text:
# Quantum Memory: Write, Read and Reset

CERN-TH/2002-096

## Abstract

> A model is presented for the quantum memory, the content of which is a pure quantum state. In this model, the fundamental operations of writing on, reading, and resetting the memory are performed through scattering from the memory. The requirement that the quantum memory must remain in a pure state after scattering implies that the scattering is of a special type, and only certain incident waves are admissible. An example, based on the Fermi pseudo-potential in one dimension, is used to demonstrate that the requirements on the scattering process are consistent and can be satisfied. This model is compared with the commonly used model for the quantum memory; the most important difference is that the spatial dimensions and interference play a central role in the present model.

(1) It is the purpose of this paper to propose a model for quantum memory (sometimes called a quantum register), which is an essential component of any quantum computer. While a classical memory contains a number, a quantum memory contains a superposition of quantum states. In this model, writing on the quantum memory, reading the content of the quantum memory, and resetting the quantum memory are all performed by scattering from the quantum memory. Because of this reliance on scattering pikesabatier2002 , spatial dimension plays a central role.

Writing: The issue here is how a given superposition of quantum states can be written on a quantum memory after the memory has been reset to a standard state.

Reading: In this case the issue is how to extract from the memory whatever superposition of states has been written there.

Resetting: For a quantum memory in an arbitrary superposition of quantum states, it is desired to erase this information and replace it by a standard state. This should be done without violating unitarity and time-reversal invariance. It may be noted that while time reversal is not an invariance of nature, its violation involves the second and third generations of quarks christenson1964 ; Quark2 ; aubert&abe2001 , which are not expected to play any significant role in quantum memory.

(2) Let $`|j`$ be linearly independent quantum states for the memory; a state for the memory is of the form $`_ja_j|j`$. Note that this is a pure state, as the content of a quantum memory should be. Without loss of generality, let the standard state be $`|1`$.

In order to perform any operation on the memory, a wave or equivalently a particle, or perhaps several particles, is sent in from the outside to interact with the memory. Thus the in field for the scattering process is

$$\mathrm{\Psi }^{\text{in}}=\left(\underset{j}{}a_j^{\text{in}}|j\right)\psi ^{\text{in}}.$$
(1)
It should be emphasized that $`\psi ^{\text{in}}`$ is our choice to accomplish whatever the purpose of the scattering is.

The corresponding out state is in general a sum of products

$$\mathrm{\Psi }^{\text{out}}=\underset{j}{}|j\psi _j^{\text{out}}.$$
(2)
This $`\mathrm{\Psi }^{\text{out}}`$ contains information about the state of the memory after scattering and the behavior of the scattered wave. Later, the scattered wave as described by $`\psi _j^{\text{out}}`$ moves away from the memory and the information contained there is no longer available. This means that the final state of the memory is given by $`\mathrm{\Psi }^{\text{out}}`$ averaged over this information that is no longer available. On the other hand, in order for the quantum memory to function, the final state of the memory must be a pure state. This condition of being a pure state leads to the conclusion that $`\mathrm{\Psi }^{\text{out}}`$ must also be of the form of Eq. (1), namely, Eq. (2) reduces to

$$\mathrm{\Psi }^{\text{out}}=\left(\underset{j}{}a_j^{\text{out}}|j\right)\psi ^{\text{out}}.$$
(3)
In other words, not only the in state but also the out state are unentangled. This leads to the important concept of admissible $`\psi ^{\text{in}}`$.

A $`\psi ^{\text{in}}`$ is defined to be admissible footnote  if, for all $`_ja_j^{\text{in}}|j`$, the corresponding $`\mathrm{\Psi }^{\text{out}}`$ is of the form of Eq. (3).

(3) In order to perform the required operations, it is necessary to have a sufficiently large collection of admissible $`\psi ^{\text{in}}`$. This collection is sufficient if, given any $`_ja_j^{\text{in}}|j`$ and $`_ja_j^{\text{out}}|j`$, there is at least one

$$\psi ^{\text{in}}\left(\underset{j}{}a_j^{\text{in}}|j\underset{j}{}a_j^{\text{out}}|j\right),$$
(4)
which has the property that, if Eq. (1) holds for this $`\psi ^{\text{in}}`$, then Eq. (3) holds.

With this setup, the three fundamental operations of writing on, reading, and resetting a quantum memory can be accomplished as follows.

(4) Writing. The simplest of these three operations is writing. Since the quantum memory has been reset beforehand, let $`_ja_j^{(0)}|j`$ be the given quantum state to be written on the memory. Then, writing can be accomplished by using $`\psi ^{\text{in}}\left(|1_ja_j^{(0)}|j\right)`$.

(5) Reading. Reading from a quantum memory is very different from, and more complicated than, writing on such a memory. Consider a quantum memory in a state $`_ja_j^{\text{in}}|j`$. It is desired to determine the values of these coefficients $`a_j^{\text{in}}`$ by interrogating this memory. What this means is that we choose a sequence of admissible $`\psi ^{\text{in}}`$’s, i.e.,

$$\psi ^{\text{in}(1)},\psi ^{\text{in}(2)},\psi ^{\text{in}(3)},\mathrm{},\psi ^{\text{in}(N)},$$
(5)
and then scatter them successively by this quantum memory. More precisely, consider the successive scattering processes:

$$\begin{array}{cccccccc}& _ja_j^{\text{in}}|j\psi ^{\text{in}(1)}& \hfill & _ja_j^{\text{out}(1)}|j\psi ^{\text{out}(1)}& \hfill & a_j^{\text{out}(1)}& =& a_j^{\text{in}(2)}\hfill \\ \hfill & _ja_j^{\text{in}(2)}|j\psi ^{\text{in}(2)}& \hfill & _ja_j^{\text{out}(2)}|j\psi ^{\text{out}(2)}& \hfill & a_j^{\text{out}(2)}& =& a_j^{\text{in}(3)}\hfill \\ \hfill & _ja_j^{\text{in}(3)}|j\psi ^{\text{in}(3)}& \hfill & _ja_j^{\text{out}(3)}|j\psi ^{\text{out}(3)}& \hfill & a_j^{\text{out}(3)}& =& a_j^{\text{in}(4)}\hfill \\ \hfill & \mathrm{}& & & & & & \\ \hfill & _ja_j^{\text{in}(N)}|j\psi ^{\text{in}(N)}& \hfill & _ja_j^{\text{out}(N)}|j\psi ^{\text{out}(N)}.& & & & \end{array}$$
(6)
Corresponding to the list (5), we have the list of $`\psi ^{\text{out}}`$’s, i.e.,

$$\psi ^{\text{out}(1)},\psi ^{\text{out}(2)},\psi ^{\text{out}(3)},\mathrm{},\psi ^{\text{out}(N)}.$$
(7)
From the quantities listed in (5) and (7) together with their interference, the values of $`a_j^{\text{in}}`$ are obtained. Once the $`a_j^{\text{in}}`$ are found, then the $`a_j^{\text{out}(N)}`$ can be calculated. An additional scattering using any one of the admissible $`\psi ^{\text{in}}\left(_ja_j^{\text{out}(N)}|j_ja_j^{\text{in}}|j\right)`$ returns the quantum memory to its initial state.

(6) Resetting. With reading as prescribed above, resetting is now straightforward. Suppose we want to reset a quantum memory in the initial state $`_ja_j^{\text{in}}|j`$ to the standard state $`|1`$. This resetting consists of the following two steps. (a) Read the memory as described above. \[Note that, after this process of reading is performed, the memory is in the original initial state $`_ja_j^{\text{in}}|j.`$\] (b) Apply an additional scattering using $`\psi ^{\text{in}}(_ja_j^{\text{in}}|j|1)`$. This leaves the memory in the desired standard state $`|1`$.

(7) The concept of quantum memory introduced and described here is quite general. For example, the scattering process

$$\mathrm{\Psi }^{\text{in}}=\left(\underset{j}{}a_j^{\text{in}}|j\right)\psi ^{\text{in}}\mathrm{\Psi }^{\text{out}}=\left(\underset{j}{}a_j^{\text{out}}|j\right)\psi ^{\text{out}}$$
(8)
does not have many restrictions, and may or may not be linear. Also the linearly independent states $`|j`$ are allowed to depend on time, and may or may not be the eigenstates of an operator.

Because of this generality, it is useful, and indeed necessary, to have some simple examples. One of the simplest such examples will be described below. Once this example is understood, it is not difficult to construct many other examples.

(8) The example of the quantum memory to be described below relies on the Fermi pseudo-potential in one dimension. The original idea of the Fermi pseudo-potential is to generalize, to three dimensions, the delta-function potential in one dimension. An excellent explanation of this pseudo-potential is given by Blatt and Weisskopf blattweisskopf . One of the most far-reaching applications of the pseudo-potential is to the study of many-body systems huangyangETAL .

Once the Fermi pseudo-potential in three dimensions is well understood, it is natural to ask whether similar considerations can be applied in one dimension. It turns out that, going from three dimensions back to one dimension, the interaction at a point is not limited to the original delta-function potential. In fact, the most general potential for the interaction at one point $`x=0`$ consists of three terms, the delta-function potential together with two Fermi pseudo-potentials WuCERN097 :

$$V(x,x^{})=g_1\delta (x)\delta (x^{})+g_2[\delta _p^{}(x)\delta (x^{})+\delta (x)\delta _p^{}(x^{})]+g_3\delta _p^{}(x)\delta _p^{}(x^{}).$$
(9)
Here $`V(x,x^{})`$ is defined by

$$(V\psi )(x)=𝑑x^{}V(x,x^{})\psi (x^{}),$$
(10)
while $`\delta _p^{}(x)`$ is similar to the derivative $`\delta ^{}(x)`$ of the delta function and is defined by

$$\delta _p^{}(x)f(x)=\delta ^{}(x)\stackrel{~}{f}(x)$$
(11)
with

$$\stackrel{~}{f}(x)=\{\begin{array}{cc}f(x)\underset{x0+}{lim}f(x),\hfill & \text{for}x>0,\hfill \\ f(x)\underset{x0}{lim}f(x),\hfill & \text{for}x<0.\hfill \end{array}$$
(12)
Note that, in Eq. (9), the $`g_1`$ and $`g_3`$ pieces are even while the $`g_2`$ piece is odd.

(9) One of the simplest examples for the quantum memory may be obtained as follows. First, in order to have scattering processes pikesabatier2002  and also interference between the incident and scattered waves, it is essential to have at least one spatial dimension. Secondly, the number of states $`|j`$ for the memory must be more than 1; otherwise, the information in the quantum memory consists only of one phase, and is thus no more than what is stored in a classical memory. In the language of potential scattering, this means that there are coupled channels. It should perhaps be mentioned that it has been known for several years that two-channel Schrödinger equations have some properties not expected from the one-channel case Khuri .

To get a simplest example, the number of spatial dimensions and the number of channels are both chosen to be the smallest allowed values, namely, one spatial dimension and two channels. Thus the Schrödinger equation under consideration is

$$\frac{d^2\mathrm{\Psi }(x)}{dx^2}+(V\mathrm{\Psi })(x)=k^2\mathrm{\Psi }(x)$$
(13)
on the entire real axis, where $`\mathrm{\Psi }(x)`$ has two components and $`V`$ is a $`2\times 2`$ matrix. From the knowledge of the Fermi pseudo-potential in one dimension discussed above, the most useful choice of $`V`$ for the present purpose is, with $`g_10`$ and $`g_30`$,

$$V(x,x^{})=g_1\delta (x)\delta (x^{})\sigma _1+g_3\delta _p^{}(x)\delta _p^{}(x^{})\sigma _3,$$
(14)
where the $`\sigma `$’s are the usual Pauli matrices.

Since there is no $`g_2`$ term in Eq. (14), this $`V(x,x^{})`$ is even under space reflection. Thus, the even wave and the odd wave do not mix. A straightforward calculation gives the following simple results for the $`S`$-matrix of these even and odd waves:

$$S_+(k)=\mathrm{exp}[i\sigma _1\varphi _+(k)]\text{and}S_{}(k)=\mathrm{exp}[i\sigma _3\varphi _{}(k)],$$
(15)
where

$$\varphi _+(k)=2\mathrm{tan}^1\frac{g_1}{2k}\text{and}\varphi _{}(k)=2\mathrm{tan}^1\frac{g_3k}{2}.$$
(16)
Note that $`S_+(k)`$ is independent of $`g_3`$, while $`S_{}(k)`$ is independent of $`g_1`$. Since any element of SU(2) can be expressed as a finite product of these $`S_+(k)`$ and $`S_{}(k)`$ with suitably chosen $`k`$’s, there is an infinite number of the desired $`\psi ^{\text{in}}`$ as given by (4), provided that a finite sequence of $`\psi ^{\text{in}}`$ is considered as a $`\psi ^{\text{in}}`$. Thus, writing presents no problem in this example.

Consider reading next. Let $`\left[\begin{array}{c}a_1\\ a_2\end{array}\right]`$ be the normalized quantum state of the memory. Then scattering, for example, by an odd incident wave leads to the wave function

$$\mathrm{\Psi }(x)=\left[\begin{array}{c}a_1\\ a_2\end{array}\right]e^{ikx}+\left[\begin{array}{c}a_1e^{i\varphi _{}(k)}\\ a_2e^{i\varphi _{}(k)}\end{array}\right]e^{ikx}$$
(17)
when $`x>0`$. Since

$$\mathrm{\Psi }(x)^{}\mathrm{\Psi }(x)=2[1+2\mathrm{cos}2kx\mathrm{cos}\varphi _{}(k)(|a_1|^2|a_2|^2)\mathrm{sin}2kx\mathrm{sin}\varphi _{}(k)],$$
(18)
this scattering process gives, through the interference term, the quantity

$$A_1=|a_1|^2|a_2|^2.$$
(19)
Similarly, scattering by an even incident wave gives

$$A_2=a_1^{}a_2+a_2^{}a_1.$$
(20)
These two quantities, $`A_1`$ and $`A_2`$, give the values of $`a_1`$ and $`a_2`$ except for a common phase. To obtain this common phase, it is sufficient to use a further interference with scattering from the standard state. In this way, reading and hence resetting can be accomplished.

(10) More than twenty years ago, Benioff Ben80  led the way in applying quantum mechanics to computers. After his pioneering work, there followed a number of major contributions majorcontributions . Since then, the field has flourished, as evidenced by hundreds of more recent papers, a small sample being smallsample . In the majority of the papers on quantum computing, spatial dependence is not taken into account. As a consequence, the usual model for quantum memory consists of a spin system or its generalization, and the operations on the quantum memory consist of applying unitary matrices to the quantum state in the memory. This prevailing model has led to a number of impressive results.

The present model differs from this previous one mainly in the presence of one or more spatial dimensions, making it possible to apply scattering in order to operate on the quantum memory, including the fundamental operations of writing, reading, and resetting. This is much more than a change in language, and the present model may have some advantages, including the following two. First, since a quantum memory is necessarily small in size moore1965 , scattering is the simplest way to change the content of a quantum memory. Secondly, from the point of view of physics, spatial dimensions are necessarily there, and their presence allows more possibilities of analyzing the quantum memory.

Because of the prominent role played by scattering in the present model, there are the incident, scattered, and total wave functions. They do not have any analog in the previous model. One of the consequences of this difference is that the Holevo bound holevo1973  needs to be modified. Let us recall that the phase shift blattweisskopf  of scattering is determined from the total wave function; indeed, the process of reading is nothing more than an application of the usual phase-shift analysis. In the language of quantum computing, with an admissible $`\psi ^{\text{in}}`$, both $`\mathrm{\Psi }^{\text{in}}`$ and $`\mathrm{\Psi }^{\text{out}}`$ are unentangled, but the total wave function is entangled.

(11) In addition to the fundamental operations of writing on, reading, and resetting a quantum memory, we mention one more operation related to decoherence decoherence . It is unavoidable even in principle for the $`\psi ^{\text{in}}`$ to deviate from an admissible one, a fact central to many issues, including the no-cloning theorem. When this happens, the out state of the memory is no longer precisely a pure state; this amounts to decoherence. As a quantum memory is operated on more and more times, the decoherence becomes more and more significant. It is impossible to use scattering to remove such accumulated decoherence.

It is therefore essential to have quantum memories periodically “cleaned up,” and this cleaning-up operation is outside of the operations of writing on, reading, and resetting the memory. In other words, from the point of view of physics and engineering, additional operations on the quantum memory must be provided. Consider for definiteness the simplest example where there are two quantum states which are degenerate. Suppose an external macroscopic field can be applied to the memory to lift this degeneracy; after a time much longer than the lifetime of the upper state, the memory goes into a pure state. If the external macroscopic field is then removed slowly, the memory remains in a pure state. Details will be published elsewhere.

###### Acknowledgements.

For the most helpful discussions, we are greatly indebted to John M. Myers. One of us (TTW) thanks the Theoretical Physics Division of CERN for their kind hospitality.


format: text

text:
# References

UOSTP-02105

hep-th/0208046

Thoughts on Big Bang

Dongsu Bak

Physics Department, University of Seoul, Seoul 130-743, Korea

e-mail: dsbak@mach.uos.ac.kr

> We present a consistent framework that enables us to understand the big bang singularity of our universe.

Until now there has been no theoretical framework to explain the big bang singularity consistently. String theories in principle include consistent gravity theories but so far there is no way to address big-bang-like singularities in a controlled manner.

In this short note, we like to attempt to present a consistent way of addressing such cosmological big-bang-like singularities.

One of the key observations lies in the fact that our universe should start out as a low entropic state and its entropy grows afterward according to the generalized second law. In fact the present date entropy including gravitational one may be estimated around $`10^{120}`$ and the entropy near big bang is considerably smaller and almost nothing compared to the present value. Explaining how such low entropic states arise naturally is a question seemingly impossible to answer. This is because the low entropic state immediately implies that it should be an improbable state at any rate. Thus we are facing the problem of explaining the arising of such improbable states that cannot be natural in any theoretical frameworks. Inflationary scenario is a good phenomenological attempt for the choice of the initial states which may lead to the present state of universe but cannot explain why our universe begins with such low entropic states after all.

In this note, we like to address the low entropy problem in a totally different manner. We assume that the gravitational theories governing the dynamics of our universe has a dual description in terms of quantum mechanical system of finite number of degrees. This assumption is based on the recent development of AdS/CFT correspondence and understanding of holographic principle. Further, recent observational data indicates that there presents a nonvanishing positive vacuum energy associated with our universe. If this is identified with cosmological constant, which by definition cannot be relaxed to zero by any classical means, one has to deal with a spacetime with positive cosmological constant. In this case, one may argue the degrees of freedom in the universe with positive cosmological constant is limited by $`3/(8G^2\mathrm{\Lambda })`$ with $`\mathrm{\Lambda }`$ being the cosmological constant.

The time evolution of such finite quantum mechanical system but having enough number of degrees has the following characters. Along infinite interval of time i.e. $`\mathrm{}<t<+\mathrm{}`$, the system mostly remains in its equilibrium states which correspond to the maximally entropic states for a given set of macroscopic conserved quantities. Of course, there are always fluctuations of all kinds of sizes around the equilibrium states of the quantum mechanical system. The larger the fluctuations are, one has in general the smaller chances of occurrence.

We like to identify the big bang and subsequent cosmic time evolution as a really huge fluctuation above the equilibrium occurring rarely along the evolution of the system. At the peak of one such fluctuation, the state displaced farthest from the equilibrium occurs along the one cycle of rising and subsiding of the fluctuation. If the fluctuation is huge enough, the peak corresponds to a considerably low entropic state compared to the equilibrium states. This peak will be identified with the big bang event and, thus, one has a natural explanation of the low entropy nature of big bang.

At the peak a violent relaxation toward equilibrium will follow, which certainly matches with the violent nature of big bang of our universe. For the huge enough fluctuation, the relaxation will occur for a cosmic time scale, which corresponds to the cosmological evolution we observe now. After the peak the entropy of the system tends to grow in accordance with the second law. Before the peak, however, the entropy is getting smaller for a cosmic time scale as the rising of the fluctuation. This is not in a contradiction with the second law because we are talking about fluctuations of rare occurrences.

Of course, the above framework does not provide any reason why the present state of our specific universe among all kind of possibilities is actually resulted from the big bang event. We are certainly not attempting such explanations. Here we like to merely point out that the above framework may set up a consistent arena in addressing big-bang-like singularities. Such attempts, anyway, will involve the argument of anthropic principle. For example, the universe of the above framework will remain at equilibrium states most of the time, which correspond to non-livable states and may be disregarded from the view point of the anthropic principle.

Finally, it should be commented that, in the above discussion, we implicitly identify the time in the quantum mechanical system with that in the gravity theory of our universe. This may be understood as follows. Due to the generalized second law holding both of the systems (descriptions), the directions of the time should be identified. Further utilizing the general covariance of the gravity theory, the time in the gravity theory can be identified with that in the quantum mechanical system.

We are eagerly looking for observational evidences supporting the above framework and further studies are required in this direction.

Note added: We are informed that a similar scenario is presented in Ref. .

Acknowledgment We would like to thank Jihn E. Kim for the valuable comments. This work is supported in part by KOSEF 1998 Interdisciplinary Research Grant and by UOS 2002 Academic Research Grant.


text:
# Small-Scale Cosmic Microwave Background Polarization from Reionization

## I Introduction

The angular power spectrum of cosmic microwave background (CMB) temperature fluctuations is now becoming a powerful cosmological probe , both due to our detailed understanding of physics during the recombination era  and progress on the experimental front . In addition to the primary anisotropies generated at the last-scattering surface, CMB photons are also affected by large-scale structure at low redshifts. These latter contributions result from scattering off free electrons in clusters or the reionized IGM and from modifications due the evolving gravitational field associated with the formation of structures .

The existence of such secondary signals has now become evident with the recent detection of small-scale power in excess of that from primary fluctuations . The simplest and most plausible explanation for this small-scale power is the Sunyaev-Zel’dovich (SZ; ), re-scattering of CMB photons from hot electrons in unresolved galaxy clusters. Although the power observed is considerably larger than theoretical expectations, the excess can be accommodated with a relatively small increase in the power-spectrum amplitude .

In addition to small-scale anisotropies in the temperature, increasing attention is now being devoted to detection of the CMB polarization. Besides resolving cosmological parameter degeneracies , the polarization will allow several unique cosmological and astrophysical studies to be carried out. These include a reionization signal , probes of gravitational lensing , and a signature of inflationary gravitational waves (IGW) through its contribution to the B, or curl, modes of the polarization .

Given the rapid pace of experimental progress and the rule of thumb that the polarization is typically 10% of the temperature anisotropy, it is appropriate to investigate the polarization produced by the secondary effects that have produced the recently detected small-scale power. This polarization is produced by Thomson scattering of the quadrupole moment of the radiation incident on the scatterer. The quadrupole moment can be either the primordial quadrupole that the scatterer sees  or the kinematic quadrupole that arises from quadratic terms in the Doppler shift when the gas moves transverse to the line of sight . Small-scale angular fluctuations in this polarization are produced by variations in the optical depth as a function of position across the sky.

Since the secondary polarization signals can affect cosmological studies involving the primordial polarization, and, by themselves, may provide important information on astrophysics at late times, it is important that we both quantify and understand the extent to which large-scale structure can be a potential source of CMB polarization. Here, we discuss the angular power spectra for scattering from reionized electrons and study how these may affect potentially interesting studies with CMB polarization.

Our calculation parallels that of Ref. , although differs in that we present a simplified derivation of the results based on a flat-sky approximation and use a halo-clustering approach  to describe fluctuations in the electron density, in analogy to similar recent calculations of small-scale temperature fluctuations from unresolved clusters . We also include for the first time the frequency dependence in the small-scale polarization using results for the polarization from individual clusters .

The paper is organized as follows. In § II, we introduce polarization signals associated with the scattering of the primordial CMB temperature quadrupole and with the kinematic quadrupole generated by transverse motions. We then display and discuss our results in § III. Though we present a general discussion of the polarization, when illustrating results, we will use the currently favored $`\mathrm{\Lambda }`$CDM cosmology with matter density (in units of the critical density) $`\mathrm{\Omega }_m=0.35`$, baryon density $`\mathrm{\Omega }_b=0.05`$, vacuum-energy density $`\mathrm{\Omega }_\mathrm{\Lambda }=0.65`$, Hubble constant (in units of 100 km sec-1 Mpc-1) $`h=0.65`$, and spectral $`n=1`$ for primordial density perturbations. We employ natural units with the speed of light $`c=1`$ throughout.

## II Polarization Power Spectra

If the radiation incident on a reionized electron has a nonzero quadrupole moment, then the scattered radiation will be linearly polarized. The two dominant origins for this quadrupole moment are: (a) A quadrupole from primordial CMB fluctuations, and (b) a quadrupole from the quadratic term in the Doppler shift if the scattering gas has a transverse velocity.

The statistics of the polarization produced in this way is inherently non-Gaussian: Although the amplitude of the polarization in a given direction is determined by the optical depth to Thomson scattering, the orientation is determined by the radiation quadrupole incident on the scattering gas. The power spectrum is thus in principle determined by a convolution of the optical-depth field with the quadrupole field.

In practice, however, we simplify by assuming that the quadrupole moment is smooth over large distances, and that there are small-scale variations only in the free-electron density. We can then proceed to calculate the polarization fluctuations that are linear in the electron-density fluctuations. The correlation length of the CMB quadrupole is comparable to the horizon, and so our assumptions are fully justified for this case, as long as we restrict our attention to multipole moments $`l10`$. On the other hand, the peculiar velocity is correlated only on much smaller scale, $``$60 Mpc in our fiducial $`\mathrm{\Lambda }`$CDM cosmology. Our calculations of the polarization power spectrum for the kinematic quadrupole will thus be reliable only for scales smaller than this, or multipole moments $`l100`$.

We first discuss the power spectra. A polarization map will consist of a measurement of the Stokes parameters $`Q(\widehat{𝐧})`$ and $`U(\widehat{𝐧})`$ as functions of position $`\widehat{𝐧}`$ on some patch of the sky. We can construct Fourier components $`Q(𝐥)`$ and $`U(𝐥)`$ by

$$X(𝐥)=d^2\widehat{𝐧}e^{i𝐥\widehat{𝐧}}X(\widehat{𝐧}),$$
(1)
where $`XQ,U`$, and $`𝐥`$ is a vector in the plane of a region of the sky sufficiently small to be considered flat. Since the Stokes parameters $`Q`$ and $`U`$ depend on the choice of axes, we consider the rotationally invariant combinations,

$`E(𝐥)`$ $`=`$ $`\mathrm{cos}(2\varphi _𝐥)Q(𝐥)+\mathrm{sin}(2\varphi _𝐥)U(𝐥)`$ (2)
$`B(𝐥)`$ $`=`$ $`\mathrm{cos}(2\varphi _𝐥)U(𝐥)\mathrm{sin}(2\varphi _𝐥)Q(𝐥),`$ (3)
where $`\varphi _𝐥`$ is the angle between $`𝐥`$ and the chosen x-axis in the plane of the sky. We define the angular power spectra $`C_l^{EE}`$ and $`C_l^{BB}`$ from

$$Y(𝐥)Y(𝐥^{})=(2\pi )^2\delta _D(𝐥+𝐥^{})C_l^{YY},$$
(4)
where $`YE,B`$, and the angle brackets denote an average over all realizations of the density field.

As discussed above, we suppose that the radiation quadrupole moment is smooth over the region of sky we are considering. If so, then

$`E(𝐥)E(𝐥^{})`$ $`=`$ $`B(𝐥)B(𝐥^{})`$ (5)
$`=`$ $`{\displaystyle \frac{1}{2}}\left(Q(𝐥)Q(𝐥^{})+U(𝐥)U(𝐥^{})\right),`$ (6)
while

$$E(𝐥)B(𝐥^{})=\frac{1}{2}\left(Q(𝐥)U(𝐥^{})Q(𝐥)U(𝐥^{})\right)=0,$$
(7)
where the latter equality is consistent with parity conservation. These results can be derived by noting that if the quadrupole moment is constant, then the orientation of the polarization is constant. If so, we may choose our axes on the sky so that $`U=0`$. Then, $`E(𝐥)\mathrm{sin}(2\varphi _𝐥)`$, and $`B(𝐥)\mathrm{cos}(2\varphi _𝐥)`$, but when averaged over the orientation angle $`\varphi _𝐥`$, we recover Eq. (5).

We now proceed to calculate the power spectra induced by reionization. The polarization in direction $`\widehat{𝐧}`$ due to scattering from free electrons is an integral along the line of sight ,

$$Q(\widehat{n})iU(\widehat{n})=\sqrt{\frac{3}{40\pi }}𝑑r\frac{d\tau (r\widehat{𝐧},r)}{dr}a_{22}(r),$$
(8)
where $`r`$ is the comoving distance, $`(d\tau /dr)(r\widehat{𝐧},r)=\sigma _Tn_e(r\widehat{𝐧},r)a(r)`$, $`a(r)`$ is the scale factor at a comoving distance $`r`$, $`n_e(r\widehat{𝐧},r)`$ is the free-electron density at direction $`\widehat{𝐧}`$ at distance $`r`$, and $`\sigma _T`$ is the Thomson cross section.

In Eq. (8), $`a_{22}(r)`$ is the radiation quadrupole moment at distance $`r`$. More precisely, $`a_{22}(r)`$ is the coefficient of the spherical harmonic $`Y_{22}(\theta ,\varphi )`$ in a spherical-harmonic expansion of the radiation intensity in a coordinate system in which the line of sight is the $`\widehat{𝐳}`$ direction. Note that we take $`a_{22}(r)`$ to be a function of distance only, and not direction, consistent with our assumption that the quadrupole is coherent over a large patch of the sky. Since we use Limber’s approximation below, in which angular correlations are induced only by spatial separations at the same distance, the variation of $`a_{22}(r)`$ with distance can be included consistently.

With the polarization written as a projection, Eq. (8), along the line of sight, the angular power spectrum follows in the flat-sky limit from Limber’s equation ,

$`C_l^{EE}`$ $`=`$ $`C_l^{BB}`$ (9)
$`=`$ $`{\displaystyle \frac{3}{80\pi }}{\displaystyle _0^{z_{\mathrm{rei}}}}𝑑z{\displaystyle \frac{d^2V}{d\mathrm{\Omega }dz}}|a_{22}(z)|^2P_{\tau \tau }^{(t)}({\displaystyle \frac{l}{d_A}},z),`$ (10)
where $`P_{\tau \tau }^{(t)}`$ is the power spectrum of $`d\tau /dr`$, proportional to the power spectrum of the electron density $`n_e`$, and the integral is taken up to the redshift $`z_{\mathrm{rei}}`$ of reionization using the comoving differential volume given by $`d^2V/d\mathrm{\Omega }dz`$.

We now assume that the free-electron density is distributed like the mass in the Universe and model the mass distribution following the halo approach to large-scale structure . We thus decompose the power spectrum into two parts, one that describes contributions from single halos (1-halo term) and a part that accounts for correlations between halos (2-halo term) :

$$P_{\tau \tau }^{(t)}=P_{\tau \tau }^{1h}+P_{\tau \tau }^{2h},$$
(11)
where

$`P_{\tau \tau }^{1h}(k,z)`$ $`=`$ $`{\displaystyle 𝑑M\frac{dn(M,z)}{dM}\left|\tau _l(M,z)\right|^2},`$ (12)
$`P_{\tau \tau }^{2h}(k,z)`$ $`=`$ $`P^{\mathrm{lin}}(k,z)`$ (14)
$`\times \left[{\displaystyle 𝑑M\frac{dn(M,z)}{dM}b(M,z)\tau _l(M,z)}\right]^2.`$
Here, $`(dn/dM)(M,z)`$ is the mass function of halos  and $`b(M,z)=1+\frac{\nu ^2(M,z)1}{\delta _c}`$ is the halo bias  with $`\nu (M,z)=\delta _c/\sigma (M,z)`$ the peak-height threshold with rms fluctuation within a top-hat filter at the virial radius corresponding to mass $`M`$ given by $`\sigma (M,z)`$ and threshold overdensity of spherical collapse given by $`\delta _c`$. Useful fitting functions for these quantities are tabulated in Ref. .

We define the projected scattering optical depth as $`\tau (\theta )=\sigma _Tn_e(y,\theta )𝑑y`$ where $`y`$ is the line-of-sight distance along each halo at angular distance $`\theta `$ from the cluster center. The two-dimensional Fourier transform of $`\tau (\theta )`$ is,

$$\tau _l=2\pi _0^{\theta _{\mathrm{vir}}}\theta 𝑑\theta \tau (\theta )J_0(l\theta ),$$
(15)
where $`\theta _{\mathrm{vir}}`$ corresponds to the virial radius of the halo. For simplicity, we model the electron distribution within each halo using a $`\beta `$-profile and normalize it such that the gas mass fraction of each halo produces the global baryon fraction . Finally, $`P^{\mathrm{lin}}(k)`$ is the power spectrum of the linear density field. We use the formulae of Ref.  to describe the transfer function and normalize the power spectrum to match $`\sigma _8=0.9`$ consistent with COBE fluctuations at large scales . We comment below on the $`\sigma _8`$ dependence of our results.

### A Primordial Quadrupole

The primordial quadrupole will have a coherence length comparable to the horizon. We thus expect that the amplitude of the polarization power spectrum measured on a $`𝒪(10^{})`$ patch of sky may differ by order unity from that on a different $`𝒪(10^{})`$ patch of sky (and likewise that our calculation should break down for $`l10`$). However, when averaged over the entire sky, the amplitude of the power spectrum should be given by replacing the quantity $`|a_{22}(z)|^2`$ in Eq. (10) by its expectation value, $`C_2^{\mathrm{\Theta }\mathrm{\Theta }}(z)`$, the variance of the temperature quadrupole at redshift $`z`$. At redshift $`z=0`$, with the power-spectrum tilt fixed at unity, COBE finds $`C_2^{\mathrm{\Theta }\mathrm{\Theta }}(z=0)=(27.5\pm 2.4\mu \mathrm{K})^2`$ . At higher redshifts, the mean quadrupole moment evolves due to the integrated Sachs-Wolfe effect and possibly, if the power spectrum is not flat, due to any scale dependence since the quadrupole probes smaller distances at earlier times. We calculate $`C_2^{\mathrm{\Theta }\mathrm{\Theta }}(z)`$ following Ref.  for our fiducial $`\mathrm{\Lambda }`$CDM cosmology and show the result in Fig. 1.

Finally, note that Thomson scattering from cold electrons will not change the photon frequency. Thus, there will be no frequency dependence of the primordial quadrupole if we use Stokes parameters in temperature units—rather than the intensity units used by Ref. —as we do throughout this paper.

### B Kinematic Quadrupole

As discussed in Ref. , an electron gas moving with a transverse velocity $`v_t`$ relative to the CMB rest frame sees an $`a_{22}`$ quadrupole moment (in a coordinate system in which $`z`$ is along the line of sight),

$$a_{22}=g(x)\sqrt{\frac{4\pi }{30}}v_t^2e^{2i\varphi _v},$$
(16)
where $`\varphi _v`$ is the orientation angle for $`v_t`$ on the plane of the sky. To obtain this result, note that in a coordinate system in which the $`\widehat{𝐳}`$ axis is aligned with the cluster’s motion, the quadrupole dependence of the radiation temperature is $`g(x)v_t^2(\mu ^21/3)=g(x)v_t^2(2/3)\sqrt{4\pi /5}Y_{2,0}`$, where $`\mu `$ is the cosine of the angle between the radiation direction and the $`\widehat{𝐳}`$ direction. However, in a coordinate system in which the $`\widehat{𝐳}`$ axis is taken to be along the line of sight, $`(\mu ^21/3)=(1/3)\sqrt{4\pi /5}Y_{2,0}+\sqrt{2\pi /15}(Y_{2,2}+Y_{2,2})`$. Thus, the coefficient of $`Y_{2,2}`$, the component of the quadrupole moment that gives rise to polarization in our direction, is only a fraction $`\sqrt{3/8}`$ of the total quadrupole moment.

Unlike the primordial quadrupole, the kinematic quadrupole has a frequency dependence which we denote by $`g(x)`$, where $`x=h\nu /kT_{\mathrm{CMB}}`$. Following Refs. , this frequency dependence can be calculated by expanding the spectral intensity distribution of the CMB in the rest frame of electrons, $`I_\nu x^3/(e^{x\gamma (1+v\mu )}1)`$, in terms of velocity $`v`$, with $`\gamma =(1v^2)^{1/2}`$ and $`\mu `$ the cosine of the angle between velocity and incident photon direction. We then obtain the frequency dependence of the quadrupole term, in temperature units instead of intensity units, to be $`g(x)=(x/2)\mathrm{coth}(x/2)`$. In Fig. 2, we show the frequency dependence of the kinematic quadrupole, which was neglected in Ref.  ***Note that our Figure for the frequency dependence differs from Fig. 4 of Ref.  due to our use of temperature units and their use of intensity units.. For reference, we also plot the frequency dependence of the thermal Sunyaev-Zel’dovich effect,

The bulk flows associated with large-scale structure have coherence scales of order $``$ 60 Mpc. At first, we might be tempted to think that if we were to survey some region of sky small compared with the coherence length $`1^{}`$ for the peculiar velocity when projected at a typical redshift of order unity, then the power-spectrum amplitude might generally differ by order unity from the power-spectrum amplitude on some other similarly sized patch of sky. This would be true if all the fluctuations were produced at one distance. However, since there will be $`𝒪(100)`$ 60-Mpc coherence patches along the line of sight, these will tend to average out, and the polarization power-spectrum amplitude should be roughly the same from one $`1^{}`$ degree patch to another. It is thus appropriate to replace $`|a_{22}(z)|^2`$ in Eq. (10) by its expectation value,

$$|a_{22}|^2=\frac{4\pi }{30}g^2(x)v_t^4=\frac{16\pi }{135}g^2(x)v_{\mathrm{rms}}^4,$$
(17)
where we have used $`v_t^4=(v_x^2+v_y^2)^2=(8/9)v_{\mathrm{rms}}^4`$, since $`v_x^2=v_y^2=v_{\mathrm{rms}}^2/3`$, $`v_x^4=v_y^4=3v_x^2^2=v_{\mathrm{rms}}^2/3`$, and $`v_x^2v_y^2=v_x^2v_y^2=v_{\mathrm{rms}}^4/9`$. We calculate the linear-theory rms peculiar velocity from

$$v_{\mathrm{rms}}^2(r)=\frac{k^2dk}{2\pi ^2}\left(\frac{\dot{G}}{k}\right)^2P^{\mathrm{lin}}(k,0),$$
(18)
where $`G`$ is the linear-theory density-perturbation growth factor, and the overdot represents a derivative with respect to radial distance. According the halo-clustering model , peculiar-velocity fields are correlated over large distances and the nonlinear corrections to $`v_{\mathrm{rms}}^2`$ are small. The resulting linear-theory rms kinematic quadrupole is also shown in Fig. 1 assuming $`g(x)=1`$ as relevant for Rayleigh-Jeans (RJ) part of the frequency spectrum when $`x0`$, and for $`\nu =150`$ GHz and $`\nu =220`$ GHz.

Before moving on to discuss our results, a few words on how our derivations compare with those of Hu  are necessary. Note that our Eq. (10) agrees with Eq. (63) of Ref.  after converting to the logarithmic power spectrum, $`\mathrm{\Delta }^2(k)=k^3P(k)/2\pi ^2`$, using Limber’s approximation with $`k=l/d_A`$, and substituting $`|a_{22}(z)|^2=(4\pi /5)Q_{\mathrm{rms}}^2`$ for the temperature quadrupole. Similarly, our derivation for the polarization power spectrum due to the kinematic quadrupole agrees with that of Ref. , though this comparison requires an additional step. The kinematic quadrupole which replaces $`Q_{\mathrm{rms}}^2`$ in Eq. (63) of Ref.  is given in Eq. (58) as $`(8/45)(1f_{\mathrm{kin}})v_{\mathrm{rms}}^4`$. The factor $`f_{\mathrm{kin}}`$ accounts for mode coupling associated with the velocity field and is given by the mode-coupling integral in the second line of Eq. (58) of Ref. . If we take the limiting case of $`f_{\mathrm{kin}}`$ with $`y_11`$ and $`y_21`$, such that the two velocity power spectra decouple from each other, then $`f_{\mathrm{kin}}=1/6`$ exactly and the relevant kinematic quadrupole becomes $`(8/54)v_{\mathrm{rms}}^4`$. This is consistent with Eq. (17) of this paper. This can be verified by substituting our Eq. (17) into our Eq. (10), which recovers Eq. (64) of Ref. . The fact that Hu finds numerically that $`f_{\mathrm{kin}}=1/6`$ to a very good approximation justifies our assumption that the velocity and density fields are effectively decoupled.

## III Results and Discussion

We summarize our results on the polarization power spectra in Fig. 3. Note that the secondary polarization discussed here contributes equally to E- and B-modes. While the 1-halo term dominates at arcminute angular scales and below, correlations between halos are important and determine the total effect due to secondary polarization at angular scales corresponding to a few degrees. The dependence of our results on the inclusion of the 2-halo term is consistent with the result obtained for the temperature power spectra from the kinetic SZ effect , while it is inconsistent with the thermal SZ effect, where contributions are dominated by the 1-halo term over the whole range of angular scales. The latter behavior is explained by the fact that the thermal-SZ effect is highly dependent on the most massive halos, while the kinetic SZ effect, and the secondary polarization signals calculated here, are independent of the gas temperature and thus can depend on halos with a wider mass range.

As shown in Fig. 3, the secondary E-mode polarization is several orders of magnitude below the E polarization from the surface of last scattering. The secondary polarization is therefore unlikely to be a source of confusion when interpreting polarization contributions to E modes. The amplitude of the primary effect in B modes, due to gravitational waves, is highly uncertain and depends on the energy scale of inflation . For illustration, we show in Fig. 3 the inflationary gravitational wave (IGW) signal assuming an energy scale for inflation of $`E_{\mathrm{infl}}=10^{16}`$ GeV; the amplitude of the power spectrum scales as $`E_{\mathrm{infl}}^4`$. At large angular scales the secondary polarization is several orders of magnitude below the peak of this hypothetical IGW polarization signal. If the energy scale of inflation is lowered considerably, say to $`E_{\mathrm{infl}}10^{15}`$ GeV, then we might guess that the secondary polarization could ultimately constitute a background.

As also shown in Fig. 3, however, there is a contribution to the B-mode power spectrum that arises from conversion of the primary E modes to B modes by gravitational lensing , and this is considerably larger than the secondary polarization. Moreover, we also show (the dot-dash curve) the contribution to the irreducible B-mode power spectrum that remains even after the lensing has been optimally subtracted with higher-order correlations . This residual lensing power spectrum is considerably larger than the polarization from reionization. If the power spectrum is measured at a frequency $`\nu 220`$ GHz, then the polarization power spectrum from the kinematic effect will be boosted by a factor $`5`$ from the $`g(x)=1`$ power spectrum shown in Fig. 3. Moreover, if $`\sigma _8=1`$ (rather than the value $`\sigma _8=0.9`$ assumed in Fig. 3), then both the secondary power spectra will be increased for the same reasons that the temperature power spectra increase by a factor $`3`$.However, the boost in the polarization power spectra will be smaller due to the fact that much of the polarization is induced by electrons in smaller halos, rather than the massive clusters that induce the temperature fluctuation. Even with the possible frequency and $`\sigma _8`$ boosts, the secondary effects we consider here will be unlikely to be a factor for either gravitational-lensing or gravitational-wave studies with B modes.

In Fig. 4, we show the fractional contributions to polarization power spectra associated with the scattering of the temperature quadrupole as a function of redshift. We show the total and the 1-halo term for three specific values of $`l`$ corresponding to degree scales to arcminute angular scales. Though not shown here, we find consistent behavior for the polarization power spectrum generated by the scattering of the kinematic quadrupole. As shown, contributions come over a broad range in redshift out to the assumed reionization redshift of 10 with a decrease at highest redshifts due to the decreasing abundance of massive halos at higher redshifts. At arcminute scales with $`l10^4`$, the signal arises from halos at $`z>1`$. A comparison of this behavior to Fig. 1 reveals that at redshifts greater than 1, the primary temperature quadrupole at the cluster positions results from a projection of the SW effect only. Thus, at small angular scales, scattering contributions come only from the quadrupole associated with the SW effect and not the total that includes the ISW effect as well.

In Fig. 5, we show the mass dependence of the secondary polarization signal, again using the scattering of the temperature quadrupole for illustration purposes. We show the total, the 1-halo, and the 2-halo term at three different values of $`l`$. While the 1-halo term is dominated by halos at the high-mass end of the mass function, the 2-halo term arises from a wide range in halo mass. At tens of arcminute scales equal contributions come from halo masses in the range of 1010 to 1014 $`M_{}`$. This is consistent with the equivalent result for the kinetic SZ effect where a wide range of masses contribute.

Note that in addition to the auto-correlation of polarization, one expects secondary temperature fluctuations due to galaxy clusters to be correlated with that of the secondary polarization involving the E-mode. The temperature-polarization cross-correlation with the B-modes is expected to be zero based on parity considerations. We considered all combinations between secondary polarization and temperature anisotropies involving thermal and kinetic SZ effects and found them to be zero based on simple geometric arguments.

While our simple flat-sky derivation of the secondary polarization anisotropy from reionization agrees with the all-sky approach of Ref. , our calculational method complements the one used there. We use the halo model to describe the non-linear power spectrum of electrons while in Ref. , electrons of the intergalactic medium were assumed to trace the dark-matter-density field. Our numerical results agree well with those of Ref. , particularly at large angular scales where they should both converge to the same linear-theory calculation. Here we have neglected to consider the expected smoothing of the electron density on small scales from reheating of the IGM gas. However, as Ref.  shows, these effects are easily included and reduce the power spectrum substantially only on angular scales $`l10^4`$ smaller than those we have considered here.

While our halo-based approach is likely to be affected by uncertainties related to the mass function or the distribution of electrons within halos, we expect our calculations to accurately reflect the polarization anisotropy power at small angular scales. In the case of the kinematic quadrupole, it is likely that we have overestimated the power at scales of a few degrees or more due to our assumption that the velocity field is coherent at such angular scales. We expect this assumption to only affect the 2-halo term of correlations and to result in an overestimate of $`C_l`$ when $`l`$ is less than $``$ 1000.

###### Acknowledgements.

We thank K. Sigurdson for useful discussions. This work was supported in part by NSF AST-0096023, NASA NAG5-8506, and DoE DE-FG03-92-ER40701.


text:
# 1 GX 339–4 as a transient: our campaign

## 1 GX 339–4 as a transient: our campaign

After almost three years of quiescence, the “persistent” BHC GX 339–4 became active again on 2002 March 26 . This source is important , as in the past it has shown in the past all of the “canonical” states of BHCs .

The full RossiXTE/ASM light curve from the start of the mission is shown in Fig. 1. We started our observations with RossiXTE on April 3rd and obtained roughly one pointing per week since then. The ASM rate (1.5-1 keV) increased to 0.8 Crab in less than two months, then decreased to $``$0.5 Crab in three weeks, to start rising again to 1 Crab, and at the time of writing it is still brightening (see Fig. 1).

We present here preliminary results of the timing analysis of a subset of PCA observations: four during the early phase of the outburst, when the source count rate was increasing monotonically with time, and one a few days into the decay. The times of the five observations considered here are marked with dotted lines in the bottom panel of Fig. 1.

## 2 Timing analysis of the early phase

For each of the first four observations, we produced a Power Density Spectrum (PDS) by selecting the energy range 3-15 keV, dividing the observation in shorter segments and averaging the corresponding PDS. The resulting PDS can be seen in Figure 2. A strong evolution with time is evident. The PDS of the first observation, on the initial rise of the outburst, is very similar to the typical Low-State PDS observed before with RTXE (e.g. ). A weak QPO is seen at $``$0.25 Hz. During the second observation, on the flattening part of the initial rise, the PDS is similar, but shifted to higher frequencies (the QPO is now around 0.2 Hz). The third observation was made just before a sharp brightening. The characteristic frequencies are even higher, with two harmonically-related QPOs at 0.6 and 1.2 Hz. At a much higher count rate, the fourth PDS shows even higher frequencies, with a 6 Hz QPO with complex harmonic content. This PDS is almost indistinguishable from the VHS examples in . At the same time, the X-ray colors measured with the PCA show that the first three observations follow a softening curve, while the fourth is much softer.

It is remarkable that we are observing here a smooth transition in the timing properties from LS to VHS, with no discontinuity seen, while the energy spectral parameters change abruptly.

## 3 A transient QPO!

Our fifth observation, on 2002 May 17, shortly after the ASM flux started to decrease, is different. In the first RXTE orbit, the 1s binned light curve does not show much variability and the PDS shows a power-law noise component with a weak and broad bump between 6 and 10 Hz (Left panel in Fig. 3). In the second RXTE orbit, the power-law noise is stronger, as can be seen from the light curve directly, and a very strong QPO at 6 Hz appears in the PDS. A detailed analysis of a dynamical power density spectrum shows that this QPO is not present during the first 150 seconds of the orbit, then appears suddenly within a time scale shorter than 16 seconds.

## 4 A long-awaited outburst

Our preliminary results show that the timing properties of the source move gradually from the LS to the VHS, despite sudden changes in spectral shape. When at high flux, the source entered a HS, with reduced timing variability, but the appearance of a strong transient QPO at 6 Hz makes the HS interpretation questionable, as rapid oscillations between different “flavors” of VHS have already been observed .


text:
# Surface characterization and surface electronic structure of organic quasi-one-dimensional charge transfer salts

## I Introduction

In strictly one-dimensional (1D) metals many-body theory predicts unusual behavior of the electronic properties due to their fundamental instability against an infinitesimal small perturbation of the Coulomb interaction. Such systems can no longer be described by conventional Fermi liquid (FL) theory. Instead, the concept of a Luttinger liquid (LL) has been introduced which is characterized by generic 1D features. These comprise e.g. bosonic excitation modes rather than fermionic quasi-particles, a power-law decay of the momentum integrated spectral weight towards the Fermi energy $`E_F`$ or spin-charge separation.Voit95  Most of these signatures are best seen in the (momentum resolved) single particle excitation spectrum as directly probed by (angle resolved) photoemission spectroscopy ((AR)PES). Indeed, (quasi-)1D metals were found to display marked deviations from conventional metallic behavior using (AR)PES.Dardel91 ; Hwu92 ; Dardel93 ; Coluzza93 ; Claessen95 ; Sekiyama95 ; Takahashi96 ; Gweon96 ; Zwick97 ; Zwick98 ; Vescoli00 ; Claessen02  Basically all 1D materials studied so far show no clear Fermi cut-off. Only recently, we obtained convincing evidence for spin-charge separation in the charge-transfer salt TTF-TCNQ based on an analysis within the 1D Hubbard model.Claessen02  However, PES is extremely surface sensitive and any deviation from conventional metallic behavior could simply be due to the surface being different from the bulk. Unfortunately, up to now only little effort has been spent on the investigation of the actual nature of the surface under study. This would be especially important for organic materials which are particularly susceptible to rapid photon induced decomposition in the vacuum ultraviolet (VUV). In this paper we aim to fill this gap for TTF-TCNQ and deal with another charge-transfer salt, (TMTSF)2PF6, to exemplify the importance of both intrinsic and extrinsic surface effects.

## II Organic charge-transfer salts

The organic charge-transfer salts comprise a vast variety of molecular crystals containing almost planar organic donor and/or acceptor molecules as essential structural building units. These are stacked on top of each other with a possible tilt of the molecular planes relative to the stacking direction. Several types of stacks can occur, e.g. consisting of only one species, or with molecules A and B alternating along one stack or being segregated to form two types of chains as in TTF-TCNQ. However, the interesting electronic properties of these compounds are not of molecular origin but arise from the interaction of adjacent molecules. Depending on the “side by side” and “face to face” interaction strength the crystals show predominantly one- and two-,Torrance87  or even three-dimensional features in their electronic behavior.Ishida01  The intermolecular interaction involves the $`\pi `$ orbitals pointing perpendicular to the molecular plane and ranges from van der Waals-type over weakly covalent to ionic in character. An on-molecule Coulomb repulsion energy in the range between 0.5 and 2 eV together with the relatively small band widths puts these systems in an intermediate coupling regime where correlations may be important.Torrance87  It is the quasi-tunability of the correlation strength and the dimensionality which makes the organic charge-transfer salts so interesting and produces this wealth of symmetry-breaking ground states including spin- (SDW) and charge-density waves (CDW), spin-Peierls states and even superconductivity. In this paper we focus on two systems, TTF-TCNQ and (TMTSF)2PF6 which could be classified within the above-sketched scheme as quasi-one-dimensional mixed valency segregated stack conductors. In TTF-TCNQ the mixed valency is due to incomplete charge transfer of 0.59 electrons from TTF to TCNQ while in the so-called Bechgaard salt (TMTSF)2PF6 it arises from the $`2:1`$ ratio between the radical cation TMTSF and the counter anion PF6.Torrance87  In the following we only show data which were recorded in the normal metallic state, i.e. above the CDW-transition temperature of 54 K for TTF-TCNQ Kagoshima88  and above the 1D-2D crossover temperature of about 110 K for (TMTSF)2PF6.Moser98

TTF-TCNQ (C18H8N4S4) crystallizes in a monoclinic structure (Fig. 1), space group $`P2_1/c`$, with lattice parameters $`a=12.298`$ Å, $`b=3.819`$ Å, $`c=18.468`$ Å, and $`\beta =104.46^{}`$.Kistenmacher74  The segregated TTF and TCNQ stacks run along the crystallographic b direction. The molecular planes are tilted (with opposite signs) by $`24.5^{}`$ (TTF) and $`34.0^{}`$ (TCNQ) with respect to b around a. The two types of chains alternate along a while they do not along c. Within a unit cell there are two TTF (TCNQ) chains with opposite tilting angles of the molecules thus leading to a herringbone-type of arrangement.

The crystal structure of (TMTSF)2PF6 (2C10H12Se4.PF6) is triclinic, space group $`P\overline{1}`$, with lattice parameters $`a=7.297`$ Å, $`b=7.711`$ Å, $`c=13.522`$ Å, and angles $`\alpha =83.39^{}`$, $`\beta =86.27^{}`$, $`\gamma =71.01^{}`$ at 300 K.Thorup81  The easy axis, the crystallographic a direction, is made up by TMTSF stacks stabilized by the negatively charged PF6 counter ions in between. The molecular plane is almost perpendicular to a.

## III Experimental details

The TTF-TCNQ and (TMTSF)2PF6 single crystals were grown by diffusion (in pure acetonitrile) and electro-crystallization, respectively. They had typical dimensions of $`0.8\times 3.0\times 0.2`$ mm3 and $`1.5\times 0.5\times 0.1`$ mm3, respectively, with their 1D direction along the long sample axes. Their lancet-like shape makes it only possible to perform PES measurements on the (001) ($`(𝐚,𝐛)`$) plane for both TTF-TCNQ and (TMTSF)2PF6.

For both systems clean surfaces were exposed by in situ cleavage of the crystals at a base pressure in the low $`10^{10}`$ mbar range through knocking off a post glued on the sample surface. PES spectra were recorded using an OMICRON Multiprobe surface analysis system equipped with an EA 125 analyzer. For x-ray induced photoemission spectroscopy (XPS) the total energy resolution was set to 0.6 eV while for photoemission in the ultraviolet (UPS) the energy resolution amounted typically to $`70`$ meV and $`150`$ meV for TTF-TCNQ and (TMTSF)2PF6, respectively. The acceptance angle was $`\pm 8^{}`$ for XPS and $`\pm 1^{}`$ for UPS. Monochromatized Al Kα radiation ($`h\nu =1486.6`$ eV) and unmonochromatized He I photons (21.22 eV) from a conventional discharge lamp were taken as excitation sources. Calibration of the binding energy scale was achieved by measuring the Fermi edge of a freshly sputtered Au foil at low temperatures. All XPS spectra were recorded at room temperature whereas the UPS spectra on TTF-TCNQ and (TMTSF)2PF6 were taken at 60 K and 150 K, respectively.

## IV TTF-TCNQ

### IV.1 Ideal and actual sample surface in direct space

First of all it is important to note that the natural cleavage plane of TTF-TCNQ is parallel to the (001) lattice plane. If we regard the extended molecules for a moment as represented by point charges it is immediately seen that this (001) lattice plane essentially bears no net surface charge since it contains as many TTF- as TCNQ- molecules (Fig. 1). Thus there is no charge imbalance and the surface created by exposing this plane should essentially be stable. Taking into account more realistically the planar shape and the bulk arrangement of the TTF- and TCNQ-molecules the same holds for the (001) layer. However, due to the broken translational symmetry the Madelung potential at the surface will differ from that in the bulk.

Thus it is conceivable that there will occur some electronic charge redistribution probably concomitant with a structural surface relaxation. Since the intramolecular covalent bonds are quite strong and hence the molecules themselves rigid and since, in addition, there are no dangling bonds perpendicular to the surface such a structural relaxation most likely will happen by changes in the tilting angles with respect to the bulk. One could speculate that structural changes at the surface will take place such that a better screening of the Madelung potential is achieved, i.e. by a stronger hybridization of the $`\pi `$ orbitals perpendicular to the plane of the molecules. These ideas will be discussed in more detail below.

Figure 2 shows a typical scanning electron microscopy (SEM) image of a cleaved TTF-TCNQ crystal. One clearly sees the good quality of the exposed surface with large flat terraces. Thus, the actual sample surface indeed can be viewed as representing the (001) lattice plane.

### IV.2 Surface characterization by XPS

The surface composition of the TTF-TCNQ crystals was investigated by means of XPS. Figure 3 shows an overview spectrum of a TTF-TCNQ surface. Each spectral feature in the spectrum can be identified and classified according to its physical origin, i. e. as stemming from core levels or Auger processes. In addition, one can find satellite structures to each intense core level at multiples of about 22 eV away from the main line. These are related to inelastic losses suffered by the photoelectrons due to plasmon excitations of all the valence electrons. Except for a slight O contamination (see below) we find only signatures of the constituent elements of TTF-TCNQ.

For a quantitative analysis it is important to assure that the individual core lines and their plasmon satellites are well separated from each other so that there is no contribution of other origin except for a structureless background due to secondary electrons. In order to determine the spectral weight of a certain core excitation a Shirley background was subtracted before integration. The areas thus obtained were weighted by the inelastic mean free path of the photoelectrons (which is a function of kinetic energy), the transmission function of the analyser (also a function of kinetic energy), and the photoexcitation cross sections. Using experimentallyWagner81  and theoreticallyYeh85  derived cross sections basically yields identical results. In Tab. 1 we summarize values obtained for a typical sample in normal-emission (NE) geometry employing the experimentally determined cross sections. Note that the error amounts to about 20 %, mainly due to the uncertainty of the tabulated cross sections used. Nevertheless, the agreement of the surface composition as determined by XPS and the nominal composition given by the bulk stoichiometry of the material is striking. Especially there is no excess of carbon detectable and only a weak contamination with oxygen is observed.

Additional information beyond a qualitative and quantitative elemental analysis as discussed so far may be extracted from the line shapes and the fine structure of a certain core level. We first turn to the C 1$`s`$ and S 2$`s`$ lines since they can be discussed on equal basis. Their XPS-spectra recorded in NE geometry are displayed in Fig. 4. The C 1$`s`$ and S 2$`s`$ lines both consist of one single peak with an asymmetrically decaying tail at the higher binding energy side. From the peak maxima we derive a binding energy of 285.2 eV and 228.4 eV for the C 1$`s`$ and S 2$`s`$ level, respectively. The corresponding line widths (FWHM) amount to about 2.3 eV and 2.7 eV.

Spectra of the above mentioned core levels are rarely discussed in the literature for TTF-TCNQ.Butler74 ; Fraxedas98  As for the C 1$`s`$ level the reason is obvious. Carbon is not specific for either the TTF or the TCNQ molecule, and there are many (9) inequivalent sites in the crystal structure. Since at each of these the chemical environment is different the corresponding C 1$`s`$ signals are shifted in energy relative to each other. However, due to the finite experimental resolution and the lifetime broadening of the photoemission final states they overlap to one single relatively broad line as seen in Fig. 4.

A closer look at the S 2$`s`$ line seems to be more promising. Sulphur is specific for the TTF molecule and there are only two crystallographically different sites in a ratio $`1:1`$. Nonetheless, these cannot be resolved (s. Fig. 4). However, provided that there exist no further lines, e.g. due to a surface species with different binding energy and relative intensity, the superposition of two symmetric line shapes contributing with equal strength is always symmetric. Thus, from the S 2$`s`$ spectrum we conclude that the asymmetric tail indeed is inherent to each single component.

That the situation actually is more subtle can be seen from the S 2$`p`$ line shown in Fig. 5. In contrast to the S 2$`s`$ line, the S 2$`p`$ signal is split into two maxima at about 163.8 eV and 164.8 eV. The former maximum is about 15% higher in intensity than the latter. An additional shoulder is situated at about 165.9 eV. Again an asymmetrically decaying tail is seen at higher binding energies. It is obvious that the two maxima about 1 eV apart cannot be identified with the spin-orbit split 2$`p`$ doublet. They exhibit not only a quantitatively wrong intensity ratio (expected to be $`2:1`$ between lower and higher binding energy peak), but it is even reversed with the lower binding energy peak being significantly weaker. Furthermore, the splitting of the order of 1 eV seems far too high to be explained by a chemical shift of the binding energies due to the two inequivalent S sites. The bonding lengths of the S(1) and S(2) atoms (s. Fig. 1) are almost equal.Kistenmacher74  Also the intermolecular environment of the S(1) and S(2) atoms is topologically similar and in particular exhibits similar distances of the S sites to the neighboring TCNQ molecules. One has to conclude that there exist two significantly different S signals with possibly different relative strength which questions the above reasoning regarding the S 2$`s`$ line. Thus, in order to clarify the situation it is necessary to perform a line shape analysis of the S 2$`p`$ line. In accordance with our conclusion above we used two doublets with the spin-orbit splitting (intensity ratio $`2:1`$) fixed at 1.18 eV. Moulder92  If the observed asymmetric tail is intrinsic for each core level and not only caused by a superposition of different lines it would be readily explained by collective screening of the conduction electrons as is well known for metals.Doniach70  Hence, to each component in our analysis we assigned the so-called Doniach-Šunjić line shape describing the metallic screening. Besides the energy position and width a parameter $`\alpha `$ enters its definition which determines the asymmetry. A Lorentzian is recovered for $`\alpha =0`$. We used one single $`\alpha `$ for all components. In the fitting procedure included was also a convolution by a Gaussian of variable width to account for the experimental resolution ($`0.6`$ eV) and contributions to the line width which do not stem from purely exponential decay e.g. due to the coupling to phonons. Allowing for larger Gaussian widths than justified by the experimental resolution alters the line shapes of each component in that the onset at lower binding energies gets steeper, i.e. more Gaussian-like in character. The overall width and the peak asymmetry as well as all other fit parameters remain essentially unchanged. The results are displayed in

Fig. 5. The experimental spectrum is reproduced very well. The asymmetry parameter $`\alpha `$ comes out to be 0.11, in reasonable agreement with values for simple metals.Huefner96  From this analysis we infer the intrinsic character of the asymmetric tail due to the coupling of the photohole to the conduction electrons and confirm that essentially two S signals are observed which, as stated above, cannot be reconciled by the chemical shift of the binding energies of the two inequivalent S sites. The most interesting quantity to be explained is the intensity ratio of the lower to the higher binding energy contribution, which from the fit is found to be $`0.44:0.56`$.

Before further elucidating the origin of the two components of the S 2$`p`$ line and their intensity ratio we first turn to the line most intensively discussed in the literature, Grobman74 ; Epstein75 ; Swingle75 ; Metzger75 ; Epstein76 ; Grobman76 ; Ritsko78 ; Fraxedas98 ; Rojas01  the N 1$`s`$ core level excitation. As is obvious from Fig. 5 it consists of at least three contributions, a distinct maximum at about 398.0 eV and two shoulders at higher binding energies of about 399.5 eV and 401.4 eV. Note that for similar arguments as in the case of sulphur these energy differences are too large to be accounted for by possible chemical shifts of the two inequivalent N sites. Looking closer at the shoulder at highest binding energy one can actually distinguish additional fine structure which may be connected to two underlying components (marked by ticks in Fig. 5). Since they appear to be equally spaced and to display a similar intensity ratio as the two structures at lower binding energy we identify them simply as accompanying satellite features of two different components. This assignment is in line with the N 1$`s`$ spectrum of pure TCNQ crystals, which consists of one main line and a satellite structure well separated by about 2.6 eV.Lindquist88  This satellite was attributed to an intramolecular shake-up process between the highest occupied molecular orbital of the neutral and the lowest unoccupied molecular orbital of the ionized TCNQ molecule. Due to the only weak covalent bonding similar local excitations will persist in TTF-TCNQ.

We fitted this model to our data where again we simulated the line shapes according to Doniach and Šunjić. This applies also to the satellites although their actual spectral form is microscopically of other origin. Without any additional information the two main lines and one of the satellite peaks (the more pronounced one at lower binding energy) have to be varied independently while the second satellite is coupled to its main line in the same way, i.e. with respect to energy position, width, and weight, as the first one. In addition, we employed for simplicity only one single asymmetry parameter. The results of the fit are displayed in Fig. 5. The important quantities we can extract are the main line–satellite splitting of about 2.6 eV, the asymmetry parameter $`\alpha =0.11`$ and the intensity ratio of about $`0.65:0.35`$ between lower and higher binding energy contributions.

We note that the 2.6 eV main line–satellite splitting perfectly agrees with the experimental value for pure TCNQ and thus confirms our fit model. It is now interesting to correlate the intensity ratio for lower and higher binding energy contributions with that obtained for S 2$`p`$. Intriguingly, the ratios have within the accuracy of this evaluation just reciprocal values. The idea suggests itself that this may have something to do with the electron transfer from TTF to TCNQ. This leaves the TTF and TCNQ molecules in a mixed valent state of 0.59+ and 0.59-, respectively. If the charge fluctuations between TTF0 and TTF+ on the one hand and TCNQ0 and TCNQ- on the other take place on a slower time scale than the photoemission process itself one would observe two peaks corresponding to the two chemical states of TTF and TCNQ, respectively. Moreover, due to less effective screening of the core potential the TTF+ state should show up in the S 2$`p`$ spectrum at higher binding energy compared to the neutral chemical state. The reverse is true for TCNQ- and the N 1$`s`$ line. In both cases the charged state should have a larger spectral weight with a ratio $`0.59:0.41`$. Indeed, this scenario matches qualitatively our data and is even in fair quantitative agreement with our line shape analysis.

We only briefly mention here the controversial debate regarding the correct interpretation of the N 1$`s`$ spectral features in the 70’s. Partly, it was caused by the minor quality of the data which showed quite large intensity variations depending on the method of sample preparation.Grobman74 ; Swingle75 ; Ritsko78  In particular, none of these measurements were done on cleaved single crystals as in this work. Thus, a reliable quantitative analysis was highly impeded although the idea of two chemical states of N to be seen in the spectra was used early in order to determine the amount of charge transfer.Grobman74  Moreover, much of the persuasive power of our above argumentation is owed to the correlation of the results of our analysis for the N 1$`s`$ and S 2$`p`$ spectra which previous work failed to attempt.Ikemoto77 ; Tokumoto82  Instead, it was argued from calculations of the Madelung potentials that Coulomb energy differences may account for the observed relative energy shifts.Epstein75 ; Metzger75 ; Epstein76  However, it was shown that as no polarization effects in the solid state were taken into account such calculations were of little use.Grobman76

Not least because of some reports on evidence for strong angle dependent intensity variations in XPS spectra of TTF-TCNQ, especially regarding the N 1$`s`$ level, Swingle75 ; Ritsko78  some space is given to that issue here. Since 95 % of the detected photoelectrons at a certain kinetic energy which were not scattered inelastically stem from a layer of thickness $`3\lambda \mathrm{cos}\theta `$, where $`\lambda `$ is the inelastic mean free path at that energy, the information depth of XPS can be varied on a scale of about $`30`$ Å by changing the detection angle with respect to the surface normal. The results of our measurements at 0 (NE), 40 and 70 are displayed as solid, dashed and dotted lines in Fig. 4 and the insets of Fig. 5. The spectra are normalized to the background intensity at low binding energies. Note that the background might be angle dependent as well. Hence, only pronounced intensity variations as a function of emission angle should be taken seriously. In view of this caveat the S 2$`s`$, S 2$`p`$, and N 1$`s`$ lines are not conspicuous. The slightly decreasing peak heights with increasing emission angles are most probably just a matter of the normalization being systematically wrong. On the contrary, the C 1$`s`$ line displays at the biggest emission angle some additional spectral weight at higher binding energies. This is likely due to a slight surface contamination. Remarkable, however, is the angular dependence of the O 1$`s`$ line. While only a weak signal is seen at NE and 40 off NE a strongly enhanced peak emerges at 70 off NE. This behavior provides striking evidence that the O must be accumulated on the topmost surface layer. It originates probably from the residual gas molecules in the vacuum chamber. The observed O contamination takes place on a very short time scale and has saturated within minutes. However, since the amount is small it does not severely affect the UPS measurements discussed below.

To make the comprehensive discussion of the XPS spectra conclusive with respect to our aim, i.e. to relate surface and electronic structure, we summarize the results of this paragraph as follows: XPS is a valuable diagnostic tool for the characterization of the surfaces of the organic charge-transfer salt TTF-TCNQ. Both the elemental and line shape analysis point to the fact that we are dealing with perfectly reproducible, well-defined, and hence intrinsic surfaces of metallic character. Determination of the charge transfer per molecule at the surface provides no hint for a significant deviation with respect to the bulk. However, so far nothing is anticipated regarding the question, if the surface electronic properties are really representative for the bulk material.

### IV.3 Crystalline surface order and ARPES

From the above paragraph we know that the chemical composition of the surfaces under investigation is stoichiometric. In addition the line shape analysis indicates a metallic surface character. This may hint at long-range crystalline order. To validate this conjecture the method of choice is diffraction with low energy electrons (LEED). This probes the surface atomic order on a lateral scale given by the coherence length which amounts to typically 100 Å. Our attempts to obtain a LEED pattern failed, however. In the light of various scanning tunneling microscopy (STM) studies on both TTF-TCNQ filmsAra95  and as-grown crystal surfacesSleator88 ; Nishiguchi98  we ascribe this lack of observation to the destruction of the ordered surface by the electron beam itself.

That the TTF-TCNQ surfaces indeed are long-range ordered can be inferred from the ARPES measurements depicted in Fig. 6. The left-hand panel shows angle-resolved measurements along the $`\mathrm{\Gamma }`$Z-direction, i.e. along the one-dimensional b axis, whereas the series of the right-hand panel was recorded perpendicular to it (including the $`\mathrm{\Gamma }`$-point). At the $`\mathrm{\Gamma }`$-point two peaks are observed at about 0.19 eV (marked a) and 0.54 eV (marked b), respectively. Looking first at the left-hand panel of Fig. 6 one can follow the dispersion of these two features (the dashed lines are intended as a guide to the eye) both approaching the Fermi energy at an angle around 7. Two other features can be identified. Feature c disperses away from the Fermi energy starting at an angle of about 7 while feature d seems to be split off feature b at the $`\mathrm{\Gamma }`$-point and moves to higher binding energies with increasing angles (see dashed lines).

Switching to the right-hand panel, containing data measured perpendicular to b, a completely different behavior is observed. If one follows again peaks a and b as a function of emission angle starting with the spectrum at the $`\mathrm{\Gamma }`$-point essentially no dispersion is observed. The pronounced dispersions along the 1D direction clearly indicate long-range surface order. These together with the lack of any dispersion perpendicular to the 1D axis on the other hand truly reflect the electronic 1D character of the TTF-TCNQ surfaces. We refrain here from a detailed discussion of the observed dispersions along the b axis. We just note that we could demonstrate previously that they can be reconciled within the one-dimensional Hubbard model. Thus the data bear evidence for spin-charge separation where feature a represents the spinon and feature b the holon branch of the excitation spectrum.Claessen02

Rather another issue from our previous work we like to stress here. A comparison of the ARPES derived bands with the results of band calculations based on density functional theory (DFT) showed experimental band widths being larger by about a factor of 2. Otherwise good agreement of the DFT results with bulk properties, e.g. regarding the Fermi vectors as reflected in the periodicity of the CDW, were taken as evidence for a renormalization of the hopping integral $`t`$ and hence the band width at the surface. A possible explanation for the mechanism behind the renormalization might be the following. In the bulk the relatively rigid TTF and TCNQ molecules are tilted in opposite directions around the a direction by 24.5 and 34.0, respectively. At the surface the Madelung potential is different from the bulk and hence the balance between Coulomb and hybridization interaction may readjust. This most likely involves different tilting angles for the TTF and TCNQ molecules. Indeed it was shown that TTF-TCNQ films sublimed onto mica as a substrate exhibit two kinds of phases.Ara95  One of them was identified with that as known also from STM measurements on crystal surfaces. The other was interpreted with a rearrangement of at least the TCNQ molecules such that they are oriented steeper with respect to the surface. It was argued that both arrangements deviate only slightly in energy from each other. Since it is difficult to determine the actual tilting angles from the STM images if possible at all, it might be well the case that the phase only seen on evaporated thin films is the stabilized bulk phase while the other represents the reconstructed surface of single crystals. We conclude that regardless of the actual reconstruction intrinsic surface effects are important in TTF-TCNQ and reflected in the electronic structure of the surface.

### IV.4 VUV-radiation induced surface damage

Radiation induced surface damage both in the VUV and x-ray regime is a well-known but rarely talked about phenomenon in the context of PES. This is due to the fact that any time-dependent spectral changes regardless of their origin are usually unwanted since in most cases they signal some kind of surface degradation and hence hinder the observation of intrinsic surface properties. Up to now only in cases of technological interest such as in the field of polymers there exist a number of systematic studies related to this problem.Briggs90  Nevertheless, for several other even inorganic materials such effects have been reported, in particular at low temperatures.Purdie99  In any case it is important to be aware of this issue, especially using synchrotron radiation where the high photon flux may reduce the time scale on which surface damage occurs down to seconds. In the following we will address some of these aspects for TTF-TCNQ.

Figure 7 displays PES spectra taken at the Fermi vector kF and 60 K using the He I radiation (21.22 eV) of a conventional unmonochromatized hollow-cathode discharge lamp. For each curve the total VUV exposure until the spectrum was recorded is indicated. The observed spectral changes are twofold. First, the intensity of the structure at $`E_F`$ significantly decreases upon radiation exposure on a time-scale of about 2–3 hrs. Secondly, also the energy position of this structure changes. It shifts by about 50 meV to higher binding energies. That these time-dependent changes are really radiation-induced is shown in the inset of

Fig. 7. There it is demonstrated that the spectrum taken on a freshly cleaved crystal after 42 min VUV exposure is fully recovered even after about 4 hrs, if one measures a previously unexposed sample spot. Measurements using synchrotron radiation (not shown) reveal that these degradation effects are predominantly dependent on the photon energy (and not so much on the intensity). Using slightly higher photon energies (25 eV) the tolerable VUV exposure time does not scale with the photon flux compared to the measurements in the lab while 35 eV photons damage the surface within minutes. From this we conclude that there exists a threshold or a resonance energy in the VUV regarding beam damage. The observation that the electron beam of a LEED optics with typical energies above 25 eV destroys the surface almost instantly points to the scattering of the photoexcited electrons rather than to the photoabsorption process itself as the genuine cause for the observed damages. Note that the observed energy shift of the spectral feature at the Fermi energy is intrinsic and not caused by surface charging. From conjugated $`\pi `$-electron systems such irradiation effects are well-known and were attributed to the generation of structural and chemical defects, i.e. bond breaking and/or cross-linking.Koch01  These defects hinder the formation of delocalized molecular $`\pi `$-orbitals and thus affect first the corresponding states close to $`E_F`$.

We make a short remark regarding a more sophisticated explanation of the observed phenomena. We start from the microscopic physical picture of the undestroyed surface in terms of the 1D Hubbard model.Claessen02  Since the 1D Hubbard model and the LL picture are asymptotically equivalent within certain limits Voit95  it is tempting to discuss irradiation damage under the notion of the so-called bounded LL.Voit00 ; Meden00  There the effect of finite chain length onto the spectral properties of a LL is treated. It is conceivable that the irradiation induced defects are local in nature and just have the effect of cutting off the 1D chains. Introducing more and more defects means a continuous decrease of the mean chain length. Hence the spectral changes upon VUV irradiation would reflect the crossover to a bounded LL. Clearly, this issue demands further exploration.

## V (TMTSF)2PF6

### V.1 Ideal and actual sample surface in direct space

In the case of TTF-TCNQ we have seen that following simple considerations regarding the net charge of the exposed cleavage surface one already gets a clue of how the surface eventually will behave in terms of reconstruction. Our heuristically deduced findings were confirmed by STM imaging and ARPES measurements. The main point was to realize that the natural cleavage plane exposes non-polar surfaces. The situation is different for (TMTSF)2PF6.

Here the natural surface of as grown crystals is parallel to the (001) plane. The topmost surface layer contains either only TMTSF molecules or PF6 counter ions. Thus it clearly bears a positive or negative net surface charge (cf. Fig. 1) which is energetically highly unfavourable and makes the surface especially susceptible to electronic or atomic reconstruction. The former possibly would lead to a modified charge transfer at the surface changing the electronic properties severely with respect to the bulk. On the contrary, the latter probably would induce quite a high defect density, if there is no easy and unique way to rearrange the surface molecules such that a distinct energy minimum is achieved. Moreover, the polar character of the (001) lattice plane means that in a sense there is no well-defined natural cleavage plane. Instead of cleaving the crystal one will rather rip it off between the (001) lattice planes. It is conceivable that the obtained surfaces will at least be rough and resemble more a fractured surface than being shiny and flat. Actually, this is what we see in an SEM micrograph of an in situ cleaved crystal (s. Fig. 8). However, this does not exclude the possibility of finding areas which are with or without reconstruction undisturbed and well ordered on an atomic scale. Indeed, STM images were reported showing a regular arrangement of molecules.Fainchtein90  However, non-local probes will average over macroscopic length scales and hence may yield another picture.

### V.2 Surface characterization by XPS

It was just shown that the surfaces of our cleaved (TMTSF)2PF6 crystals are rather rough compared to the ones of TTF-TCNQ and thus might hinder the observation of dispersing electronic states by means of ARPES. However, the chemical composition should be unaffected by the surface morphology. Again we used XPS for the analysis of the surface stoichiometry. An XPS overview spectrum is displayed in Fig. 9. The most important lines are labeled according to their physical origin. Note that the P 2$`s`$ and P 2$`p`$ core levels interfere with various Se-Auger features and thus cannot be clearly discriminated. Otherwise, every line in the spectrum can be identified. Except for C and O (see below) only elements which are constituents of (TMTSF)2PF6 are found. In addition to the main lines plasmon loss features are found corresponding to a plasmon excitation energy of about 22 eV similar to the value seen in TTF-TCNQ.

Due to the overlap of various lines only a limited number of core levels was suited for the determination of the surface composition using the same evaluation method as above for TTF-TCNQ. The results for the cleavage surface which displayed the weakest O signal are summarized in Tab. 2.ann1  We give here the mean of the values which one gets using the cross sections of both Ref. Wagner81,  and Yeh85, , respectively. Compared to TTF-TCNQ the discrepancy between the nominal values and those derived from XPS is striking. It amounts to almost 80 % excess of carbon and about 40 % deficiency of Se.

Moreover, a non-negligible amount of oxygen is observed. We note that all surfaces were freshly prepared. It should be added that the measured compositions of the investigated surfaces scattered unsystematically with relative deviations from the averaged values of Tab. 2 by up to 50 % in contrast to the case of TTF-TCNQ. One thus could be led to suspect that this just reflects the bad quality of our crystals in general. However, measurements of the dc and microwave resistivity as well as electron spin resonance (ESR) data on our samples neatly show the SDW transition at 12 K.Dumm00  The pronounced deviation of the surface composition from the nominal one may be explained by severe reconstructions of at least parts of the surface due to its polar character. Just as well it could be related to processes taking place already during crystal growth, e.g. to the substitution of Se by the chemically equivalent O from the solvent or to microscopic cracks or precipitations (cf. Fig. 8) which are chemically modified. In any case, already from the XPS elemental analysis we must conclude that the surfaces of (TMTSF)2PF6 as exposed by in situ cleavage of well-characterized single crystals are not only not representative for the bulk material, they even are not intrinsic surfaces.

This conclusion is further corroborated, if one has a closer look at the various core lines. The F $`1s`$ line is expeditiously treated (s. Fig. 10). A single almost perfectly symmetric line is observed at a binding energy of about 686.6 eV. There exist three crystallographically inequivalent lattice sites for the fluorine atoms whose P–F bond length and angles, however, do not much differ. In addition, the distance of the PF6 complexes to the TMTSF stacks is very large. This excludes a notable chemical shift of the binding energies. Since the PF6 counter ions do not much hybridize with the TMTSF molecules and thus do not participate in forming delocalized conduction bands one would not expect any asymmetry of the F 1$`s`$ line as well.

Turning to the XPS spectrum of the Se 3$`d`$ doublet shown in Fig. 10 we only see one single line at about 56.5 eV binding energy because the spin-orbit splitting is too small to be resolved. For similar arguments as above possible chemical shifts in the binding energies of the four inequivalent Se atoms should not be important. The bonding lengths and environment of the Se atoms within the TMTSF molecule are quite the same and their distances to the adjacent TMTSF molecules and PF6 counter ions are large. What is remarkable is the lack of a pronounced asymmetric tail up to higher binding energies as it was observed for TTF-TCNQ and explained by the coupling of the photohole to the conduction electrons. The Se atoms are located on the 1D conducting stacks and a coupling of similar size as in TTF-TCNQ would be expected. This again manifests what we concluded already above from the chemical analysis that apparently the (TMTSF)2PF6 surfaces not at all reflect bulk properties.

We refrain from a thorough discussion of the C 1$`s`$ line as it overlaps with spectral weight due to Se Auger electrons and discuss it here only in the context of the angle dependence of the various XPS lines (Figs. 10 and 11). In contrast to the F 1$`s`$ and Se 3$`d`$ lines the C 1$`s`$ line shows a significant dependence upon variation of the emission angle. The line is split into two components at about 284.7 eV and 286.6 eV binding energy. The intensity of the latter increases notably at the biggest off-normal emission angle of 70 thus indicating a surface species. A similar even more pronounced behavior is observed for the O 1$`s`$ line at about 533.2 eV. We draw two conclusions from those observations: Firstly, the cleavage surface even if not as good as in the case of TTF-TCNQ is sufficiently well-defined to show angle dependencies at all. An irregularly rough surface as generated by fracture (as opposed to cleavage) of crystals would not display angular dependencies due to the averaging of exit angles and shadowing effects.Briggs90  Secondly, only part of the O signal can be attributed to an O contamination on top of the topmost surface layer. In the same way one can argue that also only part of the C 1$`s`$ intensity is intrinsic due to the C atoms in the TMTSF molecules, part stems from contamination of the topmost surface layer, and part originates from C contamination built in the crystal e.g. at microcracks.

### V.3 Crystalline surface order and ARPES

In the light of the results of the preceeding paragraph it might appear questionable whether one should anticipate long range surface order for (TMTSF)2PF6 at all. In any case, our attempts to see a LEED pattern failed. Obviously, if there was any long range surface order before, it is destroyed by the electron beam as in the case of TTF-TCNQ. Again we could use ARPES to reveal long range order by the observation of dispersing electron states. ARPES spectra along the 1D direction of (TMTSF)2PF6 are shown in the left hand panel of Fig. 12. In the energy range reaching to 2 eV below $`E_F`$ only one broad structure is observed with a maximum at about

1 eV. This structure sits on a relatively high inelastic background which artificially introduces a small shift to higher binding energies. If one corrects the data for those secondary electrons essentially no dispersion is seen. In the right hand panel of Fig. 12 we have summed up the ARPES spectra to simulate an angle integrated spectrum which can be compared to data previously published by Vescoli et al.Vescoli00  The agreement is almost perfect. In the context of bulk-probing optical and transport data in that paper the strong suppression of spectral weight at $`E_F`$ as well as the specific power-law decay of the leading edge towards the Fermi level was consistently interpreted as evidence for a LL scenario. Only the exponent governing the power-law decay would come out too high. However, it was argued that this observation together with the absence of any dispersion in related Bechgaard salts should rather be taken as indirect manifestation of the LL phenomenology: while the bulk properties can be reconciled within a standard LL picture, impurities at the surface induce localization of the spin and charge excitations which have to be described by a so-called bounded LL.Voit00 ; Meden00  The finite length chains and the thereby imposed boundary conditions would renormalize and thus explain the unusual high power-law exponent. In the light of our surface analysis we must however conclude that the measured (AR)PES spectra do not represent intrinsic surface let alone bulk properties of the Bechgaard salts.

Our reasoning on the Bechgaard salts in the context of ARPES measurements may be parallelled and further corroborated by the results published so far for the two-dimensional organic BEDT-TTF salts. As in the Bechgaard salts their surfaces comprise either anion or cation layers. Reconstruction/relaxation induced structural modulations have been revealed on the surfaces of various BEDT-TTF based compounds by STM.Ishida01  And again PES fails to see a clear Fermi cut-off in the metallic BEDT-TTF materials and notable dispersion of the electronic excitations close at $`E_F`$.Liu95a ; Liu95b ; Soederholm95 ; Soederholm97 ; Sekiyama97  Thus one is led to speculate that it is indeed the influence of surface effects, in particular their polar character, which in many organic charge-transfer salts hampers the observation of the electronic structure intrinsic for the bulk or a well-defined and reproducible surface by means of PES. So PES often may only pretend unconventional electronic behavior as it has been reported previously.

## VI Conclusion

In this paper we comprehensively studied the surfaces of two organic charge-transfer salts, TTF-TCNQ and (TMTSF)2PF6, in comparison. Strong limitations regarding employable probing techniques are imposed by their high sensitivity to chemical decomposition due to electron and photon irradiation. We showed that against this background x-ray induced photoemission spectroscopy is a valuable diagnostic tool which does not destroy the surfaces within reasonable time scales and provides information on surface contaminations, surface stoichiometry, and even metallicity of the surface. Thus it is possible to decide if such a surface most probably exhibits intrinsic – as is the case for TTF-TCNQ – or extrinsic – as is the case for (TMTSF)2PF6 – surface properties. In how far intrinsic surfaces represent bulk properties, however, is another question as we demonstrated for TTF-TCNQ. There photoemission spectra of the valence band showed clear indication for renormalized electronic properties at the surface with respect to the bulk. From our investigations we are able to confirm the observation of generic one-dimensional features in terms of spin-charge separation for TTF-TCNQ while we can definitely rule out unambiguous indications of Luttinger liquid behavior in (TMTSF)2PF6 as stated previously.

###### Acknowledgements.

We gratefully acknowledge financial support by the Deutsche Forschungsgmeinschaft (DFG) under CL 124/3-2.