ; sps\_zwiller ; sps\_moreau ; sps\_pelton ; twop\_santori ; sps\_yuan ; sps\_vuckovic  and is more generally useful in studying spectral emission lines and determining how they are connected. xc\_moreau ; xc\_regelman2 ; xc\_kiraz ; polcor\_santori ; polcor\_shields  For the measurements presented below, several setups were used, but in all cases the samples were held in a cryostat at temperatures ranging from 4-15K and excited from a steep angle (about 54) by 3 ps pulses every $`T_{\mathrm{rep}}=13\mathrm{ns}`$ from a modelocked Ti-Sapphire laser. The emission was collected by a lens (NA=0.5), and imaged onto a pinhole to define a collection region, approximately 6 $`\mu `$m wide, on the sample. A single linear polarization was selected by a half-wave plate followed by a fixed polarizer. The emission was then spectrally filtered using a diffraction grating in a monochromator-type configuration, providing spectral resolutions from about 0.1 nm to 0.35 nm for the various setups. The spectral filter allows one to collect just a single emission line of a quantum dot.

The HBT portion of the setup consists of a beamsplitter with each output leading to a photon counter. The photon counters were EG&G SPCM avalanche photodiodes, having about 200 s-1 dark counts. The timing resolution varied from about 400 ps to 1.3 ns, depending on how narrowly the light was focused onto the detector active areas. Coincidence electronics, consisting of a time-to-amplitude converter (TAC) followed by a multi-channel analyzer (MCA) computer card, generated a histogram of the relative delay $`\tau =t_2t_1`$ between photon detections at the two counters ($`i=1,2`$) at times $`t_i`$.

The two types of memory effects we have observed appear in the photon correlation measurements shown in Fig. 2. The peaks at $`\tau =nT_{\mathrm{rep}}`$ correspond to events for which one photon was detected from some pulse $`m`$, and a second photon was detected from pulse $`m+n`$. The area of the central peak at $`\tau =0`$ gives information about photon number statistics within a single pulse. The side peaks at $`\tau 0`$ give information on how the emission from different pulses is correlated. Both histograms were obtained from the same quantum dot on sample A, dot 1. The emission was collected from a bright spectral line at about 932 nm, shown in Fig. 3. In Fig. 2(a), the excitation laser was tuned above the bandgap of the GaAs material surrounding the quantum dot, and the excitation intensity was chosen so that the collected emission intensity was far below its maximum value. The decrease of the side peaks near $`\tau =0`$ indicates a long-term (27 ns) anticorrelation between photons in consecutive pulses. This is a new effect not previously reported. In Fig. 2(b), the excitation laser was resonant with an excited level of the quantum dot at 904 nm. Such resonances are found through a photoluminescence excitation (PLE) measurement. res\_kamada ; rel\_toda ; res\_finley  The photoluminescence intensity is monitored as a function of laser wavelength, and typically 2 or 3 peaks are found. The rise of the side peaks in the photon correlation histogram near $`\tau =0`$ is opposite from the behavior in (a), and suggests a blinking of the quantum dot between a configuration that can emit light at the wavelength of our spectral filter, and one or more other configurations that cannot emit at this wavelength (but could possibly emit at other wavelengths). The fact that emission from the same quantum dot can have either positive or negative correlations over large timescales, depending on the laser wavelength, implies that there must be an important difference in how carriers are injected into the quantum dot for above-band and resonant excitation.

Fig. 3(a,b) shows photoluminescence spectra from dot 1. The measurements in Fig. 2 were performed on the bright emission line at 932 nm. In (a), the excitation was at 750 nm, above the GaAs bandgap, and many emission lines appear. Some of these are probably from the same quantum dot (trion and biexciton lines, for example) while others could be from other quantum dots. In (b), resonant excitation at 909 nm was used, and most of the other peaks have disappeared, demonstrating the selective nature of resonant excitation. Fig. 3(c) shows data obtained by sending light from the main emission line through a Michelson interferometer. This setup is described in Ref. twop\_santori,  and is similar to the one in Ref. linw\_kammerer2, . This measurement, performed without a polarizer, reveals fine structure though an oscillation or “beating” in the interference fringe contrast as the path length is varied, indicating that the emission line is actually a doublet with a 13 $`\mu `$eV splitting. Further measurements have shown that the two components have orthogonal linear polarizations, as in Ref. ex\_kulakovskii, . The existence of such a splitting suggests that this line originates from a neutral-exciton transition, rather than a charged-exciton (trion) transition, which would be polarization-degenerate in the absence of a magnetic field. ex\_bayer  For the measurements in Fig. 2, just one component of the doublet was used, selected through polarization.

Several photon correlation measurements taken at different excitation powers are shown in Fig. 4. In this figure, only the normalized areas of the peaks from the measured histograms are shown, plotted versus peak number, with peak 0 at $`\tau =0`$. For an ideal $`g^{(2)}`$ measurement, the normalized peak areas can be written as,

$$g^{(2)}[n]=\frac{n_1[m]n_2[m+n]}{n_1[m]n_2[m]},$$
(1)
where $`n_i[m]`$ is the number of photons measured on detector $`i`$ from pulse $`m`$. The light source is assumed to be stationary: a shift in $`m`$ does not change the expectation values in the numerator or denominator. The histogram peak areas obtained from our setup are approximately proportional to the numerator, as long as the mean count rates are small compared with the inverses of the relevant dead times ($`50\mathrm{ns}`$ for the photon counters, $`1\mu \mathrm{s}`$ for the electronics). The effects of these dead times can also be corrected through calibration relative to scattered laser light. The denominator can be calculated from the mean count rates on the detectors.

For the quantum dots we have studied, when absolute normalization using measured count rates was performed, the peak areas $`g^{(2)}[n]`$ converged to $`1`$ as $`n\mathrm{}`$, and were well fit by a simple two-sided exponential function:

$$g^{(2)}[n0]=1+g_1\mathrm{exp}[(|n|1)T_{\mathrm{rep}}/\tau _b],$$
(2)
where $`g_1`$ and $`\tau _b`$ are fitting parameters that characterize the amplitude and timescale of the memory effect, respectively. This shows that there were no additional blinking effects occurring with timescales greater than $`\tau _b`$, up to $`100\mathrm{s}`$. The fits using Eq. 2 typically have errors that can be explained in terms of statistical Poisson $`\sqrt{N}`$ fluctuations in the measured peak areas. As discussed below, this implies that a two-state Markov process is sufficient to describe the observed memory effects. When absolute normalization was not possible (due insufficient count-rate data), relative normalization was performed by fitting Eq. 2 to the data with an additional fitting parameter, a normalization coefficient multiplied by the entire right-hand side. This procedure was necessary for the data in Fig. 4, while absolute normalization was possible for the data from dots 3, 4, 6, and 7 in Figs. 6 and 7, presented below.

Both the negative and positive correlation effects in Fig. 4 display a strong dependence on laser excitation power. The four measurements in Fig. 4(a) were taken from dot 1 under above-band excitation, while the excitation power was varied to produce mean count rates on one photon counter of 25, 50, 100, and 200 kcps (kilocounts/second), as indicated. The measurements in Fig. 4(b) were taken from dot 2, another quantum dot on sample A (results from this dot appear in Ref. sps\_vuckovic, ). The emission wavelength was 920 nm, and the excitation laser was tuned to a resonance at 905 nm. Four excitation powers were used, 50, 200, 500, and 1200 $`\mu `$W, as indicated. For both data sets, the timescale of the memory effect clearly becomes shorter as the excitation power increases. This suggests that the fluctuations are primarily optically induced, at least for the excitation powers used here.

To enable comparisons between different quantum dots and with theoretical models, the laser excitation powers must be normalized in a useful way. When the excitation intensity is weak, the injection rate of carriers into the dot is expected to be proportional to intensity. However, the efficiency of this process depends on many experimental variables, such as the size of the focused laser spot, the size and shape of the pillar structure containing the dot, and the wavelength of the laser. The collected emission intensity also depends on many factors. In Fig. 5, the emission intensity from three quantum dots under pulsed excitation is plotted as a function of excitation power. In Fig. 5(a), dot 3, another quantum dot on sample A emitting at 919 nm, was excited above-band at 750 nm. In Fig. 5(b), dot 2 was excited on resonance at 905 nm. In both cases, a saturation behavior is observed that is well fit by an empirical model,

$$I/I_0=1e^{P/P_0},$$
(3)
where $`I`$ is the measured intensity, $`P`$ is excitation power, and $`I_0`$ and $`P_0`$ are constants characterizing the saturation intensity and power, respectively. The normalized excitation power is $`pP/P_0`$. This behavior is typical of an “incoherent” excitation process. On the other hand, a simple two-level system without dephasing excited on resonance is expected to undergo Rabi oscillations, characteristic of “coherent” excitation. This behavior can in fact occur in quantum dots when an isolated sharp resonance with little background can be found in the PLE spectrum. rabi\_kamada1 ; rabi\_htoon  Partially coherent behavior is shown in Fig. 5(c) for a quantum dot on sample B emitting at 877 nm and excited at 864 nm. Oscillations in the emission intensity are seen as the laser power is increased. However, the quantum dots discussed elsewhere in this article did not show this coherent effect when excited at the chosen PLE resonances.

Finally, Figs. 6 and 7 summarize the behavior of the memory timescale $`\tau _b`$ and amplitude $`g_1`$, both defined in Eq. 2, as a function of normalized excitation power for several quantum dots. In Fig. 6, dot 3 was excited at 750 nm, above the GaAs bandgap. Fig. 6(a) is a log-log plot showing the fitted value of $`\tau _b/T_{\mathrm{rep}}`$ as a function of $`p`$. The points approximately follow a line of slope $`1`$, indicating that the blinking rate $`1/\tau _b`$ is approximately proportional to the excitation power. The memory timescale can be as long as 130 ns for small excitation powers, and less than one pulse period for large powers. For large enough powers, the memory timescale becomes so short that even the innermost peak areas in the photon correlation histogram have areas close to $`1`$, and it becomes difficult to extract a value for $`\tau _b`$. Fig. 6(b) is a semilog plot showing the amplitude $`g_1`$ as a function of excitation power. Fig. 7 shows similar data for dots 2, 4, 5, 6, and 7 under resonant excitation. Various parameters of these quantum dots are summarized in Table 1. Dots 2, 4, 5, and 6 are from sample A, while dot 7 is from sample B. The blinking rate $`1/\tau _b`$ is again approximately proportional to excitation power below the saturation regime ($`P/P_0<1`$). The memory timescale was as long as 770 ns for dot 4 under weak excitation power. The blinking amplitude $`g_1`$ shows similar behavior as with above-band excitation, except that it is positive. The curve fits in these two figures are based on the theoretical model to be introduced next.

## IV Theoretical Model

The simple exponential decays in the measured photon correlation histograms (Fig. 4, for example) suggest that the memory effects can be described by a two-state Markov process. In such a process, only the most recent state of a system is needed to determine its future evolution. Suppose a quantum dot has two stable states $`1`$ and $`2`$ in which it can remain long after an excitation pulse. The effect of a single excitation pulse is described by:

$$\left(\begin{array}{c}p_1\\ p_2\end{array}\right)\left(\begin{array}{cc}1a& b\\ a& 1b\end{array}\right)\left(\begin{array}{c}p_1\\ p_2\end{array}\right),$$
(4)
where $`p_i`$ is the probability to be in state $`i`$, and $`a`$ and $`b`$ are the $`12`$ and $`21`$ transition probabilities, respectively. We next assume that, if we have detected a photon immediately after an excitation pulse, the system must have ended in state $`1`$. This is reasonable in our experiment, since we spectrally select an emission line corresponding to a unique transition. If a photon was detected from pulse $`0`$, the system evolves according to,

$$\left(\begin{array}{c}p_1[m]\\ p_2[m]\end{array}\right)=\frac{1}{a+b}\left(\begin{array}{c}b\\ a\end{array}\right)+\frac{a(1ab)^m}{a+b}\left(\begin{array}{c}1\\ 1\end{array}\right),$$
(5)
where $`p_i[m]`$ is the probability of the system to be in state $`i`$ after pulse $`m`$. Finally, let $`\eta _i`$ be the probability of emitting a photon immediately after an excitation pulse, given the dot was in state $`i`$ before the pulse. One can then calculate $`g^{(2)}[n]`$, obtaining a two-sided exponential function as in Eq. 2 with parameters,

$`\tau _b`$ $`=`$ $`{\displaystyle \frac{T_{\mathrm{rep}}}{\mathrm{ln}(1ab)}},`$ (6a)
$`g_1`$ $`=`$ $`{\displaystyle \frac{a(\eta _1\eta _2)}{b\eta _1+a\eta _2}}.`$ (6b)
If $`\eta _1>\eta _2`$, $`g_1`$ is positive, as observed experimentally with resonant excitation. If $`\eta _1<\eta _2`$, $`g_1`$ is negative, as observed with above-band excitation. Another important parameter is the internal efficiency, that is, the probability of emitting a photon after any given excitation pulse. The result is,

$$\eta _{\mathrm{tot}}=\frac{b\eta _1+a\eta _2}{a+b}.$$
(7)
We next consider the nature of states $`1`$ and $`2`$. They can have lifetimes approaching 1$`\mu `$s, so they cannot be optically active states such as excitons, biexcitons, and trions, which have nanosecond lifetimes. For quantum dot 1 discussed above, spectroscopy suggests that the studied emission line is a neutral-exciton transition, and thus state $`1`$ is the neutral ground state (empty dot). For state $`2`$, the “dark” state, recent spectroscopy literature on self-assembled quantum dots dark\_bayer ; spec\_hartmann ; spec\_finley ; ex\_bayer  and chemically synthesized nanocrystals nanocrystal1  suggests two main possibilities: a “dark exciton” or a charged state. Dark excitons are electron-hole pairs with spins oriented such that optical recombination is forbidden. Although these states can have microsecond lifetimes in chemically synthesized nanocrystals with typical diameters less than 5 nm, it is unlikely that they could be as long-lived in our self-assembled quantum dots. Self-assembled dots can have reduced symmetry, so that the dark-exciton transition is not entirely forbidden. ex\_bayer  Additionally, if the energy splitting between the bright and dark exciton levels is proportional to the inverse cube of the dot radius, nanocrystal1  spin flip processes might occur much faster in our samples, with typical dot radii of 30 nm. Dark excitons in InAs quantum dots have not yet been adequately studied, and we cannot reject this possibility with certainty. Nevertheless, we favor the other possibility, that state $`2`$ is a charged state. This choice allows one to explain all of the observed memory effects with a single model. Charge fluctuations in quantum dots under continuous-wave (cw) above-band excitation have been observed through correlations between exciton and trion photon emissions, xc\_kiraz  and we have seen similar behavior in our samples. The assumption below is that the extra charges reside inside the quantum dot. An alternative possibility not considered here is that extra charges could be associated with impurities outside the quantum dot; this would not explain the negative correlations observed with above-band excitation.

The model is shown schematically in Fig. 8. Level $`0`$ is the neutral ground state, and level $`X`$ is the single-exciton state. Level $`e^{},h^+`$ is a charged state. There could in reality be more than one charged state involved significantly with the dynamics, but we consider only one charged state in this model. Level $`X^\pm `$ is a trion (charged-exciton) state. Some of these levels can have degeneracies, but in these cases we are interested only in the total occupation probabilities.

The system evolves in two steps. First, a strong optical field is applied for a short time duration $`\mathrm{\Delta }t`$, during which upward transitions are induced. Two of these transitions, with rates $`\alpha `$ and $`\beta `$, change the total charge of the dot from $`\mathrm{neutral}\mathrm{charged}`$ and from $`\mathrm{charged}\mathrm{neutral}`$, respectively. These transitions correspond physically to the capture of single electrons and holes from the surrounding region into the quantum dot. The third transition, with rate $`x`$, brings the quantum dot from $`0`$ to $`X`$. This transition could occur either through resonant excitation, or through the capture of an entire electron-hole pair. During the second step, which could last several nanoseconds, the system relaxes back down to levels $`0`$ and $`e^{},h^+`$ through electron-hole recombination. This is assumed to be a charge-conserving process. If a relaxation occurs from $`X`$ to $`0`$, a photon is emitted at the special wavelength that our setup detects.

This model can be solved to give the following parameters for the general Markov process in Eq. 4:

$`a`$ $`=`$ $`{\displaystyle \frac{\alpha }{\alpha +\beta }}(1e^{(\alpha +\beta )\mathrm{\Delta }t}),`$ (8a)
$`b`$ $`=`$ $`{\displaystyle \frac{\beta }{\alpha +\beta }}(1e^{(\alpha +\beta )\mathrm{\Delta }t}),`$ (8b)
$`\eta _1`$ $`=`$ $`1ae^{(\alpha +x)\mathrm{\Delta }t},`$ (8c)
$`\eta _2`$ $`=`$ $`b.`$ (8d)
To fit this model to the experimental data, we make a further assumption, that the rates $`\alpha `$, $`\beta `$, and $`x`$ are proportional to the excitation power $`p`$. Inserting Eqs. 8 into Eq. 7 gives the saturation behavior,

$$\eta _{\mathrm{tot}}=\frac{\beta }{\alpha +\beta }(1e^{(\alpha +x)\mathrm{\Delta }t}).$$
(9)
Comparing this with the empirical Eq. 3 allows the assignment $`(\alpha +x)\mathrm{\Delta }t=P/P_0=p`$. We then introduce two fitting constants, $`C_1=(x\beta )/(x+\alpha )`$ and $`C_2=\alpha /\beta `$. Substituting these and Eqs. 8 into Eqs. 6 gives the final result:

$`\tau _b`$ $`=`$ $`{\displaystyle \frac{T_{\mathrm{rep}}}{(1C_1)p}},`$ (10a)
$`g_1`$ $`=`$ $`C_2\left({\displaystyle \frac{e^{C_1p}1}{e^p1}}\right).`$ (10b)
The parameter $`C_1`$ has special significance, since it determines whether electrons and holes are more often added individually or in pairs. If they are added individually ($`C_1<0`$), Eq. 10b predicts negative correlation ($`g_1<0`$) in the detected photons. If they are added more often in pairs ($`C_1>0`$), Eq. 10b predicts positive correlation ($`g_1>0`$). These behaviors have simple qualitative explanations. It follows from Eqs. 1 and 2 that the quantity $`1+g_1`$ is proportional to the conditional probability, given that a photon was detected from pulse $`0`$, that a second photon will be detected from pulse $`1`$. When a first photon is detected, the dot is empty immediately afterward. For single-carrier injection, two injections must occur before another photon can be emitted, and thus it is unlikely that another photon will be emitted from pulse $`1`$ if the injection rate is small. The opposite argument applies for the injection of entire electron-hole pairs. If a photon was emitted from pulse $`0`$, it is especially likely that another photon will be emitted from pulse $`1`$, since only a single additional pair needs to be injected. Otherwise, the dot could be charged, in which case the quantum dot will appear dark at the selected wavelength.

The lines in Figs. 6(a) and 7(a) were obtained by fitting Eq. 10a to the measured blinking timescales. The values of $`C_1`$ obtained from these fits are summarized in Table 1. As expected from the preceding discussion, $`C_1`$ is negative for above-band excitation, and positive in all five cases for resonant excitation. Substantial variation in the value of $`C_1`$ is seen among the different dots under resonant excitation, however. $`C_1`$ is much closer to its maximum value of $`1`$ for dots 4 and 5, than for dots 2 and 6. In our model, $`C_1`$ characterizes how “clean” the resonant excitation process is, or in other words how rarely extra charges are added and removed from the quantum dot. Perhaps the differences among these dots are related to the emission wavelength. It is also possible that for one or more of these dots, the studied emission line could be a trion (charged exciton) transition. In those cases our model should still apply (after changing the labels in Fig. 8), but it would not be surprising if the values of the fitting parameters were different.

The curves in Figs. 6(b) and 7(b) were obtained by fitting Eq. 10b to the data using the values of $`C_1`$ already obtained and using $`C_2`$ as a fitting parameter. The fits do not match the data perfectly, a sign that the model is too simple. The saturation regime ($`P/P_0>1`$) is difficult to model accurately, since a large number of states are involved. The model does correctly predict that $`g_1`$ tends to zero for large excitation powers, as observed in the data. The parameter $`C_2`$ has practical importance, since according to Eq. 9, the maximum internal efficiency at the selected wavelength is $`\eta _{\mathrm{max}}=\beta /(\alpha +\beta )=1/(1+C_2)`$. It should be cautioned, however, that using this formula with the fitted values of $`C_2`$ may not give the correct efficiency in the saturation regime, where the model is least accurate.

An important question is why the charge of a quantum dot should ever change when the excitation wavelength is tuned below the GaAs bandgap and below the InAs wetting layer band edge. This could be related to the “wetting layer tail” observed in PLE spectra. This feature has been attributed to continuum states associated with the combined wetting layer-quantum dot system. rel\_toda  If these states are not localized to a single quantum dot, electrons and holes excited into these states by a laser pulse could be captured by different quantum dots, changing their charges, for example. It has also been suggested that an Auger-type process, which would allow an electron to escape from the quantum dot, could play an important role in the relaxation of electron-hole pairs from excited states. auger\_norris ; auger\_sanguinetti  Two-photon processes are an unlikely mechanism when the excitation power is far below saturation. This is because the blinking rate $`1/\tau _b`$ is observed to vary approximately linearly with the excitation power.

## V Conclusions

We have observed sub-microsecond memory effects in quantum-dot photoluminescence on two samples, one with optical microcavities and one without. Other groups have not yet reported similar behavior, but other studies have not, to our knowledge, explored pulsed resonant excitation, or pulsed above-band excitation far below the saturation level, the two regimes important in our study. These memory effects imply the existence of multiple long-lived states, which are most likely states with different total charge. If this interpretation is correct, it is apparently difficult to prevent the charge of a semiconductor quantum dot from changing during optical excitation.

Fluctuations in the charge of a quantum dot could pose serious difficulties for proposed applications. Light emitters based on single quantum dots will have reduced internal efficiencies at a particular wavelength. Even though the blinking seems to disappear at large excitation powers in photon correlation measurements, our model suggests that the efficiency still suffers, due to the presence of multiple configurations. Optically induced charge fluctuations could also be problematic in schemes for quantum computation that involve optical control of single charges or excitons.

Better stability might be achieved using laser excitation resonant with the fundamental exciton transition. We did not attempt this because of the difficulty of removing scattered laser light, but at least one group has performed single-dot measurements under these conditions. spec\_bonadeo1  Another option might be to design the optical excitation process so that the transition rate into an unwanted configuration is much smaller than the transition rate out of it. In this case, the quantum dot would spend most of its time in the desired configuration. Finally, if charge fluctuations are, in fact, related to continuum states, then fabrication of quantum dots with a low density and without a wetting layer might be advantageous.

###### Acknowledgements.

Supported in part by MURI UCLA/0160-G-BC575. The authors thank A. Scherer and T. Yoshie from Caltech for providing access to CAIBE and for help with fabrication, and M. Pelton for patterning of sample B and for useful comments.


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# Untitled Document

##

In our previous papers  we have presented the arguments in favour of that the Kaluza-Klein picture of the world is confirmed by the experimentally observed hadronic spectra.

In papers  the nucleon-nucleon dynamics at very low energies has been studied and we have found that geniusly simple formula for KK excitations provided by Kaluza-Klein approach gives an excellent description for the mass spectrum of two-nucleon system. In articles  we have presented additional arguments in favour of Kaluza and Klein picture of the world. In fact, we have shown that simple formula provided by Kaluza-Klein approach with the fundamental scale calculated early  gives an excellent description for the mass spectrum of two-pion and three-pion systems. Taking this line, we have performed an analysis of experimental data on mass spectrum of the resonance states containing strange mesons and compared them with the calculated values provided by Kaluza-Klein scenario . By this way we have found out quite an interesting correspondence shown below

7-storey

$$(\mathrm{?})\sigma (650)M_7^{\pi \pi }(640644)K^{}(892)M_7^{K\pi }(893898)$$

15-storey

$$f_2(1275)M_{15}^{\pi \pi }(12731275)K_2^{}(1430)M_{15}^{K\pi }(14311434)$$

17-storey

$$f_{0,2}(1430)M_{17}^{\pi \pi }(14351438)K_2^{}(1580)M_{17}^{K\pi }(15791582)$$

18-storey

$$f_0(1522)M_{18}^{\pi \pi }(15181520)K^{}(1680)M_{18}^{K\pi }(16541657)$$

19-storey

$$f_{0,\mathrm{?}}(1580)M_{19}^{\pi \pi }(15991601)K_3^{}(1780)M_{19}^{K\pi }(17301733)$$

22-storey

$$\eta _{\mathrm{?},2}(1840)M_{22}^{\pi \pi }(18451846)K_0^{}(1950)M_{22}^{K\pi }(19601963)$$

23-storey

$$f_4(1935)M_{23}^{\pi \pi }(19271928)K_4^{}(2045)M_{23}^{K\pi }(20382040)$$

27-storey

$$\rho _5(2250)M_{27}^{\pi \pi }(22562257)K_5^{}(2380)M_{27}^{K\pi }(23522354)$$

From this correspondence it follows that $`K\pi `$-system looks like a system built from two-pion system by replacement of some one pion with a kaon. In fact, all experimentally observed hadronic states in $`K\pi `$-system have the corresponding partners in two-pion system. However, some hadronic states in two-pion system do not have the corresponding strange partners in $`K\pi `$-system experimentally observed so far. That is why the further study of $`K\pi `$-system is quite a promising subject of the investigations.

Concerning three-pion system we have found out that

$$a_2(1311)M_{10}^{3\pi }(13091313),a_2(1311)M_{10}^{\rho \pi }(13101312).$$
(1)
Moreover, we predict the strange partner of $`a_2`$-meson which we would like to call as $`a_2^s`$-meson; see Table 17 and Table 21 in

$$\overline{)a_2^s(1520)M_{10}^{K2\pi }(15171523),a_2^s(1520)M_{10}^{K\rho }(15191522)}.$$
(2)
Apart of isospin $`a_2^s(1520)`$-meson may have the same quantum numbers as $`a_2(1311)`$-meson. We call up to search $`a_2^s(1520)`$-meson and other strange partners of the three-pion states experimentally observed till now. In this respect it seems the factory with an intensive kaon beams would be a very good device to realize such programm.


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# Flat-band ferromagnetism proposed for an organic polymer crystal

## Abstract

Motivated from the flat-band ferromagnetism conceived theoretically for a single chain of five membered rings (polyaminotriazole) by Arita et al., \[Phys. Rev. Lett. 88, 127202 (2002)\], we have studied whether the magnetism can indeed occur as a bulk, i.e., in a three-dimensional crystal of the polymer, by means of the spin density functional calculation. We find that the intra-chain ferromagnetism is robust against crystallization as far as the flat band is made half-filled. We have further investigated the actual crystal doped with various compounds, where HF2 is shown to put the system close to the bulk ferromagnetism while stronger anions such as BF4 or PF6 should be promising.

Materials design, especially that from the standpoint of many-body effect, is one of the most challenging avenues in condensed matter physics. In particular, designing magnets in materials consisting entirely of non-magnetic elements is an issue of great interest. In fact, a variety of ideas for exotic ferromagnetism have been proposed in this decade, where first-principles calculations are combined with electron-correlation studies for models exemplified by the Hubbard model. In this context, organic ferromagnets are of special interest. While organic ferromagnetism has been realized in localized-spin systems such as TDAE-C60, whether we can have a band (i.e., itinerant) ferromagnetism in organics remains a challenging question.

Recently, we have proposed a new possibility of itinerant ferromagnetism in an organic polymer of five-membered rings, polyaminotriazole (PAT), and have explained the origin of the magnetism in terms of Mielke and Tasaki’s flat-band ferromagnetism by coupling a first-principles band calculation with a study for the Hubbard model. Concisely, the flat-band ferromagnetism occurs when there is a dispersionless band which satisfies a special condition (called connectivity condition) in the one-electron band structure. Note that the magnetism is distinct from the usual narrow-band limit in that the magnetism occurs as a quantum interference effect in the repulsively interacting system for a finite transfer energy.

While the monomer (aminotriazole) is commercially available, experimental attempts at its polymerization have just begun. Experimentally, we have to aim at a bulk magnetization, so theoretically it is imperative to study whether we can have a ferromagnetism in three-dimensional crystals, which is of fundamental as well as practical interests.

The key issues are (i) the robustness of the intra-chain ferromagnetism to start with (i.e., whether the inter-chain interaction in the crystal disturbs the intra-chain ferromagnetism), (ii) whether the inter-chain interaction can be ferromagnetic (i.e., the competition between the ferromagnetic (direct-exchange) inter-chain interaction and the inter-chain energy gained by the antiferromagnetic order), and their energy scale, and (iii) which chemial dopants should be opted to bring the flat-band close to half-filling, a necessary condition for the flat-band ferromagnetism. The present paper addresses these problems.

Problem (i) is non-trivial, since the presence of adjacent chains can affect the magnetism within the chain. Conversely, if the inter-chain interaction does not destroy the intra-chain ferromagnetism, this is already interesting for experimental opportunities, since if we can for example epitaxially grow the organic crystal on a metallic substrate with a large work function such as platinum, the interface state of the PAT chain can possibly have a net polarization. In fact, we shall show that the presence of neighboring chains in the crystal does not destroy the intra-chain ferromagnetism for the realistic chain-chain distance.

On the other hand, problem (ii) on the inter-chain magnetic coupling, we shall show that ferromagnetic and antiferromagnetic interactions are both small in magnitude and their competition is subtle.

As for (iii), we we have studied various anions as dopants in PAT crystal to examine the magnetic property. We shall conclude that, while the dopant studied here, ClO4, F, and HF2, bring the system close to, but not in, the ferromagnetic phase, the chemical trend indicates that stronger anions having higher electron affinity (BF4 and PF6) are expected to realize the flat-band ferromagnetism.

We have adopted a first-principles band calculation within the framework of the generalized gradient approximation based on the spin-density functional theory (GGA-SDFT) to compare the total energy of various magnetic states. In the GGA-SDFT calculations the exchange-correlation functional introduced by Perdew, Burke, and Wang is adopted with the ultra-soft pseudopotential in a separable form. The wave functions are expanded by plane waves up to a cut-off energy of 20.25 Ry.

To clarify the physics the doping has been done in two ways. We first look at the band-filling dependence by reducing the number of electrons, where a uniform negative background charge is introduced to make the system charge-neutral as in Ref.. The latter part of the paper examines actual anions as dopants, where the charge transfer across the anion and PAT is calculated self-consistently.

We start with the atomic configuration of the (undoped) PAT crystal obtained by the structure-optimization, shown in Fig.1, where the total energy is minimized with the conjugate gradient scheme. We have assumed that the unit-cell is orthorhombic and contains two chains of PAT which form a herringbone structure. We have studied two types of the crystal structure, A(non-staggered) and B(staggered). Similar crystal structures have been considered in recent calculations for polythiophene and poly-phenylene-vinylene, where PT2 and PT1 in Ref. correspond to our A and B, respectively.

We have determined the size of the unit-cell as follows. We first determined the dimension of the unit-cell along the chain to be 7.17 Å, which minimizes the ground state energy of an isolated chain. For the unit-cell size perpendicular to the chain, we have calculated the total energies by changing the linear dimension with the increment of 1.0 au (i.e., $`0.529`$ Å) to search for the energy minimum. The resulting unit-cell size is 8.46Å$`\times `$ 6.35Å.

We have then doped the system, first by reducing the number of electrons. We focus on the case of the half-filled flat band, for which the flat-band ferromagnetism is originally conceived. In the present crystal, top four valence bands are nearly flat to be precise (corresponding to the presence of four five-membered rings in a unit cell), and the half-filling refers to the case of one carrier per ring. We have obtained four types of solution for both A and B crystal structures in the doped case: an intra-chain ferromagnetic(F) and inter-chain antiferromagnetic(AF) state (which we call interAF hereafter), an intra-chain AF and inter-chain F state (intraAF), a state antiferromagnetic both for intra-chain and inter-chain (AF2), and finally the ferromagnetic state.

The band structure for the doped system is shown in Fig.2 for the ferromagnetic solution. For both A and B structures, we can see that the dispersion along the chain is quite similar to that of an isolated PAT chain (shown in the inset), from which we can see that the effect of the inter-chain interaction is small for the ferromagnetic state.

The total energies of the three AF states for the structure A(B), as measured from those of the F state in respective structures, are, respectively : $`E(\mathrm{interAF})=40`$ (0) meV, $`E(\mathrm{intraAF})=130`$ (100) meV and $`E(\mathrm{AF}^2)=40`$ (100) meV. If we estimate the “intra-chain magnetic coupling” as $`J_{\mathrm{intra}}=(\mathrm{intraAF})E(\mathrm{F})`$, and “inter-chain magnetic coupling” as $`J_{\mathrm{inter}}=E(\mathrm{interAF})E(\mathrm{F})`$, $`J_{\mathrm{intra}}`$ is $`100`$ meV ($`<0`$, i.e., ferromagnetic) for both A and B structures. If we compare this value with that for a single PAT chain (estimated to be $`50\times 2=100`$ meV, where the factor 2 is required for comparison with the present value for two chains per unit cell), the intra-chain ferromagnetism is seen to be quite robust even in the crystal.

On the other hand, the situation is subtle for $`J_{\mathrm{inter}}`$. While $`J_{\mathrm{inter}}`$ is estimated to be 40 meV ($`>0`$, i.e., AF) for structure A, $`J_{\mathrm{inter}}0`$ meV (paramagnetic) for B. This implies that F and AF interactions are both small in magnitude, so that the value of $`J_{\mathrm{inter}}`$ should depend on details of the crystal structure.

This is why we move on to first-principles calculation of the flat-band ferromagnetism for actual chemical dopants introcuded in PAT crystal. We should opt for anions having large electron affinities, because the bands of the dopants to which the charge transfer from PAT occurs will then lie well away from the bands around the Fermi energy (i.e., the flat bands). In the present study, we have studied halogens (Cl, F) and halogen compounds (ClO4, HF2). To make the flat bands half-filled, we put four dopants in each unit-cell that contains four five-membered rings. As for the polymorph we focus here on structure A, and we have adopted a slightly larger unit-cell size (9.52Å$`\times `$ 7.41Å$`\times `$ 7.17Å) to accommodate ClO4 and HF2.

We first found that we can exclude the Cl-doped case since the paramagnetic solution has a total energy lower than that for the ferromagnetic one by $``$ 270 meV. For ClO4, F and HF2, on the other hand, the ferromagnetic state becomes lower in energy than the paramagnetic state. In Fig.3(a), we show the optimized atomic configuration for the ferromagnetic solution in the ClO4-doped crystal. We can see that the insertion of the ClO4 molecules significantly changes the relative position of the two PAT chains in the unit-cell from those in Fig.1, which suggests that the molecules may crucially affect the electronic properties and unfavors the intra-chain ferromagnetism.

So let us turn to the band structure in Fig.3(b) to see whether the states around $`E_F`$ are modified. If the electron affinity of ClO4 were sufficiently larger than that of PAT, the ClO4-charactered bands would not hybridize with the states around $`E_F`$. However, the result shows that the hybridization occurs for the flat (valence-top) bands, and the Mielke-Tasaki’s orbits are severely affected.

For a more quantitative argument, we have looked at the charge distribution by adopting a method due to Aizawa and Tsuneyuki for estimating the Mulliken charge for plane-wave basis band calculations. We divide the whole system into subsystems with each subsystem containing one atom, and calculate the valence charge for each. Summing the valence charges for dopant (ClO4 here), we can estimate the charge transfer from PAT to the dopant($`Q`$). For PAT-ClO4, we have found that $`Q`$ for each dopant molecule (i.e., for each five-membered ring) is $`0.88`$, i.e., the charge transfer is incomplete. This suggests that the bands (Mielke-Tasaki’s) to which we wanted to hole-dope are hybridized with the dopant (ClO4) band. We can indeed confirm this from the plot of the (majority-spin) wave function as a sum ($`\rho `$ hereafter) of the squared absolute values of flat bands at $`\mathrm{\Gamma }`$ in Fig.3(c). We can see that the amplitude extends substantially to ClO4, especially on O sites. In fact, the ground state becomes antiferromagnetic even within the chain, with $`J_{\mathrm{intra}}=60`$ meV and $`J_{\mathrm{inter}}=20`$ meV.

Let us now move on to the fluorine-doped case. We show the optimized atomic configuration and the band structure in Fig.4. The band structure is similar to those plotted in Fig.2 with the charge transfer estimated to be $`Q0.78`$. The wave function in Fig.4(c) indicates that the amplitudes on C atoms becomes considerably small, which means that the connectivity condition, necessary for the flat-band ferromagnetism, is violated. The exchange energies are estimated to be $`J_{\mathrm{intra}}=40`$ meV and $`J_{\mathrm{inter}}=20`$ meV, so that the ground state is antiferromagnetic both within and across the chains.

Let us finally discuss the result for HF2, which has the largest electron affinity among the dopants studied here. While the band structure and wave function in Fig.5 suggest that Mielke-Tasaki’s states hybridize with anion states to some extent, the charge transfer is calculated to be $`Q=1.1`$, so that this case is more promising than that of ClO4 or F. While $`J_{\mathrm{intra}}10`$ meV and $`J_{\mathrm{intra}}30`$ meV are still both antiferromagnetic, $`J_{\mathrm{intra}}`$ becomes considerably smaller than those for ClO4 and F, reflecting the high electron affinity of HF2. From the chemical trend, we may expect that a favorable situation (similar to the uniform doping described in the first half of the paper) for the ferromagnetism is expected to be realized for BF4 or PF6, which are known to have higher electron affinity, although a first-principles calculation for BF4 or PF6 would be too demanding, since these have many valence electrons or require large cut-off energies in the plane-wave expansion.

To summarize, a spin density functional calculation shows that the three-dimensional crystal of chains of five-membered rings has a robust intra-chain ferromagnetism originally conceived for an isolated polymer. For the chemical doping BF4 or PF6 with high electron affinity should be promising. The magnetism in the organic crystal may also be controlled by the pressure effect.

We would like to thank H. Nishihara, Y. Yamanoi and S. Nakao for fruitful discussions. This work was supported in part by a Grant-in-Aid for Creative Research (No.14Gs0297) and Special Coordination Funds for Promoting Science and Technology from Japanese Ministry of Education. The GGA calculation was performed with TAPP (Tokyo Ab-inito Program Package), where RA and YS would like to thank J. Yamauchi for useful discussions. Numerical calculations were performed on SR8000 in ISSP, University of Tokyo.