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# Single-electron transistors in electromagnetic environments

## I Introduction

The single-electron transistor (SET), which consists of two small-capacitance tunnel junctions in series and a gate electrode, is an important example of the single-electron-tunneling circuit. Although the SET is more complex than the single junction, the SET has an advantage over the single junction in that the single-electron charging effects typified by “Coulomb blockade” are easily observed in the SET. As a result, the SET can be used, e.g., as an electrometer with an extremely high sensitivity, $`e/\sqrt{\text{Hz}}`$ (e.g., Ref. Averin and Likharev, 1991). When the electrodes of the tunnel junctions in the SET are in the superconducting state, the SET is also important from the viewpoint of quantum computing; the first one-quantum-bit operation in solid-state electronic devices was demonstrated in a circuit with small-capacitance Josephson tunnel junctions, and the state of the quantum bit was read out by measuring the Josephson-quasiparticle (JQP) current of a superconducting SET.Nakamura et al. (1999) The supercurrent of superconducting SETs has also been studied extensively.Joyez (1995) One expects that the supercurrent is $`2e`$ periodic in the gate-induced charge. In many experiments, however, a period of $`e`$ has been seen, which suggests the existence of subgap quasiparticle states,Joyez (1995) or “quasiparticle poisoning.” The periodicity of the current was also discussed at finite voltages.Geerligs et al. (1990); Tuominen et al. (1992); Amar et al. (1994) The periodicity depends strongly on how the leads connected to the sample are filtered,Joyez (1995) so that the “quasiparticle poisoning” would be viewed as an environmental effect.

Theoretically,Ingold and Nazarov (1992) the details of single-electron charging effects in SETs depend on the impedance of the electromagnetic environment, $`Z(\omega )`$, both in the normal state and in the superconducting state. It is predicted that as $`\text{Re}[Z(\omega )]`$ is increased, the voltage scale of the Coulomb blockade in the normal-state current–voltage ($`I`$$`V`$) characteristics becomes larger, and in the superconducting state, the supercurrent is replaced by the Coulomb blockade. The experimentsJoyez (1995); Geerligs et al. (1990); Tuominen et al. (1992); Amar et al. (1994) on superconducting SETs mentioned above were done in the low-impedance environment, where $`\text{Re}[Z(\omega )]`$ was much smaller than the quantum resistances: $`R_Qh/(2e)^26.5`$ k$`\mathrm{\Omega }`$ for Cooper pairs and $`R_Kh/e^226`$ k$`\mathrm{\Omega }`$ for quasiparticles. In order to obtain higher $`\text{Re}[Z(\omega )]`$, thin-film resistorsHaviland et al. (1991); Cleland et al. (1992) can be used for the on-chip leads. A superconducting SET was biased with $``$50 k$`\mathrm{\Omega }`$ Cr resistors, and a Coulomb blockade was observed in the $`I`$$`V`$ curve.Haviland et al. (1994) Similar resistors ($`220`$ k$`\mathrm{\Omega }`$) were also employed for the study of Cooper-pair cotunneling in superconducting SETs.Lotkhov et al. (2003) A drawback of these thin-film resistors is that the resistance is not tunable, i.e., the same SET cannot be measured in different environments. A tunable environment has been realized by capacitively coupling a two-dimensional electron gas to a SET.Kycia et al. (2001); Rimberg and Lu (2002) In the work presented here, a simpler method is employed to create tunable environments for superconducting SETs.

We use one-dimensional (1D) arrays of dc superconducting quantum interference devices (SQUIDs) for the on-chip leads,Watanabe and Haviland (2001, 2003) which can be fabricated simultaneously with superconducting SETs. The SQUID configuration enables us to vary in situ the effective impedance of the arrays by applying a weak external magnetic field ($`110`$ mT) perpendicular to the SQUID loop. The superconducting SET in our samples, on the other hand, does not have a SQUID configuration, and therefore its parameters are practically independent of the external magnetic field. The zero-bias resistance of SQUID arrays at low temperatures can be controlled over several orders of magnitude (e.g., Fig. 13 of Ref. Watanabe and Haviland, 2003), and SQUID arrays are especially suitable for achieving a high-impedance environment. In fact, distinct Coulomb blockade was observed in single Josephson junctions by biasing with SQUID arrays.Watanabe and Haviland (2001) When the sample is driven to the normal state, the array leads are no longer tunable, but the resistance can be much larger than $`R_K`$. Hence, it is still possible to study the environmental effects on SETs by comparing the samples with and without array leads. In this paper, the environmental effects on SETs is discussed both in the normal state and in the superconducting state. An emphasis is placed on the case of a high-impedance environment, which has not been thoroughly experimentally studied.

## II Experiment

### II.1 Fabrication of small-capacitance tunnel junctions

The tunnel junctions (Al/Al2O3/Al) were fabricated on a SiO2/Si substrate with Au/Ni bonding pads. We employed a process based on electron-beam lithography and double-angle shadow evaporation, which is similar to the one described in Ref. Watanabe and Haviland, 2003. The evaporation of Al was done at an rate of $`0.10.2`$ nm/s in a vacuum system with the base pressure of $`10^8`$ Pa. During the evaporation, the pressure was usually $`(24)\times 10^6`$ Pa. The Al2O3 tunnel barrier was formed by exposing the base Al layer to $`120`$ Pa of O2 for $`0.52`$ min. before the deposition of the top Al layer. The thickness of the barrier determines the normal-state resistance of the junction per unit junction area. The normal-state resistance is a key parameter of the sample, and will be discussed in Sec. II.3.

Figure 1 shows a scanning electron micrograph of a sample. The SET is biased with two pairs of leads enabling four-point measurements. A part of each lead close to the SET consists of a 1D array of dc SQUIDs.

### II.2 Measurement at low temperatures

The samples were measured in a 3He–4He dilution refrigerator (Oxford Instruments, Kelvinox 400) mainly at $`T=0.020.6`$ K, and the normal-state resistance was determined at $`T=1.84.5`$ K. (Note that the superconducting transition temperature of Al is 1.2 K.) The temperature was calculated from the resistance of a ruthenium-oxide thermometer fixed to the mixing chamber. Magnetic fields on the order of $`110`$ mT were applied by means of a superconducting solenoid. In this magnetic-field range, the temperature error of ruthenium-oxide thermometers due to magnetoresistance is negligibly small (e.g., a typical value of the error at $`T=0.05`$ K is less than 0.1%).Watanabe et al. (2001) The samples were placed inside a copper can which was thermally connected to the mixing chamber. Because there was no low-temperature filtering, we inserted low-pass filters between the cables connected to the cryostat and the measurement circuit.

The $`I`$$`V`$ curve of the SET was measured in a four-point configuration (see Fig. 1). The bias was applied through one-pair of leads, and the potential difference was measured through the other pair of leads with a differential voltage amplifier (DL Instruments, 1201, $`>1`$ G$`\mathrm{\Omega }`$ input impedance). The current was measured with a current amplifier (DL Instruments, 1211). The SQUID arrays could be measured in a two-point configuration (same current and voltage leads). When we measure the arrays on the same side of the SET (e.g., $`I+`$ and $`V+`$ in Fig. 1), current does not flow through the SET, and the series resistance of two arrays is obtained. The zero-bias resistance measured in this configuration will be discussed in Sec. II.3.

### II.3 Characterization of the samples

In this work, we measured the three pairs of SETs listed in Table 1.

Each pair (e.g., samples 1a and 1b) was fabricated simultaneously on the same chip. One SET has SQUID-array leads with $`N=65`$ junction pairs in each array, while the other SET has no SQUID-array leads ($`N=0`$). For all the samples, the junction area was designed to be 0.1$`\times `$0.1 $`\mu `$m2 in the SET and 0.3$`\times `$0.1 $`\mu `$m2 in the SQUID arrays.

The uniformity of the SQUID arrays could be estimated by measuring the normal-state resistance in all two-point configurations (six in total). In some configurations, current flows through the SET and thus the normal-state resistance $`R_n`$ of the SET has to be subtracted from the measured resistance in order to obtain the series resistance of two arrays. For our samples, the results of the two-point measurements agreed with one another within 3%–4%. By averaging all the results, the normal-state resistance $`r_n^{}`$ per junction pair of the arrays is calculated, and shown in Table 1. If the tunnel-barrier thickness is identical for all junctions on the same chip, one would expect $`R_n/r_n^{}12`$ from the junction area. From Table 1, the ratio is $`1621`$, which is the correct order of magnitude.

From the normal-state resistance, I calculate the Josephson energy, which is an important parameter of the samples. For example, the maximum Josephson energy $`E_{J0}^{}`$ between adjacent islands in the SQUID arrays is given by the Ambegaokar-Baratoff formula,

$$E_{J0}^{}=\frac{h\mathrm{\Delta }_0}{\mathrm{\hspace{0.17em}8}e^2r_n^{}},$$
(1)
where $`\mathrm{\Delta }_0`$ is the superconducting energy gap ($`0.2`$ meV for Al). Because of the SQUID configuration, the effective Josephson energy $`E_J^{}`$ in the arrays is modulated periodically by applying an external magnetic field $`B`$ perpendicular to the SQUID loop,

$$E_J^{}=E_{J0}^{}\left|\mathrm{cos}\left(\pi \frac{BA}{\mathrm{\Phi }_0}\right)\right|,$$
(2)
so long as $`B`$ is sufficiently smaller than the critical field, where $`\mathrm{\Phi }_0=h/2e=2\times 10^{15}`$ Wb is the superconducting flux quantum, and $`A`$ is the effective area of the SQUID loop, which is 0.7$`\times `$0.2 $`\mu `$m2 in our samples. Equation (2) is a key to understand Fig. 2, which shows that the zero-bias resistance $`R_0^{}`$ of two SQUID arrays in series oscillates as a function of $`B`$ until $`B`$ becomes comparable to the critical field. Note that the first peak appears at $`B=7`$ mT, where the normalized flux $`BA/\mathrm{\Phi }_0`$ is 0.5 for our samples with $`A=0.14`$ $`\mu `$m2. In Ref. Haviland et al., 2000, the SQUID array was modeled as a network of capacitors and inductors, and the real part of the array impedance was shown to be proportional to $`1/\sqrt{E_J^{}}`$ at low enough frequencies. At $`B60`$ mT in Fig. 2, the superconductivity is suppressed, and $`R_0^{}`$ takes a value comparable to $`2Nr_n^{}`$. The small temperature dependence in this magnetic-field regime is due to the single-electron charging effect. In general, the $`I`$$`V`$ curve of SQUID arrays is nonlinear (e.g., Fig. 3 of Ref. Watanabe and Haviland, 2003), and therefore, SQUID arrays are not described by a linear impedance model.Haviland et al. (2000) However, it would be a good approximationWatanabe and Haviland (2003) to use $`R_0^{}`$ for characterizing the electromagnetic environment of the SET. I also assume that the SET is in a high-impedance environment when $`R_0^{}R_K`$. As for the samples without SQUID arrays, the resistance of the leads is always much smaller than $`R_K`$, and the SET is in a low-impedance environment. The Josephson energy in the SET is calculated in a similar way, but note that it does not oscillate as a function of $`B`$ because the junctions in the SET do not have a SQUID configuration.

Another important parameter is the charging energy, which is inversely proportional to the capacitance of the junction. The capacitance can be estimated from the junction area with a specific capacitance on the order of $`10^2`$ fF/$`\mu `$m2. In our samples, the junction area is much larger, or the charging effect is much weaker, in the SQUID arrays than in the SET. In the normal state, for example, the $`I`$$`V`$ curve of the SQUID arrays is almost linear (data not shown, similar to the bottom curve in Fig. 3 of Ref. Watanabe and Haviland, 2003) even when the SET shows a well developed Coulomb blockade like in Fig. 6(b), which would be favorable when the arrays are used as leads.

The capacitance $`C_g`$ between the island electrode and the gate electrode is determined by the period of the gate modulation in the normal state. An example is shown in Fig. 3. Though the design of the SET is the same for all the samples, the values of $`C_g`$ in Table 1 are divided into two groups: 6 aF for samples 1a and 1b, and $`<`$5 aF for the others. The reason could be that we used two SiO2/Si wafers whose thickness $`t`$ of the SiO2 layer is different, and that we fabricated samples 1a and 1b on one wafer ($`t=0.2`$ $`\mu `$m) and samples 2a–3b on the other ($`t=0.5`$ $`\mu `$m).

## III Results and discussion

### III.1 Single-electron transistors in the normal state

At $`T=0`$, the $`I`$$`V`$ curve of the SET in the normal state is expected to have a region where $`I=0`$. Such a region is called a “Coulomb gap,” and depends not only on the gate voltage $`V_g`$ but also on the electromagnetic environment.Ingold and Nazarov (1992) The circuit considered in the theoryIngold and Nazarov (1992) is shown in Fig. 4, where $`C_i`$ and $`R_i`$ ($`i=1,2`$) are the capacitance and the tunnel resistance, respectively, for the $`i`$th junction, and $`Z(\omega )`$ is the impedance of the electromagnetic environment. The theory assumes that $`R_iR_K`$ and $`R_i\text{Re}[Z(\omega )]`$. In Fig. 4, the gate is not drawn explicitly because when $`C_iC_g`$, which is the case in our samples, the influence of the gate can be included in the effective island charge,

$$q=ne+C_gV_g+Q_0,$$
(3)
where $`n`$ is an integer and $`Q_0`$ is the background charge.

In the theory, the drift of $`Q_0`$ is not considered, and thus for simplicity, $`Q_0=0`$ in Eq. (3). In the experiment, however, the drift often becomes a problem. In samples 1a, 1b, 3a, and 3b, the drift was usually $`<0.1e/\text{day}`$, which is negligible for the discussion in this paper. In samples 2a and 2b, on the other hand, the drift was not slow enough ($`e/\text{hour}`$) compared to the time needed to measure hundreds of $`I`$$`V`$ curves at different values of $`V_g`$ in our experimental setup. Thus, for samples 2a and 2b, we mainly measured $`I`$ vs $`V_g`$ keeping the source voltage $`V_s`$ constant.

Figure 5 shows the theoretical Coulomb gap on the $`V_g`$$`V_s`$ plane for $`Z(\omega )=0`$ (low-impedance environment) and for $`\text{Re}[Z(\omega )]R_K`$ (high-impedance environment). The Coulomb gap is periodic in $`V_g`$ for both the cases. However, the magnitude of the gap is different, and e.g., at $`V_g=0`$, $`\pm e/C_g,`$ $`\pm 2e/C_g,\mathrm{},`$ the gap in the high-impedance environment is about twice as large as that in the low-impedance environment. It is important to note a qualitative difference at $`V_g=\pm 0.5e/C_g,`$ $`\pm 1.5e/C_g,`$ $`\pm 2.5e/C_g,\mathrm{}`$ . The gap vanishes in the low-impedance environment, but survives in the high-impedance environment. These theoretical predictions have been confirmed in our experiments. Figure 6 shows the normal-state $`I`$$`V`$ curves at $`T=0.02`$ K for samples 1a and 1b. We drove the samples into the normal state by applying a magnetic field of 0.1 T perpendicular to the substrate. In the normal state, the SQUID arrays of sample 1b have $`R_0^{}=1.4`$ M$`\mathrm{\Omega }`$ $`R_K`$ at $`T=0.02`$ K, and thus, I assume that the SET in sample 1b is in a high-impedance environment. The SET in sample 1a, on the other hand, is in a low-impedance environment because it is not biased with the arrays. In the lower data set ($`q=0.0`$), the size of the Coulomb gap in Fig. 6(b) is about twice as large as that in Fig. 6(a). Moreover, in the upper data set ($`q=0.5`$), the $`I`$$`V`$ curve in Fig. 6(a) is linear, i.e., no Coulomb gap, while the curve in Fig. 6(b) still shows a considerable nonlinearity.

I have also calculated the $`I`$$`V`$ curves based on the theory assuming $`R_1+R_2=R_n`$. For the lower data set in Fig. 6(b), a perfect agreement is obtained with $`R_1/R_2=1.0`$, $`C_1/C_2=1.0`$, $`C_1+C_2=1`$ fF, and $`k_BT/E_C=0.1`$ ($`T=0.09`$ K), where $`E_C=e^2/2(C_1+C_2)`$. These parameters are employed for all the solid curves in Fig. 6. The solid curve does not always reproduce the experimental data very well, but I nevertheless conclude that our experiments have demonstrated the environmental effects predicted by the theory. I emphasize that the solid curves are calculated with the same set of parameters, and the discrepancy is reduced if the parameters are adjusted for the calculation for each data set. The dashed curves for the lower data set of Fig. 6(a) and for the upper data set of Fig. 6(b), which agree better with the experimental data, are obtained by raising the temperature in the calculation to $`k_BT/E_C=0.3`$ ($`T=0.28`$ K), keeping the other parameters constant.

At finite temperatures, nonzero current flows even within the Coulomb gap. Therefore, it is not straightforward to determine the Coulomb gap from the experiment. As an estimate of the Coulomb gap, I have calculated the offset voltage $`V_{\mathrm{off}}`$ by fitting

$$I(VV_{\mathrm{off}})$$
(4)
to the data in the high-bias regime, $`I0.3e/(R_1+R_2)(C_1+C_2)`$ for $`V_{\mathrm{off}}>0`$ and $`I0.3e/(R_1+R_2)(C_1+C_2)`$ for $`V_{\mathrm{off}}<0`$. The results for samples 1a and 1b are plotted in Fig. 7 together with the theoretical predictions for the low-impedance environment and high-impedance environment, respectively. Here, I used the same parameters as in Fig. 6. The experimental $`V_{\mathrm{off}}`$ is consistent with the theoretical prediction.

In fact, one of the assumptions in the theory for the high-impedance case, $`R_i\text{Re}[Z(\omega )]`$, is not fulfilled in the experiment. In the normal state, $`R_n<R_0^{}`$ in sample 1b, so that the SET in sample 1b is current-biased. However, I am still convinced that the comparison with the theory is meaningful, because we measured the SET in four-terminal configuration, and because the measured $`I`$$`V`$ curves are qualitatively explained within the theory. Furthermore, the parameters used in the calculations for Fig. 6 are reasonable. It is common to observe that the effective electron temperature becomes considerably higher than the temperature of the mixing chamber in the experiments of small-capacitance tunnel junctions.Watanabe and Haviland (2003) The temperature difference is likely to be large when the cryostat leads are not filtered at low temperatures, which is the case in our cryostat. Most importantly, $`C_1+C_2=1`$ fF is consistent with our junction size, and as I mentioned earlier, much larger than $`C_g`$. This value of the total capacitance will be used again in the discussion in Sec. III.2.

### III.2 Single-electron transistors in the superconducting state

For the samples with SQUID-array leads, the same superconducting SET can be studied in different electromagnetic environments by changing the external magnetic field on the order of a few mT. In this work, I look at the low-bias region of $`|V|<2\mathrm{\Delta }_0`$, where the $`I`$$`V`$ curve is sensitive to the state of the electromagnetic environment. In all the samples with SQUID-array leads, the $`I`$$`V`$ curve of the superconducting SET developed a Coulomb blockade as $`R_0^{}`$ was increased by tuning the field. Figure 8 shows the $`I`$$`V`$ curves of the SET in sample 1b in two different environments. As I mentioned earlier, the parameters of the SET should be independent of the field, because the SET does not have a SQUID configuration and the field applied in Fig. 8 is much smaller than the critical field. The electromagnetic environment for the SET (the SQUID arrays), on the other hand, is strongly varied with the field as we have seen in Fig. 2. The behavior of the SET demonstrated in Fig. 8 does not result from the magnetic-field influence on the $`I`$$`V`$ curve of the SET, but rather from an environmental effect on the SET. I note here that the SETs without SQUID arrays were also measured at $`B=0`$ and at $`B7`$ mT, and that the $`I`$$`V`$ curves were almost the same. The well-developed Coulomb blockade in Fig. 8(b) indicates that the SET is in a high-impedance environment, which is consistent with $`R_0^{}=0.3`$ G$`\mathrm{\Omega }`$ $`R_Q`$. From the viewpoint of $`R_0^{}`$, the SET is not in a low-impedance environment in Fig. 8(a) because $`R_0^{}=0.2`$ M$`\mathrm{\Omega }`$ is already larger than $`R_Q`$. Thus, in order to study the low-impedance case, we have to measure samples without SQUID-array leads. Rather surprisingly, e.g., in sample 1a, the $`I`$$`V`$ curve and its dependence on the gate-induced charge were qualitatively almost the same as Fig. 8(a), and the supercurrent was too small to be seen in the $`I`$$`V`$ curve. This is due to “quasiparticle poisoning,” which is likely to occur in our cryostat which has no low-temperature noise filters. In addition, our biasing scheme is not ideal for the supercurrent measurement because the samples without SQUID-array are voltage biased. The supercurrent was not detected in samples 2a or 3a, either.

“Quasiparticle poisoning” is also suggested by the $`e`$ periodicity in the current modulation by the gate-induced charge, which was observed in all samples without SQUID-array leads. The $`e`$ periodicity was also found in sample 1b when $`R_0^{}=0.2`$ M$`\mathrm{\Omega }`$, as shown in Fig. 9(a), where the potential drop across the SET is 0.15 mV. When $`R_0^{}`$ is increased to 0.3 G$`\mathrm{\Omega }`$ \[Fig. 9(b)\], it was replaced by $`2e`$ periodicity, which indicates Cooper-pair transport. The SQUID arrays with sufficiently large $`R_0^{}`$ acted as a filter that suppresses the contribution of quasiparticles to the charge transport. This change in the periodicity was also found in sample 2b. In sample 3b, however, only $`e`$ periodicity was seen probably because the maximum of $`R_0^{}`$ was only 9 M$`\mathrm{\Omega }`$. The curve in Fig. 9(b) is calculated from the $`I`$$`V`$ curves, because we could not fix the potential drop across the SET when it is much smaller than that across the SQUID arrays in our experimental setup.

Below I focus on the case of $`R_0^{}R_Q`$, and discuss the Coulomb blockade of Cooper-pair tunneling. In the high-impedance environment, a current-biased single Josephson junction is expected theoreticallyAverin and Likharev (1991); Schön and Zaikin (1990) to have a “back-bending” $`I`$$`V`$ curve, which has been experimentallyHaviland et al. (1991); Watanabe and Haviland (2001, 2003) confirmed. The “back-bending” is also seen in Fig. 8(b) for certain values of the gate-induced charge. When the “back-bending” is clearly seen in the SET $`I`$$`V`$ curve, I define the blockade voltage $`V_b`$ as the local voltage maximum (minimum) for $`V_b>0`$ ($`V_b<0`$) in the low-current part of the $`I`$$`V`$ curve. The measured $`V_b`$ is plotted in Fig. 10 as a function of the gate-induced charge. The dotted and broken curves represent $`V`$ at constant $`I`$ calculated from the $`I`$$`V`$ curves. These curves would also characterize the Coulomb blockade. The analytic expression of $`V_b`$ at low temperatures has been obtained for single Josephson junctions as

$$V_b0.25\frac{e}{C}$$
(5)
for $`E_J/E_C1`$, and

$$V_b\frac{e}{C}\left(\frac{E_J}{E_C}\right)^{3/4}\mathrm{exp}\left[\left(8\frac{E_J}{E_C}\right)^{1/2}\right]$$
(6)
for $`E_J/E_C1`$, where $`C`$ is the capacitance of the single junction.

The relationship between a superconducting SET and a single Josephson junction in the low-impedance environment has been discussed,Joyez (1995) and by examining the Hamiltonian, it has been shown that a superconducting SET can be viewed as a single Josephson junction with gate-tunable $`E_J`$. I have found a similar relationship for the high-impedance case, which explains the variation of $`V_b`$ in Fig. 10. In the high-impedance environment, not only the island charge $`Q_1Q_2`$ \[$`=q`$ in Eq. (3)\] but also the total charge $`(C_2Q_1+C_1Q_2)/(C_1+C_2)`$ seen from the outside contributes to the charging energy,Ingold and Nazarov (1992) where $`Q_i`$ is the charge on the $`i`$th junction. This is why in Fig. 5, the Coulomb gap is larger in the high-impedance environment. Let us compare Fig. 5(b) with the Coulomb gap for a single junction in the high-impedance environment,Ingold and Nazarov (1992) which is $`\pm e/2C`$. In this environment, a SET can be viewed as a single junction with gate-tunable $`C`$ or $`E_C`$, where the minimum of $`C`$ is $`0.25(C_1+C_2)`$ and the maximum is $`0.5(C_1+C_2)`$. I do not know the exact expression for the effective $`E_J`$ of the SET in the high-impedance environment, however, the magnitude should be similar to the low-impedance case,Joyez (1995) $`h\mathrm{\Delta }_0/8e^2R_n`$. From Table 1 and $`C_1+C_2=1`$ fF, which was obtained from the curve fit in Fig. 6, the effective $`E_J/E_C`$ of the SET in Fig. 10 is always smaller than 0.04 ($``$1). Thus, from Eq. (5), our model predicts that $`V_b`$ oscillates between $``$0.08 and $``$0.16 mV in Fig. 10. The order of magnitude is correct and the gate dependence is explained. Note that the notion of gate-tunable $`C`$ is a key because at $`E_J/E_C1`$, $`V_b`$ depends only on $`C`$.

## IV Conclusion

The transport properties of single-electron transistors (SETs) have been studied in various electromagnetic environments. In half of the samples, SQUID-array leads were employed in order to realize a magnetic-field-tunable environment in the superconducting state and a high-impedance environment in the normal state. I have demonstrated that the effective charging energy of SETs in the normal state becomes larger in the high-impedance environment than in the low-impedance environment. In the superconducting state, the current modulation by the gate-induced charge changed from $`e`$ periodic to $`2e`$ periodic in SETs with SQUID-array leads, as the zero-bias resistance $`R_0^{}`$ of the leads was increased to be much larger than the quantum resistance $`R_Kh/e^226`$ k$`\mathrm{\Omega }`$. This change in the periodicity suggests that SQUID arrays with sufficiently large $`R_0^{}`$ suppress the contribution of quasiparticles to the charge transport. When $`R_0^{}R_K`$, a sharp Coulomb blockade appears in the current–voltage characteristics, and the blockade voltage $`V_b`$ varies depending on the gate-induced charge. The variation of $`V_b`$ is explained within a model that treats a superconducting SET as a single Josephson junction with gate-tunable junction capacitance in the high-impedance environment.

###### Acknowledgements.

I am grateful to Y. Nakamura for fruitful discussion and to M. J. Dalberth for proofreading the manuscript. This work was supported by Special Postdoctoral Researchers Program and President’s Special Research Grant of RIKEN, and MEXT.KAKENHI(15740190). Sample fabrication and measurement were done at Semiconductors Laboratory (closed in March, 2003), RIKEN.


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# Propagating phase boundaries as sonic horizons

## Abstract

If certain conditions are met, a propagating phase boundary can be a sonic horizon. Sonic Hawking radiation from such a phase boundary is expected in the quantum theory. The Hawking temperature for typical values of system parameters can be as large as $`0.04`$ K. Since the setup does not require the physical transport of material, it evades the seemingly insurmountable difficulties of the usual proposals to create a sonic horizon in which fluid is required to flow at supersonic speeds. Issues that are likely to present difficulties that are particular to this setup are discussed. Hawking evaporation of the sonic horizon is also expected and is predicted to lead to a deceleration of the phase boundary.

Condensed matter analogs of gravitational systems have brought purely theoretical ideas on very large-scale gravitational structures to almost within the realm of experimental tests. A key breakthrough was the realization by Unruh Unr81  that black hole event horizons can be simulated by sonic event horizons around “dumbholes” in fluid flow. Furthermore, theoretical results from the application of quantum field theory in curved spacetimes, such as Hawking radiation Haw74 , should also apply to condensed matter analogs, thus opening the door to novel experimental tests of gravitational phenomena.

The fluid analog of black holes occurs when sub-sonic fluid flow upstream changes to supersonic flow downstream. Now the fluid flow downstream is too rapid to allow sonic perturbations to flow upstream. Sound can travel downstream from upstream but not upstream from downstream, resulting in a “sonic horizon” at the location where the flow velocity equals the sound velocity. To the upstream observer, the downstream region is a hole from which no sound can emanate, that is, it is a dumbhole. This is the classical picture. As in the black hole case, “dumbholes ain’t so dumb” and quantization of the acoustic perturbations leads to sonic Hawking radiation from downstream to upstream. Unruh found that the sonic Hawking temperature is given by:

$$T_{sH}=\left(\frac{\mathrm{}}{2\pi k_B}\right)\frac{d}{dr}(v)|_{hor}$$
(1)
where $`\mathrm{}`$ is Planck’s constant divided by $`2\pi `$, $`k_B`$ is Boltzman’s constant, $`r`$ is the radial coordinate, $`v|𝐯|`$, and the flow velocity $`𝐯`$ is assumed to be radially inward. The derivative of the velocity is evaluated at the location of the sonic horizon determined by $`v=c_s`$ where $`c_s`$ is the sound velocity. A numerical estimate gives:

$$T_{sH}3\times 10^7\text{K}\left(\frac{c_s}{300\text{m/s}}\right)\left(\frac{1\text{mm}}{R}\right)$$
(2)
where the velocity gradient is taken to be $`c_s/R`$. The estimate clearly demonstrates the challenge: even when the fluid undergoes tremendous acceleration – velocity change from 0 to $`300`$ m/s within $`1`$ mm or, equivalently, $`10^7g`$ where $`g`$ is the terrestrial acceleration due to gravity – the sonic Hawking temperature is extremely small.

The immense practical problems in creating a sonic black hole and observing Hawking radiation have been described by Unruh Unr02 , leading to a very grim picture. The crux of the problem is that the flow of fluids and superfluids suffers from instabilities at the tremendous accelerations that are required for creating a sonic horizon with a measurable Hawking temperature. If one chooses to work with a system with low sound velocity, the instabilities can be evaded, but then the Hawking temperature is unmeasurably low. At the moment these difficulties seem to be insurmountable, except possibly in Bose-Einstein condensates GarAngCirZol00 ; GarAngCirZol01 . (Proposals to test quantum processes in the presence of cosmological horizons in BEC analogs also appear promising FedFis03 .)

For the idea to be described in the present paper, a generalization of Eq. (1) made by Visser Vis98  will be very important. Visser considered the case when the sound velocity itself is a function of space and time and obtained:

$$T_{sH}=\left(\frac{\mathrm{}}{2\pi k_B}\right)\frac{d}{dr}(c_sv)|_{hor}$$
(3)
This seemingly small step opens up a conceptually new set of possible dumbhole realizations because now it is not necessary to accelerate the fluid; instead one can manipulate the function $`c_s(t,𝐱)`$.

Along these lines, the proposal of Jacobson and Volovik JacVol98  (also see UnrSch03 ) employs a domain wall in 3He-A to produce a variation of the “sound” velocity footnote1  on microscopic scales ($`500`$ Å). Modest velocities of the domain wall lead to an enhanced Hawking temperature. The gain is however somewhat offset by the rather low sound velocity ($`3`$ cm/s). The Hawking temperature in their setup is $`5\mu `$K, whereas reliable thermometry in 3He currently only goes down to $`100\mu `$K. Furthermore, gradients in the order parameter associated with the presence of the domain wall lead to additional sources of radiation that are not related to the sonic horizon. It remains to be seen if the Hawking radiation can be disentangled from these other effects.

We envisage a setup somewhat related to the Jacobson-Volovik proposal and pictured in Fig. 1. The container is initially filled with a metastable phase (Phase 1) of a material. Suppose that Phase 2 is the stable phase under the conditions of the experiment. Then a perturbation will trigger bubble nucleation of Phase 2 and this bubble will grow. The velocity $`v`$ with which the bubble grows will be subsonic in Phase 1: $`v<c_1`$ where $`c_1`$ is the sound velocity in Phase 1. The sound velocity $`c_2`$ in Phase 2 will be different from that in Phase 1. We assume $`c_2<c_1`$. More crucially we take $`c_2<v`$. For the purposes of this paper, we will simply assume that the conditions ($`c_1>v>c_2`$) are met in the system we have chosen. Then sound emanating from within Phase 2 cannot catch up with the phase boundary. Thus the phase boundary will be a sonic horizon. By the usual arguments Unr81 , sonic Hawking radiation should be seen to emanate from the bubble footnote2 .

The advantage of this setup is that it completely eliminates any instabilities associated with supersonic flow. In certain situations, the bubble wall may push on the material outside. If the system is kept at constant pressure, this would cause some expansion of the occupied volume. The height occupied by the material would increase by a fraction $`(\delta V_b)/V`$ where $`\delta V_b`$ is the increase in volume occupied by the bubble and $`V`$ is the volume occupied initially by Phase 1. This can be made small by choosing a large container. We can also imagine a situation where the transition from Phase 1 to Phase 2, does not involve a significant change in density. This might happen, for example, in the case of a fluid to superfluid transition. The bubble wall then just marks the location where Phase 1 is being converted to Phase 2, without the wall actually exerting any forces on the material outside. In this case, there is no transport of material involved. In fact, the two phases need not even be fluid, they can be solid, say the normal and superconducting phases of a Type I superconductor. Our only requirement is that we have two different sound velocities and a phase boundary velocity that satisfies $`c_1>v>c_2`$. If the velocities of ordinary (compressional) sound do not satisfy these conditions, one could consider some other excitations. However, it is advantageous to consider the excitations with the largest velocities that satisfy the conditions since then the Hawking temperature is highest.

In this setup, the Hawking temperature can be relatively large because the gradient of $`c_sv`$ occurs within the phase boundary whose thickness will be of microscopic dimensions, given by the inter-molecular spacing, or the coherence length of Cooper pairs, or some other such length scale. The sound velocity depends on what kind of excitations we are considering. We would like to take a large sound velocity, since this gives a larger Hawking temperature. With ordinary sound (compressional waves) typical sound speeds are $`300`$ m/s. This leads to the estimate:

$$T_{sH}0.04\text{K}\left(\frac{\delta c_s}{300\text{m/s}}\right)\left(\frac{100\text{Å}}{\xi }\right)$$
(4)
where $`\delta c_s`$ is the change in the sound velocity across the phase boundary and $`\xi `$ denotes the thickness of the phase boundary. This is quite large compared to Hawking temperature estimates in earlier proposals. The thermal frequency is $`\nu =k_BT/h1`$ GHz and the power emitted is $`\sigma _sT_{sH}^410^4`$ pW/cm2 where the sonic Stefan-Boltzmann constant $`\sigma _s=\pi ^2k_B^4/60c_1^2\mathrm{}^3`$ involves the sound speed and two polarizations have been assumed Unr02 .

Now let us consider some specific systems and variations on the general scheme described above. The first point to note is that we must necessarily work at low temperature since the Hawking temperature is of order $`0.04`$ K. All substances except the isotopes of Helium, solidify at such a temperature. So we need either to work with a solid, or with Helium. If we choose 4He, we will be working with a superfluid. 3He however need not be in the superfluid phase.

An existence proof that the conditions $`c_1>v>c_2`$ can be met can be found by considering the Abelian Higgs model in a cosmological setting. (The non-relativistic version of the Abelian Higgs model is the Ginzburg-Landau model used to describe simple superconductors.) For a certain set of parameters, the Abelian Higgs model is known to undergo a first order phase transition, corresponding to Type I superconductors. Imagine that the system is supercooled, so that it is stuck in the metastable state labeled Phase 1 in Fig. 2. Excitations in this metastable state are massless gauge particles (photons) and massive scalars. If these excitations are in equilibrium, they form a relativistic fluid for which the equation of state is $`p=\rho /3`$ (in units where the speed of light is one). So the sound velocity in the supercooled state is $`c_1=1/\sqrt{3}`$. If there was no plasma outside the bubble, the bubble wall velocity would be the speed of light. However, the plasma exerts a drag on the bubble wall, and reduces its speed somewhat, and one has $`vc_1`$. (In the similar case of the cosmological electroweak phase transition, calculations yield $`v0.1`$ Moo00 .) Inside the bubble, in Phase 2, all the excitations are massive and non-relativistic. Now the equation of state is $`p0`$ and the speed of sound $`c_2`$ is non-relativistic, say 300 m/s which is much less than $`v`$. Therefore the conditions $`c_1>v>c_2`$ are met, and the bubble should emit sonic Hawking radiation. Also note that any heat released by the phase transition within the bubble does not propagate to the outside since the bubble wall is moving at supersonic speeds. So oscillations of the order parameter in the true vacuum are inconsequential. The only danger arises from excitations living outside the bubble (i.e. order parameter oscillations in the metastable state) that might scatter off the bubble wall. However, if the system is sufficiently supercooled, the density of excitations in the metastable state is expected to be very low.

A one dimensional version of our setup consists of a cylindrical container filled with Phase 1 (Fig. 3). A perturbation applied on the right-hand end of the cylinder will trigger bubble nucleation of Phase 2. The bubble of Phase 2 will start growing and the phase boundary (or bubble wall) will propagate to the left. Unlike the bubble of Fig. 1, the area of the sonic horizon does not change with time and hence the setup is easier to analyze. The disadvantage of the one dimensional setup is that there is more interaction of the system with the walls of the container and hence there is greater danger of instabilities. In particular, heat released on the Phase 2 side can be transmitted to the Phase 1 side through the walls of the container.

A one dimensional condensed matter situation where a phase boundary propagates at supersonic speeds occurs in 3He. The boundary of a bubble of A phase inside a metastable B phase has been experimentally seen BucSwiWhe86  to propagate at speeds of up to 67 cm/s, while fermionic quasiparticles excitations in 3He-A propagate at only 3 cm/s. On the 3He-B side, these excitations are can propagate at 55 m/s and so the setting seems right for the creation of a sonic horizon. However, note that the bubble wall velocity is in the wrong direction in this case – we would like the wall of an A phase bubble, where the sound velocity is small, to propagate at high velocity into the B phase where the sound velocity is high. It remains to be seen if the A-B phase boundary can provide measurable Hawking radiation JacVol98  (also see Sec. 29.3 of Volbook ).

A novel feature of our proposal is that it is an example of a “non-driven” sonic horizon. In other examples, one has to arrange external forces to produce a sonic horizon. For example, in fluid flow, the fluid has to be driven under pressure. If the external conditions are designed to maintain a sonic horizon, the Hawking radiation backreaction on the sonic horizon will be lost. In the bubble nucleation proposal, however, the procedure is to nucleate a bubble of Phase 2 and then leave the system to its own devices. If the propagating phase boundary does emit Hawking radiation, it will experience a backreaction that will slow it down. Eventually the bubble wall velocity will become subsonic with respect to the sound velocity in Phase 2. In other words, the prediction is that the condition $`c_1>v>c_2`$ is quantum mechanically unstable and eventually the system will go to a state with $`c_1>c_2>v`$. This is no different from the evaporation of black holes due to Hawking radiation.

To estimate the evaporation time, note that the power in the emitted Hawking radiation is: $`\sigma _sT_{sH}^4A`$ where $`A=4\pi R^2`$ is the area of the horizon when the bubble radius is $`R=vt`$. The energy lost as a function of time is therefore: $`E_{lost}\sigma _sT_{sH}^44\pi v^2t^3`$. The kinetic energy of the phase boundary in the absence of the losses would be: $`E_{kin}\mathrm{\Sigma }Av^2`$ where $`\mathrm{\Sigma }`$ denotes the surface energy density. Therefore the evaporation time scale is given by equating the energy lost to the total kinetic energy:

$$t_{evap}10^6f^2\left(\frac{\mathrm{\Sigma }\xi ^3c_1}{\mathrm{}}\right)\left(\frac{\xi }{100\text{Å}}\right)\left(\frac{300\text{m/s}}{c_1}\right)\text{s}$$
(5)
where $`fv/c_1`$. The evaporation time depends very crucially on the surface energy density. We would like to have a large surface density so that the evaporation is relatively slow. The surface density depends on the system that is being used. However, we can get an idea for its value by considering the phase boundary to be a domain wall. For a domain wall in a $`\lambda \varphi ^4`$ model, we have:

$$\frac{\mathrm{\Sigma }\xi ^3c_1}{\mathrm{}}=O\left(\frac{1}{\lambda }\right)$$
(6)
Hence if the coupling constant $`\lambda `$ is small, the evaporation time will be long. This is exactly as for black holes where the Hawking evaporation time is long because gravity is so weakly coupled. One way in which black hole evaporation is different from dumbhole evaporation is that the black hole necessarily gets hotter as it gets smaller. The dumbhole may get hotter or colder with evaporation, depending on the gradient of $`c_s(t,𝐱)`$ at the location of the sonic horizon $`v=c_s(t,𝐱)`$.

If it is difficult to find a system in which the condition $`v>c_2`$ holds, one could consider driving the phase boundary by some external forces. This might be easy to implement if the substance undergoes a phase transition when an electromagnetic field is applied. Then the electromagnetic fields could be varied externally to drive the phase boundary at high velocities. The only danger is that the application of dynamical external forces could give rise to additional heating that could swamp the signal. We will not consider the “driven” setup any further here.

We now discuss potential difficulties in implementing the current proposal.

The first danger is that the phase boundary may have instabilities during propagation. Such instabilities need to be avoided since they will introduce noise in the Hawking emission. Fingering and other instabilities are system-dependent, and the success of the proposal will depend on finding a system in which such instabilities are absent.

An important issue is that, since the phase boundary is propagating, eventually the whole container will be filled with the second phase. So there is only a limited time $`(L/vL/c_1)L/v`$, where $`L`$ is the size of the container, to make measurements. This time had better be long enough to detect excitations at the thermal frequency $`\nu =k_BT_{sH}/h1`$ GHz and we obtain a lower bound on the required length of the container: $`L>hv/(k_BT_{sH})10^5`$ cm. This condition does not seem difficult to meet in the laboratory where samples are typically on the scale of centimeters. However, a sample of 1 cm size will only provide $`10^5`$ s to make measurements.

Another potential difficulty is that Phase 1 is metastable and might decay spontaneously. Hence it has to be protected from perturbations. However, the Hawking radiation itself will perturb Phase 1 and the concern is if the system might “self-destruct”. To avoid this possibility, Phase 1 should be immune to sonic perturbations at the Hawking temperature.

The bubble will have perturbations that are produced during the nucleation process. Even quantum nucleation leads to fluctuations on the bubble VacVil91 ; GarVil92 . The amplitude of fluctuations is suppressed if the bubble surface density, $`\mathrm{\Sigma }`$, is large. Hence the effects of bubble perturbations can be reduced, as well as the evaporation time made large, by choosing a system with a large $`\mathrm{\Sigma }`$.

In summary, we have shown that propagating phase boundaries can be sonic horizons provided the propagation velocity satisfies the condition $`c_1>v>c_2`$. In systems where this condition is met, the Hawking temperature can be relatively large, leading to the exciting possibility that experiments might detect Hawking radiation. In addition, in these systems the sonic Hawking radiation will lead to evaporation of the sonic horizon, providing a yet closer analog of gravitational black holes.

###### Acknowledgements.

I am grateful to Ana Achucarro, Dan Akerib, Craig Copi, Arnie Dahm, Harsh Mathur, Rolfe Petschek, Bill Unruh, and Grisha Volovik for discussions and comments. This work was supported by DOE grant number DEFG0295ER40898 at Case.


text:
# 1 Introduction

## 1 Introduction

Causality and entropy both tell us something about how time works. Cause happens before effect. In non-dissipative systems physical observables are generally invariant under the reversal of time. Irreversible dissipation gives an observable direction to the flow of time, i.e. entropy provides the ‘arrow of time’. In this paper we examine the nature of time ordering of interactions in non-dissipative quantum systems. We associate this time ordering with causality.

Classically, the mathematical function that connects cause and effect is called a Green’s function, $`G`$. This function describes how dynamic systems evolve from position ($`\stackrel{}{r}_0,t_1`$) to ($`\stackrel{}{r},t_2`$). This Green’s function is used to describe, for example, the time sequence in which interactions occur. Certain conditions are usually imposed on the Greens’ function . One such condition is causality. If an interaction occurs at $`t_1`$, no effect of this interaction should be present at an earlier time. This imposes the condition that $`G=dG/dt=0`$ for $`t_2<t_1`$. Conversely, an event or interaction at $`t_1`$ can affect the system at a later time, $`t_2`$. This is a classical example of time non-locality . The reciprocity condition imposes a symmetry between propagation from ($`\stackrel{}{r}_0,t_1`$) to ($`\stackrel{}{r},t_2`$), and time reversed propagation from ($`\stackrel{}{r},t_2`$) to ($`\stackrel{}{r}_0,t_1`$). The condition is that $`G(\stackrel{}{r},t_2;\stackrel{}{r}_0,t_1)=G(\stackrel{}{r}_0,t_1;\stackrel{}{r},t_2)`$. The effect of an interaction at ($`\stackrel{}{r},t_2`$) from ($`\stackrel{}{r}_0,t_1`$) is equal to the effect of an interaction at ($`\stackrel{}{r}_0,t_1`$) from ($`\stackrel{}{r},t_2`$), where $`t_2`$ now precedes $`t_1`$, cleverly satisfying causality. Moreover to specify a unique physical solution to a differential equation boundary and/or initial conditions are required. In solving Newton’s equations for particles, one often specifies the initial values of $`\stackrel{}{r}_0`$ and $`d\stackrel{}{r}_0/dt`$ to determine a unique trajectory, $`\stackrel{}{r}(t)`$ for a particle. For scattering of waves most typical is the boundary condition that the scattered waves be outgoing, corresponding to an $`e^{ikr}/r`$ scattered term. Alternatively, incoming scattering waves could be used222Actually doing such a time reversed experiment could be very difficult., corresponding to $`e^{ikr}/r`$. If waves reflect from some finite boundary, combinations of outgoing and incoming waves may be appropriate. One example  is a standing wave, corresponding to $`\mathrm{cos}kr/r`$. One way or another the flow of time must be clearly specified.

Classical waves are usually not well localized. Waves can continue for a long time, and can be modified. Radio wave propagation is an example. The modulation of a high frequency, so-called carrier wave can be used to transmit information, such as the news. Wave modulation, based on interference of waves of different frequencies, is distributed, i.e. non-local. Classically all precursors of a wave are restricted  to group velocities less than the speed of light333In anamolous dispersion a zero group velocity can achieved  when $`d\omega /dk=0`$. This can also be realized in a degenerate quantum system where all energies are the same so that $`dE/dk=0`$.. The properties of Green’s functions for waves  are similar to those for particles.

Quantum mechanics brings together particles and waves by use of finite wavepackets. This can also be done classically. Wavepackets have properties of both particles and waves. As a consequence, quantum wavepackets may not be perfectly localized in both time and frequency. A particle-like wavepacket requires many frequencies so the waves can cancel except at small distances. And a wave-like wavepacket oscillating with nearly a single frequency (small $`\mathrm{\Delta }f`$), must be spread over time (large $`\mathrm{\Delta }t`$). Here $`c\mathrm{\Delta }t`$ is the size of a wavepacket moving at a speed $`c`$. This illustrates the band-width theorem, $`\mathrm{\Delta }f\mathrm{\Delta }t1/4\pi `$. Unlike in classical mechanics, in quantum mechanics the energy is related to the frequency, e.g. $`E=hf`$. In quantum mechanics the band-width theorem appears as the uncertainty principle, which limits the resolution with which time and energy (and other conjugate variables with non-commuting operators) may be observed.

## 2 How time works in quantum systems

The quantum mechanical wavefunction, $`\mathrm{\Psi }`$, is used to give a complete description of any quantum system. If the system is dynamic, then $`\mathrm{\Psi }`$ changes with time. This is usually written as,

$`\mathrm{\Psi }(t_2)=U(t_2,t_1)\mathrm{\Psi }(t_1).`$ (1)
The time evolution propagator, $`U(t_2,t_1)`$, describes the evolution of the system from time $`t_1`$ to time $`t_2`$. The operator $`U`$ is related to the classical Green’s function, $`G`$. The quantum operator $`U`$ may be defined by ,

$`U(t_2,t_1)`$ $`=`$ $`{\displaystyle \underset{n=0}{\overset{\mathrm{}}{}}}(i\mathrm{})^n{\displaystyle _{t_1}^{t_2}}𝑑t^n^{}V(t^n^{})\mathrm{}{\displaystyle _{t_1}^{t^{\prime \prime \prime }}}𝑑t^{\prime \prime }V(t^{\prime \prime }){\displaystyle _{t_1}^{t^{\prime \prime }}}𝑑t^{}V(t^{})`$ (2)
$``$ $`{\displaystyle \underset{n=0}{\overset{\mathrm{}}{}}}{\displaystyle \frac{(i\mathrm{})^n}{n!}}{\displaystyle _{t_1}^{t_2}}𝑑t^n^{}\mathrm{}{\displaystyle _{t_1}^{t_2}}𝑑t^{\prime \prime }{\displaystyle _{t_1}^{t_2}}𝑑t^{}TV(t^n^{})\mathrm{}V(t^{\prime \prime })V(t^{})`$
$`=`$ $`Te^{i_{t_1}^{t_2}V(t)𝑑t}.`$
Here $`V(t)`$ is the interaction that causes the system to change, and $`T`$ is the Dyson time ordering operator , which imposes the causal-like constraint that $`TV(t^{})V(t)=0`$ if any $`t^{}<t`$’. That is the time ordering operator, $`T`$, is proportional to the step function, $`\mathrm{\Theta }(t_2t_1)`$, which is 1 for $`t_2>t_1`$ and 0 for $`t_2<t_1`$.

Quantum time ordering corresponds to classical causality. The invariance of physical observables under overall reversal of time, $`𝒯`$, corresponds to classical reciprocity. This is sometimes also called detailed balance. This property holds in systems with no dissipation. The time reversal operation, $`𝒯`$, corresponds to  replacing $`i`$ by $`i`$. This leaves physical variables unchanged. Expression of reciprocity (and possibly causality as well) is mathematically simpler in quantum mechanics than in classical mechanics.

The time ordering operator, $`T`$, may be generally decomposed  into two terms, namely,

$`T=T_{av}+\mathrm{\Delta }T,`$ (3)
where $`T_{av}`$ is the time average value of $`T`$, namely $`T_{av}=1`$. To understand the influence of $`T_{av}`$ and $`\mathrm{\Delta }T`$, it is instructive to look at their contributions in energy space. The Fourier transform of $`U(t_2,t_1)`$ is the energy-space Green’s function, $`G(E_0,E)`$. The step by step time-energy relation may be understood using the Fourier transform of time ordered terms, e.g. $`TV(t_2)V(t_1)`$. The Fourier transform of $`\mathrm{\Theta }(t_2t_1)`$, which influences the time propagation between interactions, $`V(t_1)`$ and $`V(t_2)`$, is ,

$`{\displaystyle d(t^{\prime \prime }t^{})\mathrm{\Theta }(t^{\prime \prime }t^{})\mathrm{e}^{i(E_0E)(t^{\prime \prime }t^{})}}`$ (4)
$`=\underset{\eta 0^+}{lim}{\displaystyle \frac{i}{E_0E+i\eta }}=\pi \delta (E_0E)\mathrm{P}_\mathrm{v}{\displaystyle \frac{\mathrm{i}}{\mathrm{E}_0\mathrm{E}}}.`$
The second relation is sometimes called the Sokhotsky formula.

In the formulation of scattering theory, $`\eta 0^+`$ corresponds to the asymptotic boundary condition444Initial conditions are usually employed in n-state coupled channel equations. We note that in a 2-state system the initial condition on the amplitude $`a_2(0)`$ is related to the first derivative of $`a_1(0)`$ since $`\dot{a}_1(0)V_{12}a_2(0)`$. This is a quantum example where initial conditions are used as in classical applications of Newton’s second law. for incoming plane waves and outgoing scattered waves , and $`\mathrm{P}_\mathrm{v}`$ is the principal value contribution that gives contributions for $`EE_0`$, and excludes the singular, energy conserving point at $`E=E_0`$. Since $`T_{av}=1`$, the $`T_{av}`$ term changes nothing. $`\mathrm{\Delta }T=TT_{av}`$ corresponds to the time-dependent sign$`(t^{\prime \prime }t^{})`$ contribution to $`\mathrm{\Theta }(t^{\prime \prime }t^{})=\frac{1}{2}(1+\mathrm{sign}(t^{\prime \prime }t^{}))`$, where sign($`x`$) = $`\pm 1`$ depending on whether $`x`$ is positive or negative. Since $`d(t^{\prime \prime }t^{})e^{i(E_0E)(t^{\prime \prime }t^{})}=2\pi \delta (E_0E)`$, it follows that, $`\frac{i}{2}d(t^{\prime \prime }t^{})\mathrm{sign}(t^{\prime \prime }t^{})\mathrm{e}^{i(E_0E)(t^{\prime \prime }t^{})}=\mathrm{P}_\mathrm{v}\frac{1}{E_0E}`$. That is, the Fourier transform of $`\mathrm{\Delta }T`$ is the principal value part of the energy propagator, which corresponds to the $`i\eta `$ asymptotic condition. Thus $`\mathrm{\Delta }T`$, time ordering, the direction of time propagation, time correlation and the sequencing of interactions all correspond to the $`i\eta `$ asymptotic condition. The direction of time propagation may be reversed by reversing the sign of $`i\eta `$, where outgoing scattered waves are replaced by incoming scattered waves. The absence of $`i\eta `$ corresponds to standing waves .

We emphasize that even though $`\eta 0^+`$, the influence of this term is usually finite and can make a significant difference. One example is the case of the Thomas peak in electron capture  where omitting the $`\eta 0^+`$ contribution reduces the Thomas peak by a factor of one half. The $`i\eta `$ term is like a worm in a bite from an apple: even a very small piece has an effect. Finite values of $`i\eta `$ yield dissipation with exponential decay of probability (or exponential growth depending on the sign of $`\eta `$).

The effect of time ordering first occurs in the second order contribution in $`V`$, where it may be expressed as a non-zero commutator of $`V(t)`$ with $`V(t^{})`$. It is easily shown  that, $`\mathrm{\Delta }TV(t^{\prime \prime })V(t^{})=\frac{1}{2}\mathrm{sign}(t^{\prime \prime }t^{})[V(t^{\prime \prime }),V(t^{})]`$. If the commutator $`[V(t^{\prime \prime }),V(t^{})]=V(t^{\prime \prime })V(t^{})V(t^{})V(t^{\prime \prime })=0`$, there is no time ordering. Here sign$`(t^{\prime \prime }t^{})=(t^{\prime \prime }t^{})/|t^{\prime \prime }t^{}|`$ is like a unit vector that defines the direction of increasing time. The commutator, $`[V(t^{\prime \prime }),V(t^{})]`$ provides an explicit time connection between interactions at different times, $`t^{}`$ and $`t^{\prime \prime }`$. This non-commutivity often arises from spatial correlation . The non-commutivity represents non-local time entanglement between electrons, as illustrated in figure 1. We note that both $`T_{av}V(t^{\prime \prime })V(t^{})`$ and $`\mathrm{\Delta }TV(t^{\prime \prime })V(t^{})`$ are invariant when either the direction of time is reversed between the two interactions, or the overall direction of time is reversed555Of course it is the action of entropy (e.g. dissipation), not time ordering or causality, that violates the invariance of physical observables under reversal of the flow of time., e.g. by reversing the sign of $`i\eta `$.

When time ordering is present, certain phases develop666In classical propagation  the principal value terms correspond to a lifetimes decay, and are not associated with fluctuations in frequency and phase. in each step of the time evolution. Specifically, each interaction step evolves as $`_{t_1}^{t_2}e^{i(E_IE_I^{})t_j}<I|V(t_j)|I^{}>𝑑t_j`$ with a phase accumulating from the $`e^{i(E_IE_I^{})t_j}`$ term. This modifies the phase from previous interaction steps. Because the $`e^{(E_IE_I^{})t_j}`$ phase modulates by the $`<I|V(t_j)|I^{}>`$ matrix element, the order of the interactions is significant. Thus time ordering of the interaction steps leads to a specific net phase in each order of the perturbation series. These phases, due to short lived quantum fluctuations in the intermediate energies consistent with the uncertainty principle, add coherently. If these phases are changed, e.g. by changing the sequencing of the interaction steps, the various perturbation terms add differently. This can affect physical quantities such as chemical reaction rates and cross sections.

We note that the phases contributions from time ordering are absent in systems where all the unperturbed eigenenergies,Time ordering is absent in degenerate quantum systems since in any step $`V(t^{})𝑑t^{}`$ and $`V(t^{\prime \prime })𝑑t^{\prime \prime }`$ may be interchanged, i.e. there is no time ordering, since $`t^{}`$ and $`t^{\prime \prime }`$ become interchangeable dummy variables. Alternatively, if all the energies, $`E_I`$, of the basis states are the same, then no principal value contributions exist since the Hilbert space of the degenerate states contains only one energy. In a degenerate Hilbert space time ordering is suppressed. There are no energy fluctuations, no principal value contribution from $`\frac{1}{E_0E+i\eta }`$, no $`\mathrm{\Delta }T`$ contribution, and no time ordering. For example if one sets $`E_I=E_{av}`$ in each interaction step (e.g. as in an eikonal or Magnus approximation), the actual time sequencing is replaced by a time-averaged time sequence of the interactions. On the other hand if the basis states allow quantum energy fluctuations, i.e. the basis states are non-degenerate, time ordering can nevertheless be zero, e.g. when $`[V(t^{\prime \prime }),V(t^{})]=0`$.

Time ordering provides time sequencing of interactions. We regard the removal of time ordering as rather severe: something that can be quite important is lost.

### 2.1 Experimental evidence for quantum time ordering

Effects due to quantum time ordering  have been observed in various experiments. In one well known experiment  a factor of two difference in double ionization in atomic helium was observed when incident protons were replaced by anti-protons. Since an anti-proton may be regarded as a proton traveling backward in time, this effect was attributed  to a reversal of the effect of time ordering. Here time reversal ($`𝒯`$) is compensated by charge conjugation ($`𝒞`$) so that the well accepted $`𝒞𝒫𝒯`$ invariance under the product of charge conjugation, parity change ($`𝒫`$), and time reversal is preserved. A more direct experiment has been done using time dependent magnetic fields to produce transitions in Yb atoms . A more recent example of time ordering was observed in the polarization of light emitted following excitation with ionization of electrons in helium caused by the impact of fast protons . Data are shown in figure 2.

## 3 Discussion

Space and time are in some ways similar. In the classical wave equation $`x`$ and $`vt`$ are mathematically interchangeable. In relativity $`ict`$ becomes the fourth space-time dimension. Many of our descriptions of classical particles involve locating objects or events in space and time, as in the case of particle trajectories. In quantum mechanics localization is tempered by uncertainty in both space and time. Space and time also have some general differences. Space has no preferred direction. Both causality and entropy give time direction.

The description of time evolution in quantum systems relies on three principal features, namely, i) an asymptotic condition imposed on a differential equation, ii) the use of dual representations, and iii) an energy-frequency relation. The asymptotic condition carried by $`i\eta 0^+`$, which may be imposed on the solution to the Schrödinger equation, gives a unique wavefunction with outgoing scattered waves. This corresponds to a forward direction of time propagation, imposed on the time evolution operator. The effect of this contribution can be measured, as we have illustrated above. By use of dual representations we mean that interrelated conjugate spaces are defined by integral transforms so that amplitudes may be analyzed using alternate representations. For example, the Green’s function $`G(f^{},f)`$ is the Fourier transform of the time evolution propagator $`U(t_2,t_1)`$. Amplitudes related by Fourier transforms are constrained by the band width theorem, $`\mathrm{\Delta }f\mathrm{\Delta }t1/4\pi `$. An energy-frequency relation commonly used in quantum mechanics is linear, namely $`E=hf`$, used for photons, while the momentum-wavelength relation is an inverse relation, $`p=h/\lambda `$. In the general time dependent Schrödinger wave equation, the linear energy-frequency relation corresponds to an energy operator777Mathematically this corresponds to $`[E_{op},t]=\mathrm{}`$, i.e. non-commutivity., $`E_{op}=i\mathrm{}/t`$.

Some difficulty with time ordering can arise. In relativity, where space and time are mixed together, it is well known that the order in which interactions or events occur can be different as seen by observers who move relative to one another. Specifically using relativity one observer could correctly deduce that person A is guilty of throwing a switch that starts a fight before B throws his switch, while another observed moving relative to the first observed can correctly reach the opposite conclusion. In quantum mechanics the observation of events requires time intervals greater than a minimum time interval, $`\mathrm{\Delta }t`$, dictated by the uncertainty principle. Within $`\mathrm{\Delta }t`$ the sequence of events observed may not be reproducible. That is, causality may be violated for different reasons in relativity and in quantum mechanics888In relativity  events are either space-like or time-like regions separated by the light cone at $`v=c`$. In quantum mechanics the light cone is subject to uncertainty..

Microscopic-macroscopic connections can arise. When states are nearly degenerate the uncertainty principle leads to large times and distances. For a 2s-2p transition in hydrogen, $`\mathrm{\Delta }E=4.37\times 10^6`$ eV, $`\mathrm{\Delta }t=7.54\times 10^{11}`$ sec, and $`\mathrm{\Delta }`$ l = c $`\mathrm{\Delta }`$ t = 2.26 cm. Since we take $`c\mathrm{\Delta }t`$ as the size of the wavepacket, within $`\mathrm{\Delta }t`$ coherence persists at macroscopically large distances where coupling to the environment can occur. A similar connection is provided by the asymptotic condition999Other, less tangible examples of non-locality occur with particle identity and EPR entanglement of quantum states. that $`i\eta 0^\pm `$. Now the effect of this condition moves to asymptotically large times101010Apparently the smallest $`\mathrm{\Delta }t`$ dominates. That is, any envelope that damps the wavepacket faster than other conditions will determine the minimum size possible for an observation. Hence this $`i\eta 0^\pm `$ condition can never set the size of $`\mathrm{\Delta }t`$ in a finite universe.. However, since $`1/\eta \mathrm{\Delta }t`$, decoherence often occurs. Of course, if $`i\eta `$ is kept finite, then (choosing the proper sign) the state dissipates with a lifetime of order $`1/\eta `$. Decoherence and measurement are both under scrutiny at the this time. At issue is the nature of the dynamic transition from quantum coherence to classically well defined, observed, decoherent events. We leave this transition from quantum to classical physics for another discussion.

Time ordering has been recently used to define time correlation , an independent time approximation  where particles evolve independently, and conditions under which different times may be used for different particles . This provides a framework for understanding how quantum particles and systems of quantum particles communicate about time. In the independent particle approximation, where spatial inter-particle interactions are removed, use of multiple times is possible, but optional. There is no communication between particles. In this limit one may use either a single time, with a single energy-time Fourier transform, or different times with a different energy-time transform for each particle. The use of different times for different particles is fully justified when coherence between single particle amplitudes is lost, e.g., if relatively strong randomly fluctuating residual fields influence each particle independently. Then the phase coherence that is needed to synchronize quantum clocks is lost. When spatial correlation is present, however, the use of multiple times is not feasible, even when the evolution of the particles is uncorrelated in time . Thus there is an asymmetry in spatial and temporal correlation: time correlation between particles is forbidden in the absence of spatial correlation, but spatial correlation between particles is permitted in the absence of time correlation.

More recently we have addressed coherent electron population transfer by eliminating quantum time ordering . In an ensemble of atoms with n states dynamically mixed with a strong external field, it can be useful to transfer the electron populations: where we want, when we want, for as long as we want, as often as we want, as completely as we want, in systems as large as we want, using simple math. This can be done in degenerate systems, i.e. systems without quantum time ordering. If fast ‘kicks’ are used, i.e. $`V(t)\delta (tt_0)`$, electron population can be transferred from a launch state to a target state instantaneously at $`t_0`$ and remain there indefinitely . Quantum transitions can occur within the time interval, $`\mathrm{\Delta }t`$, set by the uncertainty relation, but no observation of this transition can be reproducibly made within $`\mathrm{\Delta }t`$. This has application in coherent population trapping of electrons useful in quantum computing, in electromagnetically induced transparency, may be useful in slowing and stopping of light, and in genetic learning algorthims used to control chemical reactions. More details are given elsewhere in this book .

In classical physics the trajectory of a particle is constrained by Fermat’s principle: that nature seeks the most (or possibly the least) efficient way to go from A to B. The particle’s unique path is determined by minimizing the action. This is illustrated by the dark line in figure 3. On the other hand quantum mechanics may be obtained from classical mechanics  by quantizing the action. In quantum mechanics many paths from A to B may be possible, although those outside of an envelope of trajectories, whose width is proportional to $`\mathrm{}`$, are statistically improbable. The $`\mathrm{\Delta }E`$ in energy means that there are quantum fluctuations in energy, which briefly violate conservation of energy. This leads to time correlations  insuring that the electrons cooperate in seeking the most efficient way to get from A to B, subject to both the constraint of classical least action and the freedom of quantum uncertainty.

We note that our approach to characterizing how time works in quantum systems differs somewhat from Briggs and Rost  who emphasize the widespread use of a classical $`V(t)`$ in the time dependent Schrödinger equation to emphasize the similarity of time in classical and quantum systems. We emphasize the differences.

## 4 Summary

Time works somewhat differently in quantum mechanics than in classical mechanics. Unlike in classical mechanics time is not a well defined physical observable in quantum mechanics. Also in quantum mechanics there are fluctuations in phase occuring in each interaction step that enforce time ordering. While time itself is presumably the same quantum mechanically and classically, in quantum mechanics time operates in different ways.

## 5 Acknowledgments

We thank A.R.P. Rau and C. Rangan for valuable comments. KhR is supported by a NSF-NATO Fellowship.


text:
# Dynamical symmetry breaking under core excitation in graphite: Polarization correlation in soft X-ray recombination emission

## Abstract

ABSTRACT

A recombination emission spectrum is applied to study the local lattice distortion due to core excitation in graphite. The recombination emission spectrum reveals a long low-energy tail when the C $`1s`$ electron is excited to the $`\sigma ^{}`$ core exciton state. This indicates a large local lattice distortion around the excited carbon atom within a core hole lifetime ($``$10fs). Theoretical calculation based upon an ionic cluster model well reproduces the experiments. The strong polarization correlation between incident and emitted X-rays is conclusive evidence of symmetry breaking in the core exciton state due to coupling with asymmetric vibrational modes.

Innovations in X-ray experiments have greatly enhanced our understandings of the relaxation dynamics of core excited states in many condensed systems. Among them, spectroscopies of coherent second order processes, such as resonant Auger electron emission and resonant X-ray emission spectroscopies, once believed to be difficult to obtain have now become common and the best tool to study ultrafast relaxation dynamics of the core excited states Gelmukhanov99 ; Rubbenson00 ; Kotani01 ; Bruhwiler02 .

Since the core excited atom can be regarded as an electronically equivalent atom with the valence increased by 1 ($`Z+1`$ approximation), the sudden change of the charge balance around the excited atom may bring about many (shake-up or shake-off) satellites in the core level spectra. While electronic relaxation on core excitation has been much discussed, not much attention has been paid to the relaxation dynamics through electron-phonon coupling in the core excited states, especially in solid states. This is because many have long believed that the time scale of the phonon relaxation, which usually falls in sub picoseconds, is far longer than a core hole lifetime (less than several femtoseconds), so that core excited state immediately decays with electronic Auger decay process before heavy atoms start to move. In simple molecules and adsorbates on solid surface, however, recent experiments and theoretical analyses of resonant Auger and soft X-ray emission spectroscopies have clearly indicated a large atomic displacements in core excited states when a core electron is excited to a bound unoccupied state Rubbenson00 ; Ueda00 .

Meanwhile in solid states, there have been no reports on a large atomic displacement in a core excited state since the pioneering experiment of soft X-ray recombination emission in diamond and graphite done by Y. Ma et al. Ma93 . In the experiments, the soft X-ray recombination emission spectrum showed a long low-energy tail when the C $`1s`$ core electron is excited into a bound core excited state, indicating a large lattice distortion around an excited atom Ma93  in the core exciton state. According to $`Z+1`$ approximation C $`1s`$ core exciton can be regarded as a nitrogen impurity atom well known to form a deep level in the middle of band gap with a large off-center instability Jakson90 ; Mainwood94 ; Mauri95 . Tanaka and Kayanuma interpreted the characteristic feature of the recombination emission spectra of diamond with a theory in which local phonon modes are strongly coupled with the quasi-degenerate core exciton states Tanaka96 . They clarified that the off-center instability is induced by a cooperation of quasi-Jahn-Teller and Jahn-Teller effects in the core excited state, and predicted that the spectrum should have a distinct polarization correlation between the incident and emitted X-ray photons. This polarization correlation is decisive evidence that the local symmetry is broken by ionic coupling of a core exciton with lattice phonon systems, i.e. dynamical symmetry breaking  in core excited states. Our aim here is to experimentally reveal the lattice relaxation dynamics in the core excited state of a solid state with soft X-ray recombination emission spectrum.

In this Letter, we report the recombination emission in graphite which clearly shows low-energy tail in the emission spectrum. Considering the fact that the electronic configuration of the final state is just the same as in the initial state in the recombination emission process, the only possible mechanism responsible for this low-energy tail is the phonon relaxation in the intermediate core excited state. Thus this should be the direct evidence of the large distortion around the excited atom in the core exciton state in graphite. This is quite in contrast to the case of resonant Auger emission process, where the final state interaction as well plays an important role to determine the spectral feature Bruhwiler02 , which makes the interpretation of the spectrum complicated and sometimes leaves ambiguity. In addition, we report here for the first time a strong polarization correlation of the recombination emission, which reveals the dynamical symmetry breaking by the ionic couplings in the core excited state.

Graphite has regained great attention since the discovery of carbon nanotubes that show wide unique physical properties with slight change of wrapping a single graphite layer. So the study on the effect of the electron-phonon interaction in graphite is important to understand the physical properties of nanotubes.

C $`1s`$ absorption and emission of highly oriented pyrolytic graphite (HOPG) was performed using a flat field soft X-ray emission spectrometer Tokushima02  newly constructed in BL27SU at SPring-8 Ohashi01 . The energy resolution of incident and emitted photons are less than 0.1eV and 0.6eV at C $`1s`$ edge, respectively. The excitation energy was carefully calibrated using the energy position of Au $`4f`$ photoemission lines.

C $`1s`$ recombination emission spectra were measured at (A)’polarized’ and (B)’depolarized’ configurations as shown in Fig. 1. While two independent polarizations of an emitted X-ray in the polarized configuration are parallel and orthogonal to an incident X-ray polarization, they are necessarily orthogonal to that of the incident X-ray in the depolarized configuration. We show the C $`1s`$ recombination emission obtained by scanning the excitation X-ray energy across $`\sigma ^{}`$ absorption band in Fig. 2. The valence x-ray emission band appears below 284eV C1sXES , which is not shown here.

The C $`1s`$ X-ray absorption spectrum (C $`1s`$ XAS) shown in the inset is attributed to the transition of a C $`1s`$ core electron to the antibonding $`\sigma ^{}`$ conduction states. The peak at 291.7eV has been interpreted as the transition to a localized core exciton state ($`\sigma _1^{}`$), which is followed by the broad absorption band attributed to the excitation to the delocalized scattering state ($`\sigma _2^{}`$Batson93 ; Bruhwiler95 ; McCulloch96 . The excitation energies $`\mathrm{}\mathrm{\Omega }_1`$ are indicated in the absorption spectrum: (a) 290.7eV, (b) 291.7eV, (c) 292.7eV, and (d) 293eV. In Fig. 2, the emission spectra in the polarized and depolarized configurations are shown by a line with open circle and a thick red line, respectively.

The recombination emission spectra strongly depend on the excitation energy. The spectrum has a long tail starting from the elastic line (Rayleigh line) towards the low energy side when $`\mathrm{}\mathrm{\Omega }_1`$ is tuned with $`\sigma _1^{}`$ core exciton peak (Fig. 2(b)). This low energy tail almost disappears when $`\mathrm{}\mathrm{\Omega }_1`$ is 1.0eV off-resonant below the $`\sigma _1^{}`$ resonance (Fig. 2(a)). Similarly when $`\mathrm{}\mathrm{\Omega }_1`$ is increased, the low energy tail is shortened (Fig. 2(c)), and at the $`\sigma _2^{}`$ excitation, we cannot see any asymmetry in the spectral shape (Fig. 2(d)). The appearance of this low energy tail is interpreted as a hot luminescence, the photon emission taking place as the phonon relaxation proceeds Tanaka96 : The emitted soft X-ray photon energy is gradually lowered as a part of electronic excitation energy being transferred to the vibrational subsystems. When the excitation becomes off-resonant (Fig. 2(a)), the whole recombination emission process from the initial to final states becomes coherent and the intermediate core exciton state is virtually passed through. The effective time during which the core excited state can be effectively coupled with phonon systems becomes shortened, resulting in the disappearance of the low-energy tail Gelmukhanov99 . In addition, we have found out a small hump around 285eV in Fig. 2(b). This is attributed to the recombination emission when an induced coherent vibrational wave packet turns back at a turning point on an adiabatic potential surface of the core exciton state Mahan77 ; Kayanuma88 . These structures are hardly seen in the resonant Raman scattering spectrum in optical region, because the lifetime of the excited state is usually so long that the ordinary luminescence from the relaxed excited state dominates over these faint structure. Since it is these hot luminescence spectral features that well reflect the very early stage of the relaxation process Mahan77 ; Kayanuma88 , the soft X-ray recombination emission is powerful tool to study the ultrafast relaxation dynamics of the core excited state.

The most intriguing features are the polarization correlation in Fig. 2. The following two points should be stressed here; (i) The low-energy tail in recombination emission has been observed both in depolarized as well as polarized configurations; (ii) The intensity of the low-energy tail relative to the integrated intensity of the recombination emission on the $`\sigma _1^{}`$ core excitation is more pronounced in depolarized configuration than in polarized configuration. These suggest that the local symmetry around the excited atom is broken under the $`\sigma _1^{}`$ core excitation. Considering a minimal cluster consisting of four C atoms —– at the center is the excited atom surrounded by three nearest neighbor atoms —– we have three stretching vibrational modes as major coupling vibrations with the core exciton state: one symmetric and two asymmetric stretching vibrational modes. Since the depolarization process requires at least one symmetry breaking phonon emission, the asymmetric vibrations must be induced under $`\sigma ^{}`$ core excitation through the ionic coupling, while the coupling with the symmetric vibration does not change the structural symmetry. A theoretical analysis of these spectral shapes enables us to evaluate the coupling strengths of the core exciton with these vibrational modes.

Based on the cluster model, we consider a three antibonding $`sp^2`$ hybridized orbitals as an electronic basis set which are coupled with the three stretching vibrations Ueda00 . In a representation of a symmetrized basis set, the Hamiltonian for the core exciton states is represented by

$`H_e=\left[\begin{array}{ccc}ϵ_s(\alpha /\sqrt{3})Q_s& (\beta /\sqrt{3})Q_x& (\beta /\sqrt{3})Q_y\\ (\beta /\sqrt{3})Q_x& ϵ_p(\alpha /\sqrt{3})Q_s(\beta /\sqrt{6})Q_y& (\beta /\sqrt{6})Q_x\\ (\beta /\sqrt{3})Q_y& (\beta /\sqrt{6})Q_x& ϵ_p(\alpha /\sqrt{3})Q_s+(\beta /\sqrt{6})Q_y\end{array}\right]+H_0,`$ (4)
with

$$H_0=\mathrm{}\omega _sb_s^{}b_s+\underset{i=x,y}{}\mathrm{}\omega _pb_i^{}b_i,$$
(5)
where $`H_0`$ is unperturbed Hamiltonian for the vibrational systems; $`b_i`$ ($`b_i^{}`$) is boson annihilation (creation) operator for each mode: $`Q_i=1/\sqrt{2}(b_i+b_i^{})(i=s,x,y)`$; $`\mathrm{}\omega _s`$($`\mathrm{}\omega _p`$) is the energy of the vibrational system in $`s`$ ($`p=x,y`$) mode. The energies of the $`s`$ and $`p`$ states at $`𝐐=\mathrm{𝟎}`$ are denoted by $`ϵ_s`$ and $`ϵ_p`$, respectively, and $`\alpha `$ ($`\beta `$) is the coupling strength with the symmetric (asymmetric) modes. Because of the lack of inversion symmetry, the coupling with asymmetric modes $`Q_x`$ and $`Q_y`$ brings about simultaneously the Jahn-Teller coupling within $`p`$ symmetry core exciton states and the quasi-Jahn-Teller coupling between the $`s`$\- and $`p`$-symmetry core exciton states.

In Fig. 3, we depicted an aspect of adiabatic potential surfaces in the core excited state for a set of parameters shown below. The horizontal axis represents the atomic displacement of the excited atom along a bond direction. The unit of the horizontal axis is then evaluated to be $`\sqrt{(\mathrm{}/M\omega _{s,p})}`$, where $`M`$ denotes the mass of carbon atom. Doubly degenerated $`p`$ symmetry core exciton states at $`Q=0`$ is split into $`A_1`$ and $`B_1`$ states by Jahn-Teller coupling, and the lowest branch for the $`s`$ symmetry core exciton state is greatly lowered by the quasi-Jahn-Teller coupling with the upper branch. For symmetry reasons, one of the upper branches can couple with the lowest branch. It is clearly seen that as a result of the quasi-Jahn-Teller coupling the on-center position becomes unstable and the equilibrium position is shifted about 0.2Å away from the origin with about 1.27eV relaxation energy. The C $`1s`$ core electron is excited to the dipole allowed $`p`$ symmetry core exciton states, at $`Q=0`$ of the upper branch, and a nonadiabatic coupling causes it decay into the lowest branch. The low energy tail in the recombination emission is attributed to the relaxation process going along the lowest branch toward the equilibrium, and the hump structure is due to the hot luminescence at the turning point. As the lattice relaxation proceeds along with the potential surface of the asymmetric modes, the local symmetry around the excited atom is broken down, which causes the observed prominent low-energy tail structure in the depolarized configuration.

We show the calculations of the recombination emission in Fig. 4, which is calculated fully quantum mechanically by the formula for a second order optical process Tanaka96 . We have determined the parameter values so that the experiments can be well reproduced: $`\mathrm{}\omega _s=\mathrm{}\omega _p=0.15`$eV, $`ϵ_pϵ_s=0.4`$eV, $`\alpha =0`$, $`\beta =4.9`$ in unit of $`\mathrm{}\omega _p`$, and $`\mathrm{\Gamma }_{1s}=45`$meV. In our model, the damping of phonon oscillation is neglected for simplicity. This approximation is justified because the core excited state decays before reaching the thermal equilibrium, and the x-ray emission takes place only within that short lifetime of the core hole. The recombination emissions are plotted for the same excitation energies in the experiments. The calculated absorption spectrum is also shown in the inset, and the excitation energies are indicated by arrows. The calculations satisfactorily explain the experiments. The low energy tail is prominent when the excitation energy is tuned with the $`\sigma _1^{}`$ peak both in the polarized and the depolarized configurations. The relative intensity of the low-energy tail is more pronounced in the depolarized configuration than in the polarized configuration because the strong Rayleigh component is forbidden in the depolarized configuration. The couplings with the asymmetric modes are essential to reproduce the experiments; In fact the coupling with the symmetric mode has been neglected here. This is quite in contrast to the case of a BCl3 molecule with a same point symmetry, $`D_{3h}`$, where the coupling with symmetric stretching mode plays an important role Ueda00 . This may reflect a qualitative difference of the vibrational coupling effects between molecules and crystals; In graphite the expansion of the cluster may be greatly suppressed by the existence of surrounding atoms.

Under the higher excitation (Fig. 4(c) and (d)), asymmetry in the recombination emission disappears consistently with the experiments, for the reason mentioned above Gelmukhanov99 . In reality, when the $`\mathrm{}\mathrm{\Omega }_1`$ is well into high energy continuum, we should take into account itinerancy of the excited electron over the entire crystal. The delocalization of the excited electron makes the exciton-phonon coupling suppressed ToyozawaBook , letting the emission peak symmetric.

In conclusion, our experiments of the recombination emission confirm a large local lattice distortion around an excited atom in the core exciton state in graphite. A remarkable polarization correlation between incident and emitted X-rays has been observed for the first time, leading to the conclusion that the dynamical symmetry breaking in the core exciton state is mainly due to the coupling of the core exciton states with asymmetric vibrational modes.

We acknowledge for valuable technical assistance from the staff of BL27SU in SPring-8. We also thank Dr. Chainani for his critical reading of the manuscript and helpful comments. This experiment was carried out with the approval of the SPring-8 Proposal Review Committee (2002B0675).