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# Zero-Field Dichroism in the Solar Chromosphere

## Abstract

We explain the linear polarization of the Ca ii infrared triplet observed close to the edge of the solar disk. In particular, we demonstrate that the physical origin of the enigmatic polarizations of the 866.2 nm and 854.2 nm lines lies in the existence of atomic polarization in their metastable $`{}_{}{}^{2}\mathrm{D}_{3/2,\mathrm{\hspace{0.17em}5}/2}^{}`$ lower levels, which produces differential absorption of polarization components (dichroism). To this end, we have solved the problem of the generation and transfer of polarized radiation by taking fully into account all the relevant optical pumping mechanisms in multilevel atomic models. We argue that ‘zero-field’ dichroism may be of great diagnostic value in astrophysics.

Published in Physical Review Letters: Volume 91, Number 11, 111102, (2003)

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Spectropolarimetry provides key information on the physical conditions and geometry of astrophysical plasmas otherwise unattainable via conventional spectroscopy TBMS02 . The remote sensing of cosmical magnetic fields via the Zeeman effect is the most well-known example. In the presence of a magnetic field, the magnetic substates of atomic and molecular energy levels split, leading to a frequency shift of the $`\sigma ^\pm `$ ($`\mathrm{\Delta }M=\pm 1`$) and $`\pi `$ ($`\mathrm{\Delta }M=0`$) transitions MZ34 . If the Zeeman splitting is a significant fraction of the spectral line width, the polarization of the different components does not cancel out and an observable polarization pattern can then be produced via the emission process, as well as through dichroism and anomalous dispersion phenomena. The observed line polarization then depends on the strength and orientation of the magnetic field vector along the line of sight.

Yet there is a more fundamental mechanism producing linear polarization in spectral lines. In the outer layers of stellar atmospheres, where light escapes through the stellar surface, the atoms and molecules are illuminated by an anisotropic radiation field. The ensuing radiation pumping produces population imbalances among the magnetic sublevels of energy levels (that is, atomic polarization), in such a way that the population of substates with different values of $`|M|`$ are different. This is termed atomic level alignment. As a result, the emission process can generate linear polarization in spectral lines without the need for a magnetic field. This is known as scattering line polarization MZ34 . However, light polarization components will also be differentially absorbed when the lower level of the transition is polarized TBL97 ; TB99 . Thus, the medium becomes dichroic simply because the light itself is escaping from it. Since this process has nothing to do with magnetic fields, we call it zero-field dichroism. This mechanism may be of great diagnostic value because in weakly magnetized astrophysical plasmas, like the ‘quiet’ solar atmosphere, the contribution of the transverse Zeeman effect to the linear polarization is normally negligible. In order for zero-field dichroism to be operative, the atomic polarization of the lower levels must survive depolarizing effects, such as those produced by elastic collisions. Moreover, weak magnetic fields modify the atomic level polarization via the Hanle effect hanle ; TB01 , where the magnetic field strength $`B`$ (in gauss) that produces a significant change is $`B1.137\times 10^7/(t_{\mathrm{life}}g__L)`$ ($`t_{\mathrm{life}}`$ and $`g__L`$ being the level lifetime and Landé factor, respectively). Since the lifetimes of the lower levels of the transitions of interest are usually much larger than those of the upper levels, it is clear that diagnostic techniques based on this mechanism are sensitive to relatively low densities and magnetic field strengths.

In this letter, we demonstrate that zero-field dichroism is the key mechanism underlying the linear polarization of the Ca ii infrared triplet detected in observations close to the edge of the solar disk, in very quiet regions far away from sunspots. The observed fractional polarization amplitudes of the Ca ii lines at 849.8, 854.2 and 866.2 nm are $`Q/I`$ 0.035%, 0.13% and 0.12%, respectively SKG00 , the polarization signal in the 866.2 nm line being especially intriguing. This is a $`{}_{}{}^{2}\mathrm{D}_{3/2}^{}{}_{}{}^{2}\mathrm{P}_{1/2}^{}`$ transition whose upper level ($`{}_{}{}^{2}\mathrm{P}_{1/2}^{}`$) cannot be aligned. Therefore, emission following anisotropic radiative excitation cannot produce linear polarization in this spectral line and its detection has been considered ‘enigmatic’ SKG00 .

Consider a plane-parallel stellar atmosphere without magnetic fields. For reasons of symmetry, choosing the reference polarization directions as in Fig. 1, the polarization state of a radiation beam can be described in terms of the intensity $`I`$ and the Stokes parameter $`Q`$ for linear polarization. The transfer of $`I`$ and $`Q`$ along a ray path element d$`s`$ is described by the following equations:

$`\begin{array}{cc}\hfill {\displaystyle \frac{\mathrm{d}}{\mathrm{d}s}}I& =ϵ_I\eta _II\eta _QQ,\hfill \end{array}`$ (1)
$`\begin{array}{cc}\hfill {\displaystyle \frac{\mathrm{d}}{\mathrm{d}s}}Q& =ϵ_Q\eta _QI\eta _IQ,\hfill \end{array}`$ (2)
where $`ϵ_I`$ and $`ϵ_Q`$ are the corresponding emissivities, while $`\eta _I`$ and $`\eta _Q`$ are the absorption and dichroism coefficients, respectively. In a spectral line, the emissivities depend on the excitation state of the upper level of the transition. Conversely, $`\eta _I`$ and $`\eta _Q`$ are given by the excitation state of the transition’s lower level. We have considered an additional contribution to $`ϵ_I`$ and $`\eta _I`$ from a background continuum assumed to be unpolarized (i.e., $`\eta _I^{\mathrm{cont}}`$ and $`ϵ_I^{\mathrm{cont}}=\eta _I^{\mathrm{cont}}B_\nu `$, $`B_\nu `$ being the Planck function), which is a very good approximation towards the red part of the solar spectrum (see G00 ). For simplicity, we neglect stimulated emissions 111For a blackbody at the effective temperature of the Sun ($`T5800`$ K), the number of photons per mode even at 900 nm is $`\overline{n}6\times 10^21`$, and stimulated emission can be safely neglected..

We choose the quantization axis for angular momentum along the Z-axis of Fig. 1. Since the radiation field is axially symmetric around this direction, no quantum interferences are induced between magnetic sublevels and the excitation state of each atomic level is fully described by the individual populations (occupation probabilities) $`N_M`$ of each of its magnetic sublevels. Equivalently, we can describe the excitation state of each level of total angular momentum, $`J`$, by means of the following components of the atomic density matrix O77 ,

$$\rho _0^K(J)=\underset{MM^{}}{}(1)^{JM}\sqrt{2K+1}\left(\begin{array}{ccc}J& J& K\\ M& M^{^{}}& 0\end{array}\right)N_M,K=0,1,2,\mathrm{},2J,$$
(3)
which are just linear combinations of $`N_M`$. Because the radiation field in the assumed model atmosphere has no net circular polarization, we have an internal symmetry in our problem: $`N_M=N_M`$; therefore, only components $`\rho _0^K`$ with $`K`$ even can be different from zero. Of particular interest is $`\rho _0^0`$, which is $`(2J+1)^{1/2}`$ times the overall population of the level, and the alignment coefficient $`\rho _0^2`$, which quantifies the population imbalance between the magnetic sublevels. The line emissivities can be expressed as L84 ; TBL97

$`ϵ_I^{\mathrm{line}}`$ $`=ϵ_0\rho _0^0+ϵ_0w_{J_uJ_{\mathrm{}}}{\displaystyle \frac{1}{2\sqrt{2}}}(3\mu ^21)\rho _0^2,`$ (4)
$`ϵ_Q^{\mathrm{line}}`$ $`=ϵ_0w_{J_uJ_{\mathrm{}}}{\displaystyle \frac{3}{2\sqrt{2}}}(1\mu ^2)\rho _0^2,`$ (5)
where the $`\rho _0^0`$ and $`\rho _0^2`$ values are those of the upper level of the line transition under consideration, $`\mu =\mathrm{cos}\theta `$ (see Fig. 1), and $`ϵ_0=(h\nu /4\pi )A_u\mathrm{}\varphi _\nu 𝒩\sqrt{2J_u+1}`$ (where $`\nu `$ is the line frequency, $`A_u\mathrm{}`$ is the Einstein coefficient for the spontaneous emission process, $`𝒩`$ is the total number of atoms per unit volume, and $`\varphi _\nu `$ is the absorption profile). $`w_{J_uJ_{\mathrm{}}}`$ is a numerical coefficient whose value depends on the total angular momentum of the upper and lower levels, taking values $`2\sqrt{2}/5`$, $`\sqrt{2}/10`$, and 0 for the lines at 849.8, 854.2, and 866.2 nm, respectively. On the other hand, $`\eta _I`$ and $`\eta _Q`$ are given by identical expressions, but using the $`\rho _0^0`$ and $`\rho _0^2`$ values of the lower level, $`\eta _0=(h\nu /4\pi )B_\mathrm{}u\varphi _x𝒩\sqrt{2J_{\mathrm{}}+1}`$ instead of $`ϵ_0`$ (with $`B_\mathrm{}u`$ the Einstein coefficient for the absorption process), and $`w_{J_{\mathrm{}}J_u}`$ instead of $`w_{J_uJ_{\mathrm{}}}`$, where the $`w_{J_{\mathrm{}}J_u}`$ values are $`2\sqrt{2}/5`$, $`\sqrt{7}/5`$ and $`\sqrt{2}/2`$ for the aforementioned lines, respectively.

It can be deduced from Eqs. (1)-(2) and the expressions of $`ϵ_{I,Q}`$ and $`\eta _{I,Q}`$, that the emergent fractional linear polarization at the core of a strong spectral line is approximately given by TB99 ; TB01 :

$$Q/I\frac{3}{2\sqrt{2}}(1\mu ^2)[w_{J_uJ_{\mathrm{}}}\sigma _0^2(J_u)w_{J_{\mathrm{}}J_u}\sigma _0^2(J_l)],$$
(6)
where $`\sigma _0^2=\rho _0^2/\rho _0^0`$ is the fractional atomic alignment of the level under consideration. In this formula the $`\sigma _0^2`$ values are those at optical depth $`\tau =\eta _Ids`$ along the line of sight, where $`\tau 1`$. Eq. (6) shows clearly that the observed fractional polarization in a given spectral line has in general two contributions, one from the atomic polarization of the upper level caused exclusively by emission from a polarized upper level ($`\sigma _0^2(J_u)`$), and another one from the atomic polarization of the lower level ($`\sigma _0^2(J_l)`$). As shown here, the latter one (caused by the selective absorption resulting from the population imbalances of the lower level) plays a key role in producing the linear polarization pattern of the Ca ii IR triplet.

The atomic model in Fig. 1 is sufficiently realistic for modeling the Ca ii infrared triplet. Since calcium has no hyperfine structure, the only levels that may carry atomic alignment are the upper level $`{}_{}{}^{2}\mathrm{P}_{3/2}^{}`$ and the two metastable levels $`{}_{}{}^{2}\mathrm{D}_{3/2,5/2}^{}`$. Therefore, nine density matrix elements are required to describe the atomic excitation: the overall population of each of the five levels (i.e., $`\sqrt{2J+1}\rho _0^0(J)`$), the atomic alignment of the two levels with $`J=3/2`$, and the $`\rho _0^2`$ and $`\rho _0^4`$ values corresponding to the level with $`J=5/2`$. These irreducible tensorial components of the atomic density matrix are governed by the statistical equilibrium equations, $`0=\mathrm{d}\rho _Q^K(i)/\mathrm{d}t=_K^{}R_{iKK^{}}\rho _0^K^{}(i)+_{jK^{}}T_{jiKK^{}}\rho _0^K^{}(j)`$, where the relaxation matrix has the three contributions $`R_{iKK^{}}=_{\mathrm{}}R_{i\mathrm{}KK^{}}+_uR_{iuKK^{}}+D^K`$ caused by decays toward lower levels, excitations towards upper levels, and depolarization by elastic collisions, respectively, while the transfer matrix has contributions caused by decays from upper levels ($`T_{uiKK^{}}`$) and excitations from lower levels ($`T_{\mathrm{}iKK^{}}`$) L84 . The relaxation rates read

$`R_{i\mathrm{}KK^{}}`$ $`=\delta _{KK^{}}A_i\mathrm{}+\delta _{KK^{}}C_i\mathrm{},`$ (7)
$`R_{iuKK^{}}`$ $`=\delta _{KK^{}}B_{iu}J_0^0+s_{KK^{}}B_{iu}J_0^2+\delta _{KK^{}}C_{iu},`$ (8)
and the transfer rates are

$`T_{uiKK^{}}`$ $`=\sqrt{{\displaystyle \frac{2J_u+1}{2J_i+1}}}[\delta _{KK^{}}p_K^{}A_{ui}+\delta _{KK^{}}p_K^{}C_{ui}],`$ (9)
$`T_{\mathrm{}iKK^{}}`$ $`=\sqrt{{\displaystyle \frac{2J_{\mathrm{}}+1}{2J_i+1}}}[\delta _{KK^{}}p_K^{}B_\mathrm{}iJ_0^0+q_{KK^{}}B_\mathrm{}iJ_0^2+\delta _{KK^{}}p_K^{}C_\mathrm{}i],`$ (10)
where $`p`$, $`q`$, and $`s`$ are numerical coefficients that depend only on the quantum numbers of the levels involved in the transition (see Table 1). Since the radiation field is axisymmetric the absorption rates depend only on the line-integrated mean intensity ($`J_0^0`$), and on

$`J_0^2`$ $`={\displaystyle \frac{1}{4\sqrt{2}}}{\displaystyle d\nu _1^1d\mu ^{}\varphi _\nu [(3\mu ^21)I+3(1\mu ^2)Q]}.`$
It is important to note that in stellar atmospheres the polarization degree is small ($`Q/I1`$), and the main contribution to $`J_0^2`$ results from the intensity average. We call $`𝒜=J_0^2/J_0^0`$ the ‘degree of anisotropy’ of the radiation field. It determines the fractional atomic polarization that can be induced by optical pumping processes. In the solar atmosphere $`𝒜1`$, hence $`\sigma _0^21`$. Collisional rates $`C_{ij}`$ due to collisions with an isotropic Maxwellian distribution of electrons are modeled in analogy to the excitation by an isotropic unpolarized radiation field. We have used the inelastic collisional rates for Ca ii tabulated in SL74 , while the depolarizing rates $`D^{(K)}`$ due to collisions with neutral hydrogen atoms have been estimated according to Ref. LtH71 .

Figure 2 shows results of the self-consistent solution of the radiative transfer and statistical equilibrium equations in a semi-empirical model FAL91  of the solar atmosphere. The numerical solution has been obtained applying the iterative methods outlined in Ref. TB99 . The figure indicates how the degree of anisotropy corresponding to the K-line and to the 854.2 nm line vary with the K-line optical depth. These spectral lines are representative of the radiation fields in the UV doublet and IR triplet, respectively. The figure shows also the behavior of the fractional atomic alignments $`\sigma _0^2`$ of the 2nd, 3rd and 5th levels. Note that they have sizable values, even at the depths in the stellar atmosphere model where the line optical depths are unity along the line of sight.

The atomic alignment of the 5th level is governed by the radiation field in the K-line, with optical pumping in the lines at 849.8 nm and 854.2 nm playing only a marginal role. In fact, the height variation of $`\sigma _0^2(5)`$ closely follows that of the degree of anisotropy in the K-line throughout the whole atmosphere, with $`\sigma _0^2(5)\sqrt{2}/2(J_0^2/J_0^0)(\mathrm{K})`$. On the other hand, there are two optical pumping processes able to introduce atomic alignment in the lower levels of the Ca ii IR triplet (the metastable levels): repopulation pumping, which results from the spontaneous decay of the polarized 5th level; depopulation pumping, which occurs when some lower state sublevels absorb anisotropic light more strongly than others. Since the infrared triplet lines are much weaker than the ultraviolet H- and K-lines ($`\eta _I^{\mathrm{line}}/\eta _I^{\mathrm{cont}}10^5`$ for the former, while $`\eta _I^{\mathrm{line}}/\eta _I^{\mathrm{cont}}10^7`$ for the latter lines), the IR line photons escape from deeper atmospheric regions, where the $`J_0^2/J_0^0`$ values of the IR line transitions are much larger than the (negligible) $`\sigma _0^2`$ value of the 5th level at such depths (see Fig. 2). Consequently, at such atmospheric depths the long-lived metastable levels 2 and 3 are mainly aligned by depopulation pumping rather than by spontaneous emission from the upper level with $`J=3/2`$.

The solid lines in Fig. 3 show the emergent fractional polarization of the Ca ii infrared triplet calculated at $`\mu =0.1`$. Dotted lines show the emergent fractional polarizations if the metastable levels were unpolarized and dichroism negligible. Since the upper level of the 866.2 nm line cannot be aligned, the $`Q/I`$ signal in this transition is exclusively caused by dichroism \[see Eq. (6)\]. The linear polarization observed in the 854.2 nm line can, in principle, be caused by both, the emission events from the polarized upper level and to the differential absorption by the polarized lower level. However, $`|\sigma _0^2({}_{}{}^{2}\mathrm{D}_{5/2}^{})|>|\sigma _0^2({}_{}{}^{2}\mathrm{P}_{3/2}^{})|`$ at $`\tau (854.2)1`$ (see Fig. 2), while $`w_{J_{\mathrm{}}J_u}>w_{J_uJ_{\mathrm{}}}`$ in Eq. (6). Therefore, the observed $`Q/I`$ signal is de facto also mainly caused by dichroism in the solar atmosphere. The 849.8 nm line forms significantly deeper in the solar atmosphere, where the fractional alignment of its upper and lower levels are close to zero, hence its much lower polarization signal, whose sign turns out to be very sensitive to the assumed atmospheric model.

Note that the calculated $`Q/I`$ amplitudes of the 854.2 nm and 866.2 nm lines (see Fig. 3) are roughly twice the values reported in SKG00 . This can be due either to a simplified atmospheric modeling (the highly inhomogeneous solar atmosphere may not be well represented by a one-dimensional semi-empirical model), and/or to the existence of depolarizing mechanisms. Either case emphasizes the great diagnostic potential of the scattering polarization observed in the Ca ii IR triplet. For example, collisional depolarizing rates five times larger than the nominal values used here only slightly affect the ensuing $`Q/I`$ amplitudes. On the other hand, in the presence of a microturbulent magnetic field with a strength as low as 0.01 gauss, the atomic polarization of the metastable $`{}_{}{}^{2}\mathrm{D}_{3/2,\mathrm{\hspace{0.17em}5}/2}^{}`$ levels are significantly reduced and hence the emergent linear polarization in the 854.2 nm and 866.2 nm lines decreases to values similar to those observed (Hanle effect).

Zero-field dichroism may also be operating in other astrophysical objects (e.g., accreting systems) and should be fully taken into account when interpreting spectropolarimetric observations in other spectral lines besides the Ca ii IR triplet itself, whose polarization has been observed recently in supernovae SN .

Research partially funded by the Spanish Ministerio de Ciencia y Tecnología through project AYA2001-1649.


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# Coherent Anti-Stokes Raman Scattering Heterodyne Interferometry

## Abstract

A new interferometric technique is demonstrated for measuring Coherent Anti-Stokes Raman Scattering (CARS) signals. Two forward-directed CARS signals are generated, one in each arm of an interferometer. The deterministic nature of the CARS process allows for these two signals, when spatially and temporally overlapped, to interfere with one another. Heterodyne detection can therefore be employed to increase the sensitivity in CARS signal detection. In addition, nonlinear CARS interferometry will facilitate the use of this spectroscopic technique for molecular contrast in Optical Coherence Tomography (OCT).

OCIS codes: 110.4500, 300.6230, 190.4410, 120.3180, 040.2840

Optical Coherence Tomography (OCT) is an interferometric optical imaging technique capable of imaging tissue microstructure at near histological resolutions boppart1998 . Unfortunately, the linear scattering properties of pathological tissue probed by OCT are often morphologically and/or optically similar to normal tissue. To address this problem novel contrast methods for OCT have been recently developed, such as spectroscopic OCT morgner2000 , a pump and probe technique rao2003 , and the use of engineered microspheres lee2003  or microbubbles barton2002 .

Spectroscopic OCT (SOCT) measures the spectral absorption from tissues by measuring the spectral differences between the source and the backscattered interference signal to provide information about the properties of the scatterers in the sample. However, this technique is limited to the identification of scatterers that have absorption within the bandwidth of the optical source. A different method to obtain contrast enhanced OCT employs engineered microsphere contrast agents, which can be targeted to cell receptors thereby providing molecular specific contrast lee2003 . A drawback to this technique, however, is that the contrast agents may negatively impact the biology under investigation. We present a new method for achieving enhanced OCT contrast, exploiting the inherent vibrational frequency differences between molecular bonds within the tissues. The spectroscopic technique that is employed to detect these vibrational differences is Coherent Anti-Stokes Raman Scattering (CARS).

CARS is a well-known spectroscopic technique that has recently received significant attention for its applications to scanning microscopy. In CARS spectroscopy, the frequencies of two incident lasers, $`\omega _p`$ (pump) and $`\omega _s`$ (Stokes), are chosen such that the difference $`\omega _p\omega _s=\omega _v`$ is equal to a Raman-active vibrational mode of the molecule under study dermtroeder1998 . CARS is a non-linear, four-wave mixing process. Furthermore, the CARS field is a result of the interaction between four photons and is generated in the phase-matching direction at the anti-Stokes frequency $`\omega _{AS}=2\omega _p\omega _s`$, implying that the CARS signal intensity is linearly dependent on the Stokes field intensity and quadratically dependent on the pump field intensity. Note that, in addition to the CARS signal, a broadband non-resonant background is always present, limiting the vibrational contrast achieved in CARS microscopy. However, CARS is a coherent process, with the phase of the anti-Stokes field deterministically related to the phase of the excitation field. Therefore, constructive interference of the anti-Stokes field causes the CARS signal to be significantly larger than the spontaneous Raman signal, given the same average excitation power cheng2002bis . All these characteristics have allowed CARS to be successfully employed to provide vibrational contrast in scanning microscopy cheng2002bis ; duncan1982 ; zumbusch1999 ; wurpel2002 ; hashimoto2000 .

CARS scanning microscopy generally involves scanning overlapped and tightly focused pump and Stokes lasers through a sample while measuring the anti-Stokes signal amplitude point by point. The first CARS microscope duncan1982  utilized non-collinear pump and Stokes visible lasers to demonstrate microscopic imaging of the spatial distribution of deuterated molecular bonds in a sample of onion skin. Tightly focused, collinear near-infrared pump and Stokes pulses were used zumbusch1999  to achieve improved background signal suppression, and three-dimensional sectioning in living cells. In each of these CARS microscopy techniques, the anti-Stokes photons are counted in order to estimate the density of the Raman scatterers and/or Raman susceptibility magnitude in the focal volume of the microscope. However, the spectral phase information is lost in this process and can only be inferred. In this Letter we propose and demonstrate a new CARS interferometric technique called Nonlinear Interferometric Vibrational Imaging (NIVI) with the capability for heterodyne detection and the possibility to obtain a full reconstruction of the magnitude and phase of the sample Raman susceptibility.

The CARS interferometer described in this paper is presented in Fig.1.

An excitation field consisting of two overlapped pulses centered at the pump and Stokes wavelengths is divided by a beamsplitter into two separate interferometer paths, which are referred to in Fig.1 as arm ”S” (or sample arm) and arm ”R” (or reference arm). A sample of a molecule is placed into each arm into which the split excitation fields are focused. If the frequency difference between the pump and Stokes pulses is tuned to a Raman active vibrational mode present in both sample S and sample R, an anti-Stokes signal is generated in each arm of the interferometer. Because the anti-Stokes pulse phase is deterministically related to the phase of the pump and the Stokes pulses, the anti-Stokes fields are coherent with the excitation fields and also with each other. It follows (Feynman principle) that when these anti-Stokes fields are temporally and spatially overlapped, interference can be observed.

In our current setup the CARS is stimulated by a laser system similar to that employed by zumbusch1999 . A diode pumped frequency doubled Nd:YVO4 laser is used to pump a mode-locked Ti:sapphire oscillator operating at a center wavelength of 807 nm, with a bandwidth of 30 nm, a repetition rate of 82 MHz, and an average power of 300 mW. These pulses seed a regenerative chirped pulse amplifier (Coherent, RegA 9000) producing approximately 70 fs, 5 J pulses at a repetition rate of 250 kHz with an average power of 1.25 W. Ten percent of this average power is used as the pump beam while the remaining power is directed to an optical parametric amplifier (Coherent, OPA 9400) which generates a 4 mW average power Stokes beam, tunable from 400-1200 nm.

The pump and Stokes pulses, at 807 and 1072 nm respectively, are used to excite the strong, isolated Raman-active vibrational mode of benzene at 3063 cm-1. As shown in Fig.1, these pulses are collinearly overlapped using a dichroic mirror and split with a 50:50 ultrafast beamsplitter into arms S and R. In each arm, a 30 mm focal length, 12 mm diameter achromatic lens is used to focus the pump and Stokes beams into a quartz cuvette filled with benzene. The anti-Stokes signals generated in each arm are collected in the collinear phase matching direction using 30 mm focal length, 12 mm diameter singlet lenses. The two anti-Stokes pulses are overlapped in time by adjusting the relative delay and in space by adjusting the position on a second beamsplitter. A high-pass filter at 742 nm eliminates the remaining excitation light. The filtered anti-Stokes signal is spatially filtered through a 50 m diameter pin hole. The relative delay is scanned by a computer-controlled single axis translation stage at a constant rate in arm R, and the CARS signal intensity is measured with a photomultiplier tube PMT (Hamamatsu, HC 123). Lastly, the signal from the PMT is filtered with a low-pass anti-aliasing filter and sampled with a PC based data acquisition system.

Figures 2(a) and 2(b) show the observed relationship between the CARS and the Stokes intensity (pump intensity fixed) and the CARS and the pump intensity (Stokes intensity fixed), respectively. The solid lines represent linear fits of the experimental data. In agreement with theory, the slope of the fitted lines verifies the linear relationship between the anti-Stokes and the Stokes intensities and the quadratic relationship between the anti-Stokes and the pump intensities. Our signal is therefore a result of a four-wave mixing process. Moreover, this process is CARS resonance because the anti-Stokes power is maximized when the Stokes wavelength is tuned to resonance with the Raman-active benzene vibrational mode.

Fig.3 contains the measured interferogram resulting from the interference between the two anti-Stokes signals at the beamsplitter BS. The real part and the modulus of the coherence function, for the case of a Gaussian spectral distribution, are used to fit the experimental data (interferogram and envelope respectively). The resulting coherence length LC, or the axial resolution of the interferometric CARS measurement technique, is found to be equal to (32.3 +/- 0.3) $`\mu `$m (reduced $`\chi ^2`$ = 0.001).

The inset of Fig.3 shows an enlarged version of the interferogram fringes. Open circles correspond to the experimentally measured data and the solid line represents a fit of the data. This result indicates that two anti-Stokes signals generated in separate samples can be demodulated interferometrically, where the amplitude of the fringe envelope gives information about the concentration of the scatterers in the focal volume of the sample objective lens. The presence of interference clearly demonstrates the potential of CARS as a promising technique for providing molecular contrast for OCT-like interferometric imaging systems. In fact, the presence of the interference indicates that similar Raman-active vibrational frequencies are present in both the reference and the sample arm at the same path length from the detector. The “fingerprint” nature of Raman spectroscopy, combined with the possibility to switch between different samples in arm R, could permit selective detection and imaging, within the above mentioned axial resolution, of different molecular species present in the sample S.

Note finally that the interferometric detection scheme could provide numerous advantages over traditional photon counting CARS microscopy. Interfering a weak CARS signal with another strong CARS signal, can provide heterodyne sensitivity for improved S/N ratio. Moreover, with full knowledge of the excitation pulses and of the CARS interferogram, the spectral amplitude and the phase of the CARS pulse can be measured. A complete reconstruction of the Raman susceptibility may then be attained allowing for a more accurate molecular identification marks2003 .

In conclusion, we have described a new technique for CARS measurement that relies on the deterministic nature of the CARS process. The interference between two CARS signals, generated in separate samples, was observed allowing for heterodyne detection. This result is extremely promising for the development of a new molecular imaging technique (NIVI) based on non-linear, low-coherence interferometry. While this demonstration used forward CARS, epi-detected CARS cheng2002bis  is coherent as well, and is compatible with OCT coherence-ranging systems. CARS interferometry provides CARS microscopy the advantages of interferometric detection and provides OCT with molecular-specific contrast. These advantages could make CARS interferometry a powerful tool for biological imaging with OCT and for disease diagnosis at the molecular level.

This research was supported in part by a research grant entitled “A Nonlinear OCT System for Biomolecular Detection and Intervention” from NASA and the National Cancer Institute (NAS2-02057, SAB). S.A. Boppart’s email address is boppart@uiuc.edu.


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# First-principles study of the electrooptic effect in ferroelectric oxides

## Abstract

We first present a method to compute the electrooptic tensor from first principles, explicitly taking into account the electronic, ionic and piezoelectric contributions. We then study the non-linear optic behavior of three paradigmatic ferroelectric oxides. Our calculations reveal the dominant contribution of the soft mode to the electrooptic coefficients in LiNbO3 and BaTiO3 and its minor role in PbTiO3. We identify the coupling between the electric field and the polar atomic displacements along the B-O chains as the origin of the large electrooptic response in perovskite ABO3 compounds.

The electrooptic (EO) effect describes the change of refractive index of a material in a static electric field and is exploited in various technological applications lines . Ferroelectric ABO3 compounds exhibit unusually large EO coefficients and are therefore materials of choice for optical devices. Since the seventies, LiNbO3 EO modulators have been widely used in fiber-optic transmission systems ieee . More recently, there has been increasing interest in epitaxially grown BaTiO3 thin films for optical waveguide modulators apl81\_1375 . The EO effect is the origin of the photorefractive effect, exploited in non-volatile holographic data storage in LiNbO3 photore1 . It was also used to probe locally the ferroelectricity in SrTiO3 films prl89\_147601 .

Finding better EO materials is a desirable goal. However, the experimental characterization of optical non-linearities requires high-quality single crystals that are not always directly accessible nor easy to make. Input from accurate theoretical calculations allowing to predict the non-linear optical behavior of crystalline solids would therefore be particularly useful.

For many years, theoretical investigations of non-linear optical phenomena were restricted to semi-empirical approaches such as shell models ferroel234\_61  or bond-charge models prb7\_2600 ; jpc15\_825 . In the last decade, significant theoretical advances have been reported concerning first-principles density functional theory (DFT) calculations of the behavior of periodic systems in an external electric field prb63\_155107 ; prl89\_117602  and opened the way to direct predictions of various optical phenomena. Recently, particular attention has been paid to the calculation of non-linear optical (NLO) susceptibilities and Raman cross sections prb53\_15638\_prb66\_100301 ; prl90\_36401 .

In this Letter, we go one step further and present a method to predict the linear EO coefficients of periodic solids within DFT. Our method is very general, and can be applied to paradigmatic ferroelectric oxides : LiNbO3, BaTiO3 and PbTiO3. We find that first-principles calculations are fully predictive, and provide significant new insights into the microscopic origin of the EO effect. In particular, we highlight the predominent role of the soft mode in the EO coupling of LiNbO3 and BaTiO3, in contrast with its minor role in PbTiO3.

At linear order, the dependence of the optical dielectric tensor $`\epsilon _{ij}`$ on the static (or low-frequency) electric field $`_\gamma `$ is described by the linear EO tensor rijγ:

$$\mathrm{\Delta }\left(\epsilon ^1\right)_{ij}=\underset{\gamma =1}{\overset{3}{}}r_{ij\gamma }_\gamma .$$
(1)
Throughout this paper, we follow the convention of using Greek and Roman indexes (resp.) to label static and optical fields (resp.). We write all vector and tensor components in the system of cartesian coodinates defined by the principal axes of the crystal under zero field. We also refer to the atomic displacements $`\tau _{\kappa \alpha }`$ \[$`\kappa `$ labels an atom and $`\alpha `$ a cartesian direction\] within the basis defined by the zone-center transverse optic (TO) phonon eigendisplacements $`u_m(\kappa \alpha )`$: $`\tau _{\kappa \alpha }=_m\tau _mu_m(\kappa \alpha )`$.

Let us first consider the clamped (zero strain) EO tensor, $`r_{ij\gamma }^\eta `$, in which all electric-field induced macroscopic strains $`\eta `$ are forbidden. This is achieved experimentally by working at a frequency sufficiently high to avoid strain relaxations but low compared to the frequency of the TO modes. Within the Born-Oppenheimer approximation, we express the total derivative of $`\epsilon _{ij}`$ as the sum of two partial derivatives with respect to $`_\gamma `$ and $`\tau _m`$:

$$\frac{d\epsilon _{ij}}{d_\gamma }=\frac{\epsilon _{ij}}{_\gamma }|_{\tau =0}+4\pi \underset{m}{}\frac{\chi _{ij}^{(1)}}{\tau _m}|_{=0}\frac{\tau _m}{_\gamma }.$$
(2)
The derivative in the first term of the righthand side of Eq. (2) is computed at clamped atomic positions. It describes the electronic contribution to the EO tensor and is proportional to the NLO susceptibilities $`\chi _{ijl}^{(2)}`$. The second term represents the ionic contribution. It depends on the first-order change of the linear dielectric susceptibility due to atomic displacements, and is related to the Raman susceptibility $`\alpha _{ij}^m=\sqrt{\mathrm{\Omega }}_{\kappa \alpha }\frac{\chi _{ij}^{(1)}}{\tau _{\kappa \alpha }}u_m(\kappa \alpha )`$ of mode $`m`$ \[$`\mathrm{\Omega }`$ is the unit cell volume\], as well as to the amplitude of the ionic relaxation induced by the field $`_\gamma `$. $`\tau _m/_\gamma `$ can be expressed in terms of (i) the TO phonon mode frequencies $`\omega _m`$ and (ii) the TO mode polarities $`p_{m,\gamma }=_{\kappa ,\beta }Z_{\kappa ,\gamma \beta }^{}u_m(\kappa \beta ),`$ directly linked to the infrared (IR) intensities xgcl . Combining this with the previous equations, we obtain the clamped EO tensor unpublished

$$r_{ij\gamma }^\eta =\frac{8\pi }{n_i^2n_j^2}\chi _{ijl}^{(2)}|_{l=\gamma }\frac{4\pi }{n_i^2n_j^2\sqrt{\mathrm{\Omega }}}\underset{m}{}\frac{\alpha _{ij}^mp_{m,\gamma }}{\omega _m^2}$$
(3)
where $`n_i`$ and $`n_j`$ are the principal refractive indices.

Let us now consider the unclamped (zero stress) EO tensor, $`r_{ij\gamma }^\sigma `$. It can be shown unpublished  that the macroscopic expression proposed in Ref. prb50\_5941  is still valid at the microscopic level so that the the piezoelectric contribution to $`r_{ij\gamma }^\sigma `$ can be computed from the elasto-optic coefficients pijαβ and the piezoelectric strain coefficients dγαβ

$$r_{ij\gamma }^\sigma =r_{ij\gamma }^\eta +\underset{\alpha ,\beta =1}{\overset{3}{}}p_{ij\alpha \beta }d_{\gamma \alpha \beta }.$$
(4)
An expression similar to Eq. (3) was previously used by Johnston prb1\_3494  to estimate the clamped EO tensor of LiNbO3 and LiTaO3 from IR and Raman measurements. However, this semi-empirical approach was limited by the indeterminacy of the relative sign of $`𝒑_m`$ and $`𝜶^m`$. As discussed below, the direct evaluation of Eq. (3) and (4) from first principles provides an easier and more accurate estimate of the EO tensor.

We have implemented this formalism in the abinit open software abinit , within the local density approximation (LDA) to the DFT. The optical dielectric tensor, Born effective charges, phonon frequencies and eigendisplacements are computed from linear response xgcl . The piezoelectric strain coefficients dγαβ are deduced from the piezoelectric stress coefficients eγαβ and the elastic constants. These two quantities, as well as the elasto-optic tensor pijαβ, are obtained from finite differences. The non-linear response functions $`\chi _{ijl}^{(2)}`$ and $`\chi _{ij}^{(1)}/\tau _{\kappa \alpha }`$ are computed from a perturbative approach using a new implementation based on the $`2n+1`$ theorem. To reach reasonable k-point sampling convergence, we combined the recently proposed PEAD expression prb63\_155107  and the finite difference formula of Marzari and Vanderbilt prb56\_12847  to compute the perturbation expansion of the polarization. More details will be provided elsewhere unpublished . The method was tested on various cubic semiconductors and provides results in close agreement with earlier studies prl89\_117602 ; prb53\_15638\_prb66\_100301 .

For BaTiO3 and PbTiO3, we use extended norm-conserving pseudopotentials prb48\_5031 , a planewave kinetic energy cutoff of 45 hartree and a $`10\times 10\times 10`$ k-point grid. For LiNbO3, we use the same norm-conserving pseudopotentials as in Ref. prb65\_214302  as well as the Born effective charges, phonon frequencies and eigenvectors already reported in that paper. For this compound, a $`8\times 8\times 8`$ k-point grid and a planewave kinetic energy cutoff of 35 hartree give converged values for $`\chi _{ijl}^{(2)}`$ and $`\chi _{ij}^{(1)}/\tau _{\kappa \alpha }`$.

First, we study LiNbO3. This compound has a trigonal symmetry with 10 atoms per unit cell. The theoretical lattice constants and atomic positions are reported in Ref. prb65\_214302 . LiNbO3 undergoes a single transition at 1480 K from a centrosymmetric high-T paraelectric $`R\overline{3}c`$ phase to a ferroelectric low-T R3c ground state. The form of the EO tensor depends on the choice of the cartesian axes. Here, we follow the I.R.E. Piezoelectric Standards jpc2\_855 .

With this choice of axes, the EO tensor in the ferroelectric phase of LiNbO3 has 4 independent elements (Voigt notations): r13, r33, r22 and r51. The TO modes can be classified into $`4A_1+5A_2+9E`$. The A1 and E modes are Raman and IR active. Only the A1 modes couple to r13 and r33, while the E modes are linked to r22 and r51. Table 1 gives these four clamped coefficients note\_rc , as well as the contribution of each optical phonon. For comparison, we mention the coefficients computed by Johnston prb1\_3494  from measurements of IR and Raman intensities (IR + R) as well as the results of a bond-charge model (BCM) calculation by Shih and Yariv jpc15\_825 . The first-principles calculations correctly predict the sign of the four EO coefficients jpc2\_855 . The absolute values are also well reproduced by our method, especially if we take into account the fact that NLO properties are generally difficult to determine accurately. The experimental values are sensitive to external parameters such as temperature changes jap65\_2406  and the stoichiometry of the samples. For example, using crystals of various compositions, Abdi and co-workers measured absolute values between 1.5 pm/V and 9.9 pm/V for r$`{}_{}{}^{\sigma }{}_{22}{}^{}`$ jap84\_2251 . These difficulties support the need for sophisticated theoretical tools to predict NLO properties. In contrast to the models of Refs. prb1\_3494 ; jpc15\_825 , our method is predictive and does not use any experimental parameters. Moreover, it reproduces r$`{}_{}{}^{\eta }{}_{13}{}^{}`$, r$`{}_{}{}^{\eta }{}_{33}{}^{}`$ and r$`{}_{}{}^{\eta }{}_{22}{}^{}`$ better than the semiempirical models.

Our approach also provides some insight into the origin of the high LiNbO3 EO response. All EO coefficients are dominated by the ionic contribution of the A1 TO1 and the E TO1 modes. This can be explained as follows. At the paraelectric-ferroelectric phase transition, the unstable A2u and Eu modes of the paraelectric phase transform to low-frequency and highly polar modes in the ferroelectric phase prb65\_214302 , generating a large EO response if they exhibit, in addition, a large Raman susceptibility. The A1 TO1 and E TO1 modes of the ferroelectric phase have a strong overlap of respectively 0.82 and 0.68 with the unstable A2u and Eu modes of the paraelectric phase and combine giant polarity prb65\_214302  and large Raman susceptibility (see below for the A1 mode).

In Table 1, we also report the unclamped EO coefficients in LiNbO3. As the piezoelectric coefficients d31 (-1 p$`C/N`$) and d33 (6 p$`C/N`$) are small compared to d15 (55.9 p$`C/N`$) and d22 (21.6 p$`C/N`$), the piezoelectric effect is important for r$`{}_{}{}^{\sigma }{}_{22}{}^{}`$ and r$`{}_{}{}^{\sigma }{}_{51}{}^{}`$ and negligible for r$`{}_{}{}^{\sigma }{}_{13}{}^{}`$ and r$`{}_{}{}^{\sigma }{}_{33}{}^{}`$. The unclamped EO coefficient r$`{}_{}{}^{\sigma }{}_{51}{}^{}`$ is nearly twice as large as the clamped one. Moreover, its theoretical value is in better agreement with the experiment than that of the clamped one. This suggests that the piezoelectric contribution was not entirely eliminated during the measurement of r$`{}_{}{}^{\eta }{}_{51}{}^{}`$; the correct value of the clamped coefficient might be closer to the theoretical 14.9 pm/V.

Second, we study PbTiO3 and BaTiO3. Both compounds are stable at room temperature in a ferroelectric distorted perovskite structure of tetragonal P4mm symmetry with 5 atoms per unit cell Note-positions . In the P4mm phase, the TO modes can be classified into $`3A_1+4E+B_1`$. The EO tensor has only three independent elements: r13, and r33, coupling to the A1 modes, and r42, linked to the E modes. The B1-mode is IR inactive and does not influence the EO tensor. The results are shown in Table 2.

For PbTiO3, we found only measurements of r$`{}_{}{}^{\eta }{}_{13}{}^{}`$ and r$`{}_{}{}^{\eta }{}_{33}{}^{}`$, which agree well with our theoretical results. Moreover, our calculation predicts that PbTiO3 exhibits a large r$`{}_{}{}^{\eta }{}_{42}{}^{}`$, in spite of its low r$`{}_{}{}^{\eta }{}_{33}{}^{}`$. Combined with other advantageous features, such as small thermo-optic coefficients jap77\_2102 , this suggests that PbTiO3 might be an interesting candidate for EO applications if properly oriented.

In BaTiO3, the low temperature structure is rhombohedral. The P4mm phase is unstable and exhibits, in the harmonic approximation, an unstable E-mode that prevents the use of Eq. (3) to compute r$`{}_{}{}^{\eta }{}_{42}{}^{}`$. The theoretical estimates of r$`{}_{}{}^{\eta }{}_{13}{}^{}`$ and r$`{}_{}{}^{\eta }{}_{33}{}^{}`$ are reasonably accurate despite an underestimation of the theoretical r$`{}_{}{}^{\eta }{}_{33}{}^{}`$. The origin of the error can be attributed to various sources. First, the values computed for the P4mm phase correspond to an extrapolation of the EO tensor to 0 K, while experimental results are obtained at room temperature. Also, linear and NLO susceptibilities can be relatively inaccurate within the LDA. In this context, note the use of the LDA optical refractive indexes in Eq. (3), overestimating the experimental values by about 10 %.

We compare now the NLO response of the three compounds. r$`{}_{}{}^{\eta }{}_{13}{}^{}`$ is similar for all of them, while r$`{}_{}{}^{\eta }{}_{33}{}^{}`$ is significantly smaller in PbTiO3 than in LiNbO3 and BaTiO3. In the latter two compounds, the magnitude of r$`{}_{}{}^{\eta }{}_{33}{}^{}`$ is dominated by one particular phonon mode. In BaTiO3, the TO2 mode at 300 cm-1 has a similar strong overlap (92%) with the unstable mode in the paraelectric phase than the TO1 modes in LiNbO3, as previously discussed. In PbTiO3, all A1 modes contribute almost equally to r$`{}_{}{}^{\eta }{}_{33}{}^{}`$. The TO2 mode at 357 cm-1 has the strongest overlap (73%) with the soft mode in the cubic phase. Surprisingly, its contribution to r$`{}_{}{}^{\eta }{}_{33}{}^{}`$ is 23.5 times smaller than the contribution of the TO2 mode in BaTiO3.

To identify the origin of the distinctive behavior of PbTiO3, we report in Table 3 the mode polarities and Raman susceptibilities of the A1 TO modes. In the three compounds, $`𝜶`$ has two independent elements $`\alpha _{11}`$ and $`\alpha _{33}`$ that determine the amplitude of r$`{}_{}{}^{\eta }{}_{13}{}^{}`$ and r$`{}_{}{}^{\eta }{}_{33}{}^{}`$. $`\alpha _{33}`$ is large for the TO1 mode in LiNbO3 and the TO2 mode in BaTiO3. On the other hand, it is the smallest for the TO2 mode in PbTiO3, in agreement with experiments jpc3\_8695 . Combined with a higher frequency ($`\omega _{PbTiO_3}^2/\omega _{BaTiO_3}^2=1.41`$), a lower polarity ($`p_{BaTiO_3}/p_{PbTiO_3}=1.49`$), and a larger value of the refractive index ($`n_{PbTiO_3}^4/n_{BaTiO_3}^4=1.35`$), this weak Raman susceptibility ($`\alpha _{BaTiO_3}/\alpha _{PbTiO_3}=8.27`$) explains the weak contribution of the TO2 mode to r$`{}_{}{}^{\eta }{}_{33}{}^{}`$ in PbTiO3.

The microscopic origin of the lower A1 TO2 mode Raman susceptibility in PbTiO3, compared to BaTiO3, is explained by the decomposition of $`\alpha _{33}`$ into contributions of the individual atoms in the unit cell (see Table 4). In both perovskites, the major contributions to the Raman susceptibility of the A1 TO2 modes are $`\alpha _{33}(Ti)`$ and $`\alpha _{33}(O_1)`$ Note-positions ; $`\alpha _{33}`$ is mostly due to the atomic displacements of the atoms located on the Ti–O chains oriented along the polar direction. First, the derivatives of $`\chi _{33}^{(1)}`$ versus atomic displacement are of opposite sign for Ti and O1 atoms, and significantly larger in BaTiO3 than in PbTiO3. Second, the opposing displacements of Ti and O1 atoms in the TO2 mode in BaTiO3 produce contributions that add to yield a giant $`\alpha _{33}`$. On the other hand, the in-phase displacements of Ti and O1 in PbTiO3 produce contributions that cancel out, giving a small $`\alpha _{33}`$. This distinct behaviour goes beyond a simple mass effect. Changing the mass of Pb to that of Ba in the dynamical matrix of PbTiO3 has no significant effect on the relative Ti–O displacement. Large atomic displacements of opposite direction along the Ti–O chains are therefore needed to generate a large $`\alpha _{33}`$ and potentially a large $`r_{33}`$.

In summary, we presented a method to compute the EO tensor from first principles. In LiNbO3 and BaTiO3, the large EO response originates in the giant contribution of the successor of the soft mode, which combines low frequency, high polarity and high Raman susceptibility. In comparison, the contribution of the similar mode in tetragonal PbTiO3 is rather weak due to its low Raman susceptibility. In the perovskites, the Raman susceptibility is principally determined by the atomic displacements along the B–O chains in the polar direction. This suggests that the search for new perovskite oxides with good EO properties should focus on compounds with large relative B–O atomic displacements along the chains.

We thank M. Fontana, P. Bourson and B. Champagne for discussions and K. M. Rabe for reading the manuscript. MV and XG acknowledge FNRS Belgium. The work was supported by the Volkswagen Stiftung (Nano-sized ferroelectric Hybrids, I/77 737), FNRS (9.4539.00 and 2.4562.03), the Région Wallonne (Nomade, 115012), the PAI 5.01 and EU Exciting network.


text:
# Experimental Tests of the Holographic Entropy Bound

## I Introduction

Kovtun, Son and Starinets recently proposed Kovtun et al. (2003) that in nature the value111 From now on we set $`\mathrm{}=k_B=1`$.

$$\frac{\eta }{s}=\frac{\mathrm{}}{4\pi k_B}6.08\times \mathrm{\hspace{0.17em}10}^{13}Ks,$$
(1)
where $`\eta `$ is the shear viscosity of a fluid and $`s`$ its entropy density, plays a fundamental role. They showed that idealized systems, such as strongly coupled $`𝒩=4`$ supersymmetric Yang-Mills theory and similar theories in 3 and 6 dimensions precisely realize this value, while they conjectured that in general it provides a lower bound. One can easily envision that this hypothesis could be tested experimentally in the near future. While for example water under normal conditions (298.15 K, atmospheric pressure) has a value of $`\frac{\eta }{s}=2.3\times 10^{10}Ks`$, for superfluid helium 4He one can obtain values down to $`\frac{\eta }{s}=6.20\times 10^{12}Ks`$, only a factor of 10 away from the bound Kovtun et al. (2003); han (2002-2003).

What we will argue in this paper is that the viscosity bound can be thought of as a consequence of the holographic entropy bound, or more precisely from the generalized covariant entropy bound (GCEB) of Flanagan et al. (2000). Holographic entropy bounds are believed to be a generic and fundamental property of any theory of quantum gravity, (see ’t Hooft (1993); Susskind (1995) or Bousso (2002) for a review). Roughly speaking, the statement is that the number of degrees of freedom in the universe don’t scale as the volume of the universe, but only as its surface area. A precise version of this hypothesis, the Covariant Entropy Bound (CEB), has been formulated by Bousso Bousso (1999). The GCEB is an even stronger version of this bound.

So far all these bounds have been motivated by theoretical necessity. While many accept the CEB, the status of the GCEB even among believers is somewhat less clear. Experimental tests of the entropy bounds are in principle possible222For example it was argued in Hogan (2003) that in principle the CEB implies a discreteness in the temperature variations of the cosmic microwave background.. But one runs into the usual problem that current experiments are orders of magnitude away from testing quantum gravity. Showing that the GCEB implies the viscosity bound of Kovtun et al. (2003) would bring testing holography into experimental reach. We make the first steps into this direction.

## II Hydrodynamics and Viscosity

To understand the statement of the bound, we have to briefly introduce the basic notions of hydrodynamics and how it relates to strongly coupled systems with, following the nice discussion in Kovtun and Yaffe (2003). Hydrodynamics should be viewed as an effective theory, describing small fluctuations around equilibrium of a thermal system on length and time scales which are large compared to any microscopic scale in the system. The relevant hydrodynamic degrees of freedom are the conserved charge densities, in the simplest case just for the charges derived from the energy-momentum tensor, $`ϵT^{00}`$ and $`\pi ^iT^{i0}`$. One equation of motion is just the current conservation equation. In addition, one writes down the so called constitutive relations, expressing the fluxes of the conserved quantities (the spatial parts of the conserved currents) in terms of the hydrodynamic degrees of freedom. Without any further input, one has to allow here the most general set of terms consistent with symmetries. Since hydrodynamics is supposed to be an effective theory of long distances and small fluctuations, one can systematically perform a double expansion in powers of the fields and numbers of derivatives. To linear order in the fluctuations and to first order in derivatives, the constitutive relation for the spatial components of the stress-energy tensor in $`D`$ spacetime dimensions reads

$`T^{ij}`$ $`=`$ $`\delta ^{ij}\left(P+v_s^2\delta ϵ\right)\gamma _\zeta \delta ^{ij}\stackrel{}{}\stackrel{}{\pi }`$ (2)
$``$ $`\gamma _\eta \left(^i\pi ^j+^j\pi ^i{\displaystyle \frac{2}{D1}}\stackrel{}{}\stackrel{}{\pi }\right).`$
$`P`$ is the equilibrium pressure. $`\delta ϵ`$ denotes the fluctuation in $`T^{00}`$ around the equilibrium value. For an equilibrium system in its rest frame, the momentum densities are zero, so that the $`\pi `$’s are already the first order fluctuations. The three transport coefficients, $`v_s^2`$, $`\gamma _\eta `$ and $`\gamma _\zeta `$ depend on the microscopic details of the theory. The terms linear in the momentum densities have been split into two independent tensor structures. The speed of sound $`v_s`$ and the bulk viscosity coefficient $`\gamma _\zeta `$ govern the propagation and diffusion of longitudinal momentum fluctuations which form a coupled system with $`\delta ϵ`$, while the shear viscosity coefficient $`\gamma _\eta `$ governs the diffusion of transverse fluctuations with $`\delta ϵ=\stackrel{}{}\stackrel{}{\pi }=0`$, which to this order decouple from the sound waves. Conventionally one refers to the corresponding quantities $`\eta =(ϵ+P)\gamma _\eta `$ and $`\zeta =(ϵ+P)\gamma _\zeta `$ as the bulk and shear viscosity respectively. They would appear directly in the constitutive relation if we were to linearize in velocities instead of momenta. In a conformal theory like maximally supersymmetric Yang Mills theory, the stress-energy tensor has to be traceless, implying that $`\zeta =0`$ and $`v_s=\frac{1}{\sqrt{D1}}`$. The beauty of the hydrodynamic description is that it applies to any system which acts like a fluid at long distances, even strongly coupled ones. For weak coupling $`\eta `$ can be calculated perturbatively. For strongly coupled theories one has to find alternative techniques. As shown in Kovtun et al. (2003), at weak coupling $`\frac{\eta }{s}>>1`$, so that the bound only gets tested by strongly coupled systems.

## III General Strategy for Derivation of the Bound

In order to understand how viscosity could appear in holographic entropy bounds, let us briefly recapitulate how gravity enforces such bounds. If we had a fluid in flat space at rest with a finite entropy density, one could obviously violate the bound. The bound states that the entropy passing the lightsheet, which is constructed by emitting lightrays from the boundary of a given volume element inward, should be less than the area divided by $`4G\mathrm{}`$. For a volume element of the fluid in flat space, the whole fluid enclosed in a given area passes the lightsheet, so that the entropy should scale with the volume by the assumption that we have a finite entropy density. The way gravity avoids this conflict is that it makes it inconsistent to have such a fluid in flat space. The energy stored in the fluid will curve space-time sufficiently to rescue the holographic bound.

Viscosity becomes important, once the fluid has non-trivial velocity profiles. For the CEB, it does not seem to matter much whether the fluid is in motion: focus on a certain volume element of fluid. No matter what the velocities are, the whole fluid will eventually pass the lightsheet. On the other hand, no particles that where originally outside the volume can move inside fast enough to be counted by the lightsheet, since they are slower than light. The situation however is quite different for the GCEB. Here we are dealing with lightsheets that terminate, and the entropy is bounded by the area the lightsheet emanates from minus the area in which we chose to terminate it. Parts of the fluid that start out inside but sufficiently close to the spatial location at which we chose to terminate the lightsheet will be able to move outside the region before the light arrives there and avoid to be counted. Similar, fluid that starts outside the region we want to sample can move inside and might lead to a violation of the bound. This situation is sketched in Fig.1. As before, it is gravity that has to censor any possible violation. What we need is that velocity profiles lead to a curved spacetime, in which the lightsheet gets sufficiently modified. This is precisely where viscosity enters: from the constitutive relation we see that viscosity tell us how much stress $`T_{ij}`$ we have in a fluid once we turned on the velocity profile. And by Einstein’s equations this stress $`T_{ij}`$ will turn on spacetime curvature $`R_{ij}`$. In order to not violate the bound, the backreaction has to be sufficiently large, that is for a fluid with given entropy density, the viscosity is not allowed to become too small. In the next section we will show how this works quantitatively.

## IV Derivation of the Viscosity Bound

### IV.1 Review of Bousso’s Derivation of Bekenstein’s Bound

In Bousso (2003) Bekenstein’s bound on the entropy of a matter system was derived from the GCEB. The setup used there can easily be generalized to apply to the case of a fluid in motion.

Consider a large region of spacetime occupied by a fluid. We are interested in the entropy contained in a volume element bounded by surfaces $`B_+`$ and $`B_{}`$. A lightsheet (a null-hypersurface generated by non-expanding light-rays) enters the volume element at $`B_+`$ and exits at $`B_{}`$. The GCEB states that

$$S\frac{A(B_+)A(B_{})}{4G}$$
(3)
where $`S`$ is the entropy passing through the lightsheet, and $`A(B_i)`$ denotes the area of the corresponding surface. For simplicity we will work with rectangular surfaces as depicted in Fig.2, but the result is independent of the shape, since the areas involved do not change if we deform $`B_\pm `$ along the lightsheet. As in Bousso (2003) we chose the lightsheet to be given by the set of parallel light rays obeying

$$x^0=x^1;(x^2,\mathrm{},x^{D1})\text{ arbitrary constants.}$$
(4)
These are null geodesics in flat space. For the same reason that the area is invariant under deformations along the lightsheet we actually have $`A(B_+)=A(B_{})`$ and the entropy seems to be zero. In order to get a non-vanishing area difference we have to take into account the backreaction of the matter system. Due to the stress energy $`T_{\mu \nu }`$ of the fluid, non-trivial curvature $`R_{\mu \nu }`$ will be turned on, and the above hypersurface will neither be null nor geodesic. However, for weakly gravitating systems, there will be a close by null geodesic lightsheets. Bousso (2003) uses two such close by lightsheets, one that starts in B+ but misses $`B_{}`$, and one that ends in $`B_{}`$, but does not start at $`B_+`$. Plugging those into eq.3, one obtains the following bound ($`\mathrm{}=1`$):

$$S\pi \mathrm{\Delta }x𝑑x_2\mathrm{}𝑑x_D_0^{\mathrm{\Delta }x}𝑑x_1T_{\mu \nu }k^\mu k^\nu ,$$
(5)
where $`k^{\mu \nu }=(1,1,0,0)`$ is a tangent null vector to the lightsheet. For the volume element of our fluid the rhs evaluates to

$$S_{eq.}=\pi V(ϵ+P)\mathrm{\Delta }x.$$
(6)
What will be important in this expression later is that it is proportional to $`\mathrm{\Delta }x`$, so that the equilibrium configuration will lead to zero entropy in infinitesimally thin spatial slices. In Bousso (2003) it was further observed that if one were to chose a lightsheet that includes the whole region of spacetime occupied by the fluid, $`𝑑x_2\mathrm{}𝑑x_D_0^{\mathrm{\Delta }x}𝑑x_1T_{\mu \nu }k^\mu k^\nu `$ just evaluates the total ADM mass of the fluid in its rest frame and one can recover the conventional form of Bekenstein’s bound Bekenstein (1981), $`S\pi M\mathrm{\Delta }x`$.

### IV.2 Letting Things Flow

In order for viscosity to enter the game we have to allow for motion of the fluid. Consider a fluid as described above, but turn on a perturbation away from equilibrium which at $`t=0`$ has the following momentum density profile:

$$\pi _1(\stackrel{}{x},t=0)=\mathrm{sgn}(x_1\mathrm{\Delta }x/2)(ϵ+P)v_0$$
(7)
where $`ϵ`$ and $`P`$ are the equilibrium values of the energy density and the pressure.

$$v_01$$
(8)
is the velocity at which the fluid is moving with respect to the restframe of the equilibrium system (which has to be less than the speed of light). Strictly speaking, as $`v_0`$ approaches 1 (or if we go out to large values of $`x_2`$), we would have to use relativistic hydrodynamics instead and, in addition, are no longer justified to neglect the higher order perturbations in the constitutive relation. So our derivation of the bound only applies to non-relativistic systems, even though we expect the bound to be also true in the relativistic case.

We have set up the system in such a way that the fluid at negative $`x_1`$ is moving to the right (in vane trying to escape the lightsheet), while the fluid at positive $`x_1`$ is moving to the left (rushing into the lightsheet). In addition we turn on

$$\pi _2(\stackrel{}{x},t=0)=2\delta (x_1\mathrm{\Delta }x/2)x_2(ϵ+P)v_0$$
(9)
so that

$$\stackrel{}{}\stackrel{}{\pi }=_1\pi _1+_2\pi _2=0$$
(10)
and we are dealing with a purely transverse fluctuation. The linearized hydrodynamics can be solved in this case and the full time dependent solution is obtained by having the stepfunction diffuse with diffusion constant $`\gamma _\eta `$,

$$\pi _1(\stackrel{}{x},t)\mathrm{erf}(\frac{x\mathrm{\Delta }x/2}{\sqrt{4\gamma _\eta t}}).$$
(11)
In order to calculate the maximal entropy density allowed within the lightsheet bounded by $`0<x_1<\mathrm{\Delta }x`$, we follow the same logic as in the derivation of Bekenstein’s bound and find once more

$`s`$ $``$ $`{\displaystyle \frac{\pi }{V}}{\displaystyle 𝑑x_2\mathrm{}𝑑x_D\mathrm{\Delta }x_0^{\mathrm{\Delta }x}𝑑x_1T_{ab}k^ak^b}`$ (12)
$`=\pi `$ $`{\displaystyle _0^{\mathrm{\Delta }_x}}𝑑x_1(T_{00}+2T_{01}+T_{11}).`$ (13)
The equilibrium values on the right hand side as before yield $`s_{eq.}=\pi \mathrm{\Delta }x(ϵ+P)`$. In the same way, the contribution from $`T_{01}`$ gives an integral over the momentum density $`\pi `$. The way we set up the profile and the lightsheet geometry, the net momentum in our lightsheet is actually zero. But even in a more general configuration, the $`T_{01}`$ term will always give an integral over the local momentum density and vanish as we take $`\mathrm{\Delta }x`$ to zero, which as we will soon see is all we need. Last but not least let’s calculate what we get from the linear perturbation $`\delta T_{11}`$ in the $`T_{11}`$ piece. From the constitutive relation eq.2 we see that

$$\delta T_{11}=2\gamma _\eta _1\pi _1(\stackrel{}{x},t)$$
(14)
and on the right hand side we get a contribution

$$ss_{eq.}+\pi 4v_0\eta _0^{\mathrm{\Delta }x}𝑑x_1\delta (x_1\mathrm{\Delta }x/2).$$
(15)
We have neglected the fact that the delta function diffuses while being sampled by the lightsheet. Since total momentum is conserved under diffusion, the integral over the full delta function gives an upper bound on the integral of the time dependent solution333 The diffusion process will also generate entropy which can be neglected as long as $`\mathrm{\Delta }t=\mathrm{\Delta }x/c`$ is much smaller than the diffusion timescale. See also the next footnote.

The important thing to note is that the viscosity term enters via an integral of a delta-function. We only get a surface contribution from the boundary of the lightsheet, the result is independent of $`\mathrm{\Delta }x`$. Since the bound has to be satisfied for arbitrary lightsheets, it has to be true for lightsheets with infinitesimal $`\mathrm{\Delta }x`$. In this case the bulk contributions, that is both the equilibrium contribution as well as the integral over the momentum density $`T_{01}`$, drop out444 Unfortunately for a realistic matter system, for which the fluid form of the stress tensor is only a long distance approximation, this limit seems to force us to take $`\mathrm{\Delta }x`$ so small that hydrodynamics is not necessarily a good description. One certainly can still setup a flow with the initial conditions we use, but to what extend it is the viscosity alone that governs the stress is up to debate.. Using further $`v_01`$ we obtain the viscosity bound of Kovtun et al. (2003), $`s4\pi \eta `$ .

## V Interpretation and Future Direction

Should one really interpret the viscosity bound as being some subtle imprint of quantum gravity on properties of macroscopic systems? For a somewhat more conservative point of view to read our results, recall the connection between Bekenstein’s bound and the GCEB: the hypothetical holographic bound, involving both Newton’s constant $`G`$ and Planck’s constant $`\mathrm{}`$ gets combined with formulas of classical general relativity involving only $`G`$ yielding a bound that only involves $`\mathrm{}`$ and turns out to basically correspond to Heisenberg’s uncertainty principle. While one could read this as “Holography implies the uncertainty principle” a more conservative way to read this result is to say: once we chose to deal with quantum gravity, we obviously also have to treat the matter fields quantum mechanical, and the usual rules (including the uncertainty principle) will apply. Latter can be understood without ever appealing to quantum gravity.

In the same spirit we think one should read the viscosity bound. The GCEB can be used to derive a property of macroscopic systems, which presumably can also be derived by other methods. The reason it had not been obtained earlier is that it is a strong coupling phenomenon. As shown in Kovtun et al. (2003), in a weakly coupled field theory, $`\frac{\eta }{s}>>1`$. The supersymmetric models saturating the bound are formally at infinite coupling, and the only reason one was able to compute $`\frac{\eta }{s}`$ is that they have a weakly coupled gravity dual. Still, the viscosity bound can be challenged experimentally, and any experimental test automatically becomes a test of the GCEB. For the future it might be very interesting to study in the same spirit non-vanishing chemical potentials or charged fluids in background fields. Most likely one can derive bounds similar to the viscosity bound from the GCEB that govern the behavior of other transport coefficients, giving even more opportunities to probe the GCEB in the laboratory.

Acknowledgments: We would like to thank Raphael Bousso, Josh Erlich and Pavlo Kovtun for useful discussions. This work was partially supported by the DOE under contract DE-FGO3-96-ER40956.