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# Jahn-Teller instability in C6H⁺₆ and C6H⁻₆ revisited.

## I Introduction

A molecular system with a degenerate electronic ground state will spontaneously lower its symmetry to lift the degeneracy. This is the Jahn-Teller (JT) Jahn  effect, and is common in molecules Bersuker . The C6H6 (benzene) molecule has a long history of study Kistiakowsky ; Sponer . The benzene cation represents a paradigm of the dynamical JT effect Longuet . With full D6h symmetry, the highest occupied molecular orbital (HOMO) $`e_{1g}`$ is doubly degenerate, as is the lowest unoccupied molecular orbital (LUMO) $`e_{2u}`$. Hence both the cation and anion are JT unstable and prefer lower symmetry. In the lowest (linear) approximation, the Born-Oppenheimer surface has a degenerate loop in configuration space surrounding the D6h ground state. Everywhere on this loop, the HOMO and LUMO states are split by a constant JT gap. The most symmetric points on this loop represent simple D2h distortions. These distortions occur in three equivalent “acute” and three equivalent “obtuse” forms (see the inset to Fig. 2). Higher order corrections lift the degeneracy on the loop, but zero-point energy exceeds the barrier height, creating a dynamic rather than a static JT distortion.

Ab initio approaches Engstrom ; Koppel ; Raghavachari  including density functional theory (DFT) Muller ; Yoshizawa  have been used to predict the ground state geometry and the JT energy lowering in the benzene cation. Quantum chemistry methods have been used to analyze vibrational spectra of the benzene cation Eiding ; Pulay ; Lipari . A high resolution zero-kinetic-energy (ZEKE) photoelectron study by Linder et al. Linder  found values of the frequency shift of the in-plane ring-bending $`e_{2g}`$ vibrational mode. From their analysis, they deduced the JT energy lowering to be 208 cm-1. They also concluded that the cation has a global minimum for the acute D2h geometry, with a local minimum for the obtuse geometry only 8 cm-1 higher in energy. Ab initio calculations Raghavachari  suggest 4-5 times greater energy gain. The present study reconciles this discrepancy. We provide a microscopic model Hamiltonian for the $`\pi `$-electron system, which includes two independent $`e_{2g}`$ modes of JT coupling. We derive all parameters of this model from DFT calculations and find vibrational spectra for both the cation and anion using a non-adiabatic approximation. Our results for the cation permit a reinterpretation of the ZEKE spectra, allowing a larger JT energy lowering, which agrees with both our DFT and previous theory.

## II Model Hamiltonian

The starting point is a Hückel-type Hamiltonian for the non-bonding $`\pi `$ electrons, with a first-neighbor hopping integral $`t_1=<i||i\pm 1>`$ between adjacent $`p_z`$ atomic orbitals on the six C atoms. In Slater-Koster notation Slater , $`t_1`$ is called the $`(pp\pi )`$ two-site integral. In the D6h point group, all six $`t_1`$ integrals are the same. The 6-dimensional electronic Hilbert space has single-particle states with $`a_{2u}`$, $`e_{1g}`$, $`e_{2u}`$, $`b_{1g}`$ symmetries, which have energies $`2t_1,t_1,t_1,2t_1`$.

Hopping matrix elements $`t`$ decrease with distance between atoms. For small atomic displacements, $`t`$ depends linearly on the C-C bond length, $`t_1(\delta R_{i,i+1})=t_1^0g_1\delta R_{i,i+1}`$. The electron-phonon coupling constant $`g_1`$ is the same as in the Su-Schriefer-Heeger modelSu  for polyacetylene. Next we introduce second neighbor hopping $`t_2=<i1|H|i+1>=t_2^0+g_2\delta \alpha _i`$ to include a dependence on the change $`\delta \alpha _i`$ of the Ci-1-Ci-Ci+1 bond angle $`\alpha _i`$ from 120. The constant term $`t_2^0`$ does not lift the degeneracy of the $`e`$ levels. Therefore we put $`t_2^0=0`$ to keep the Hamiltonian as simple as possible. We use harmonic restoring forces $`K_1,K_2`$ for the bond stretching and angle bending vibrations. The total Hamiltonian $`=_{\mathrm{el}}+_{\mathrm{vib}}`$ has the form

$`_{\mathrm{el}}`$ $`=`$ $`{\displaystyle \underset{i=1}{\overset{6}{}}}[t_1^0+g_1\delta R_{i,i+1}|i><i+1|`$
$`+g_2\delta \alpha _i|i1><i+1|+h.c.]`$
$`_{\mathrm{vib}}`$ $`=`$ $`{\displaystyle \underset{i=1}{\overset{6}{}}}(P_i^2/2M+K_1\delta R_{i,i+1}^2/2+K_2\delta \alpha _i^2/2).`$ (1)
The coupling constants $`g_{1,2}`$ and spring constants $`K_{1,2}`$ are calculated from DFT using the program NRLMOLMark  with a Gaussian basis set and the Perdew-Burke-Ernzerhof exchange-correlation potential Perdew . This yields as the optimal geometry of neutral benzene in D6h symmetry, the C-C and C-H bond lengths of $`R_0`$=1.398 Å and 1.08 Å respectively. The energy difference between the HOMO $`e_{1g}`$ and $`a_{2u}`$ orbitals defines the hopping integral $`t_1^0=2.72`$ eV. We fix the C-H bond length and introduce a symmetric $`a_{1g}`$ breathing distortion, which alters the C-C bond lengths. The results, shown on Fig. (1), can be fitted to the predictions of the model Hamiltonian (1) $`E=E_0+3K_1\delta R^2`$ (for the total energy) and $`\mathrm{\Delta }E=t_1=t_1^0g_1\delta R`$ for the $`E(e_{1g})E(a_{2u})`$ eigenvalue difference. The results are $`g_1=5.27`$ eV/$`\AA `$ and $`K_1=47.4`$ eV/$`\AA ^2`$.

Second neighbor integrals are found from DFT energies for distortions with D2h symmetry. We fixed the C-C bond lengths and varied the bond angle $`\delta \alpha `$ as shown in the inset to Fig. (2). Specifically, angles 1 and 4 were decreased by 2$`\alpha `$, while the remaining four angles were increased by $`\alpha `$. The hydrogen atoms were fixed along the bisectors of the C-C-C angles. The results were fitted to the predictions of the Hamiltonian (1) $`E=E_0+6K_2\delta \alpha ^2`$ for the total energy, and $`4g_2\delta \alpha `$ for the splitting of doubly degenerate $`e_{1g}`$ HOMO states into $`b_{2g}`$ and $`b_{3g}`$ singlets. The results are $`K_2=7.45`$ eV/rad2 and $`g_2=0.91`$ eV/rad.

## III Adiabatic Solution

For fixed atomic coordinates, the adiabatic potential energy surface (APES) can easily be calculated using Eq. (1). For the D2h distortion shown in the inset of Fig. (2), the energy depends on three variables $`\delta R_1=\delta R_{12}`$, $`\delta R_2=\delta R_{23}`$ and $`\delta \alpha _2=\delta \alpha _1/2=\delta \alpha `$. The electronic contribution is the sum of the occupied eigenvalues of Eq. (1). The energy is not analytic at the point ($`\delta R_1,\delta R_2,\delta \alpha `$)=(0,0,0), but has a cusp, characteristic of the first-order JT splitting. Charged benzene lowers its energy by $`\delta E_1+\delta E_2+\delta E_3`$ corresponding to atomic relaxation via three types of vibrational modes. The first is the symmetric $`A_{1g}`$ distortion of D6h symmetry, $`\delta R_1=\delta R_2=\delta R_0`$ and $`\delta \alpha =0`$. The second and the third are two $`E_{2g}`$ vibrational modes: the ring-bending and C-C bond-length distortions. It is more convenient to measure distortions $`\delta R^{}`$ around the relaxed breathing positions $`R=R_0+\delta R_0=1.416`$ Å. The distorted geometry of benzene ions and corresponding energy gains are shown in Table 1.

The geometry and energies of the DFT solution (Table 1) are reasonably well reproduced by the model Hamiltonian. The energy difference (3.7 meV) found between the acute or obtuse distortions is sensitive to the choice of exchange-correlation potential and smaller than the errors of calculations Muller . The DFT energy lowering and carbon atomic distortions are affected by hydrogen distortions as well, which are left out completely in Eq. (1). We did constrained geometry optimization with hydrogens forced to follow carbons so that C-H bond divides C-C-C angle by half. The minimum energy in the constrained calculations was only 4 meV higher in energy than in the fully optimized geometry for both acute and obtuse cations. The main conclusion is that the C-C bond-length distortions contribute the most to the JT energy lowering and degenerate level splitting in both the benzene cation and anion.

## IV Vibrational Model Hamiltonian

JT-coupled vibrational modes change their frequencies on a charged molecule. The observable frequency shifts serve as a measure of the JT energy lowering. We solve the model Hamiltonian for the vibrational spectra for both cation and anion. For the case of the cation, the Hamiltonian (1) is projected on the two $`e_{1g}`$ HOMO states with symmetries $`b_{3g}`$ and $`b_{2g}`$ in the $`D_{2h}`$ point group,

$`|b_{3g}>={\displaystyle \frac{1}{\sqrt{12}}}\left(2|1>+|2>|3>2|4>|5>+|6>\right)`$
$`|b_{2g}>={\displaystyle \frac{1}{2}}\left(|2>+|3>|5>|6>\right)`$ (2)
The Hamiltonian takes form $`U_1HU_1^{}=H_0\widehat{I}+H_z\sigma _z+H_x\sigma _x`$, where $`U_1=(|b_{3g}>,|b_{2g}>)`$, and $`\sigma _\beta `$ are the Pauli matrices in the $`\{b_{3g},b_{2g}\}`$ subspace,

$`_0=`$ $`{\displaystyle \underset{i=1}{\overset{6}{}}}\left(P_i^2/2M+K_1\delta R_{i,i+1}^{}_{}{}^{}2/2+K_2\delta \alpha _i^2/2\right)`$
$`_z=`$ $`{\displaystyle \frac{g_1}{6}}(\delta R_1^{}+\delta R_3^{}+\delta R_4^{}+\delta R_6^{}2\delta R_2^{}2\delta R_5^{})`$
$`+`$ $`{\displaystyle \frac{g_2}{2}}(\delta \alpha _1+\delta \alpha _4)`$
$`_x=`$ $`{\displaystyle \frac{g_1}{\sqrt{12}}}(\delta R_1^{}\delta R_3^{}+\delta R_4^{}\delta R_6^{})`$
$`+`$ $`{\displaystyle \frac{g_2}{\sqrt{12}}}(\delta \alpha _2\delta \alpha _3+\delta \alpha _5\delta \alpha _6)`$ (3)
In adiabatic approximation, the JT orbital splitting is $`2\mathrm{\Delta }=2g_1^2/3K_1+2g_2^2/3K_2`$ and the JT energy lowering is $`E_{\mathrm{JT}}=\mathrm{\Delta }/2`$. To solve the problem beyond the adiabatic approximation we have to quantize vibrational motions. We rewrite the Hamiltonian (3) in Cartesian coordinates $`(\delta x_i,\delta y_i)`$. The kinetic energy term is diagonal. Choosing as the unit of displacement $`R`$=1.416 Å(the benzene ring radius after $`a_{1g}`$ mode relaxation), and as the energy unit $`K_1R^2`$, the potential energy of the Hamiltonian $`H_0`$ (Eq. (3)) depends on a single parameter $`K_2/K_1R^2=\mathrm{\Lambda }`$.

After diagonalizing $`H_0`$ we get twelve normal modes whose amplitudes we designate $`\mathrm{\Theta }_{\mathrm{1..12}}`$. The potential energy is independent of the motion of the center of mass ($`X=x_i`$,$`Y=y_i`$) and the ring rotation ($`\alpha =\alpha _i`$). This forces three normal modes to have frequencies zero. Since we neglect C-H stretching motions, the mass M is $`M_C+M_H`$. Choosing $`\mathrm{\Lambda }=0.0784`$ the nine remaining normal modes are: the degenerate ring bending $`E_{2g}`$ mode at $`\omega _1=581`$ cm-1 with some admixture of the C-C bond length alteration, the pure ring bending $`B_{1u}`$ mode at 962 cm-1, the breathing $`A_{1g}`$ mode at 992 cm-1, the mostly C-C bond-length-alteration doublets $`E_{1u}`$ and $`E_{2g}`$ at 1262 cm-1 and $`\omega _2=1644`$ cm-1 and the pure C-C bond-stretching mode $`B_{2u}`$ at 1718 cm-1. It is interesting to compare the model Hamiltonian normal mode spectrum with the DFT NRLMOL calculations. There are 21 in-plane vibrational modes $`\mathrm{\Gamma }=2A_{1g}+A_{2g}+4E_{2g}+2B_{1u}+2B_{2u}+3E_{1u}`$. Six of them are high frequency C-H modes $`A_{1g}+B_{1u}+E_{1u}+E_{2g}`$ around $`3100`$ cm-1. From the remaining 15 vibrations we identify the ring-bending $`E_{2g}`$ mode at $`600`$ cm-1, the breathing $`A_{1g}`$ at $`992`$ cm-1, and the bond-stretching $`E_{2g}`$ at $`1589`$ cm-1.

The off diagonal part $`H_x`$ of the Hamiltonian (3) depends only on the two JT-active $`E_{2g}`$ vibrational normal modes. Let us label the amplitudes of these modes by ($`\mathrm{\Theta }_{1a},\mathrm{\Theta }_{1b}`$) and ($`\mathrm{\Theta }_{2a},\mathrm{\Theta }_{2b}`$) and denote their frequencies by $`\omega _1`$ (ring bending) and $`\omega _2`$ (bond-stretching) as above. We also use the coordinates $`\mathrm{\Theta }_1`$, $`\mathrm{\Theta }_2`$ to denote the total displacements $`\mathrm{\Theta }_1^2=\mathrm{\Theta }_{1a}^2+\mathrm{\Theta }_{1b}^2`$ etc. Then Eq. (3) becomes:

$`_0=`$ $`{\displaystyle \frac{M}{2}}\left(\dot{\mathrm{\Theta }}_{1a}^2+\dot{\mathrm{\Theta }}_{1b}^2+\omega _1^2\mathrm{\Theta }_1^2\right)`$
$`+`$ $`{\displaystyle \frac{M}{2}}\left(\dot{\mathrm{\Theta }}_{2a}^2+\dot{\mathrm{\Theta }}_{2b}^2+\omega _2^2\mathrm{\Theta }_2^2\right)`$
$`_z=`$ $`G_1\mathrm{\Theta }_1\mathrm{cos}(\beta _1)G_2\mathrm{\Theta }_2\mathrm{cos}(\beta _2)`$
$`_x=`$ $`G_1\mathrm{\Theta }_1\mathrm{sin}(\beta _1)G_2\mathrm{\Theta }_2\mathrm{sin}(\beta _2),`$ (4)
where the angles $`\beta _1`$, $`\beta _2`$ contain arbitrary additive constants which are the choices of the orientation angles of the orthogonal eigenvectors in the two-dimensional $`E_g`$ subspaces of the two modes. Note that the adiabatic electronic eigenvalues which diagonalize $`_z\sigma _z+_x\sigma _x`$ (in the approximation that ($`\mathrm{\Theta }_{1a},..,\mathrm{\Theta }_{2b}`$) are classical variables) are $`\pm \mathrm{\Delta }_{JT}`$ where

$`\mathrm{\Delta }_{JT}^2=G_1^2\mathrm{\Theta }_1^2+G_2^2\mathrm{\Theta }_2^2+2G_1G_2\mathrm{\Theta }_1\mathrm{\Theta }_2\mathrm{cos}(\beta _1\beta _2)`$ (5)
This does not depend separately on the angles $`\beta _1`$, $`\beta _2`$. The modified electron-phonon coupling constants $`G_1`$, $`G_2`$ depend on the JT couplings $`g_1`$, $`g_2`$ and on the $`E_g`$ normal mode eigenstates. For our case ($`\mathrm{\Lambda }=0.0784`$) we find

$`G_1`$ $`=`$ $`T_1g_1/6+T_2g_2/2R=1.3\mathrm{eV}/\mathrm{\AA }`$
$`G_2`$ $`=`$ $`T_3g_1/6T_4g_2/2R=4.14\mathrm{eV}/\mathrm{\AA }`$ (6)
Let us consider further the adiabatic eigenstates of $`=_z\sigma _z+_x\sigma _x`$. What happens when we change the angle $`\delta \beta _1=\delta \mathrm{tan}^1\mathrm{\Theta }_{1b}/\mathrm{\Theta }_{1a}`$? The rotation matrix $`R=\mathrm{cos}(\alpha /2)\widehat{\sigma }_z+i\mathrm{sin}(\alpha /2)\widehat{\sigma }_x`$ has the property that $`RR^{}`$ gives a new matrix $`^{}`$ with angles $`\beta _1\beta _1+\alpha `$ and $`\beta _2\beta _2+\alpha `$. The energies $`\pm \mathrm{\Delta }_{JT}`$ are unchanged and the eigenfunctions are rotated in ($`b_{3g}`$, $`b_{2g}`$) space by $`\alpha /2`$. This type of change of distortion pattern is called a “pseudo-rotation”. A full pseudo-rotation by $`\alpha =2\pi `$ restores the molecular geometry and changes the sign of the electronic eigenstate. This sign change under adiabatic distortion is the Berry phase, and needs to be correctly incorporated when finding the system’s total wavefunction in adiabatic approximation. In particular it leads to fractional quanta of pseudorotational angular momentum. Our method will find total wavefunctions without making the adiabatic approximation and will therefore yield correct answers without explicit mention of Berry phase.

## V Non adiabatic Solution

The quantized vibrational Hamiltonian (4) depends on three parameters $`\omega _1/\omega _2=0.353`$ and the two electron-phonon coupling constants $`\kappa _1=(\mathrm{\Delta }_1/\mathrm{}\omega _1)^{1/2}=1.18`$, $`\kappa _2=(\mathrm{\Delta }_2/\mathrm{}\omega _2)^{1/2}=0.8`$, where $`\mathrm{\Delta }_1=G_1^2/M\omega _1^2=817`$cm-1 and $`\mathrm{\Delta }_2=G_2^2/M\omega _2^2=1052`$cm-1 are twice the JT energy gain due to the ring-bending and the bond stretching modes correspondingly. Similar values of $`\kappa _1=1.06`$ and $`\kappa _2=0.817`$ were obtained by Eiding et al. Eiding  using ab initio many body techniques.

To solve Eq. (4) for the vibrational spectrum, assume for the moment a zero coupling to the bond stretching vibrational mode $`G_2=0`$. Then Eq. (4) depends on a single parameter $`\kappa _1`$. The classical solution of Longuet-Higgins et al. Longuet  uses polar coordinates, which simplifies equations. Instead we seek the solution of Eq. (4) in the form

$`|\mathrm{\Psi }>={\displaystyle \underset{n_1=0}{\overset{N}{}}}{\displaystyle \underset{n_2=0}{\overset{Nn_1}{}}}`$ $`[A_{n_1,n_2}{\displaystyle \frac{(c_a^{})^{n_1}}{\sqrt{n_1!}}}{\displaystyle \frac{(c_b^{})^{n_2}}{\sqrt{n_2!}}}|0>|b_{3g}>`$
$`+`$ $`B_{n_1,n_2}{\displaystyle \frac{(c_a^{})^{n_1}}{\sqrt{n_1!}}}{\displaystyle \frac{(c_b^{})^{n_2}}{\sqrt{n_2!}}}|0>|b_{2g}>]`$ (7)
Note that we are not making the adiabatic approximation where the electronic wavefunction $`\mathrm{\Psi }_{\mathrm{el}}`$ is strictly held in the lower of the two Jahn-Teller split levels. In adiabatic approximation the double valuedness of $`\mathrm{\Psi }_{\mathrm{el}}`$ under rotation by $`\beta =2\pi `$ is compensated by a restriction on the vibrational wavefunctions. This effect is automatically handled in our non-adiabatic treatment. The operators $`c_a^{}`$, $`c_b^{}`$ create harmonic oscillator states in the two-dimensional manifold of $`e_g`$ vibrations, with their origin at the symmetric ($`D_{6h}`$) benzene ion coordinates. Although different from the basis of Longuet-Higgins et al. Longuet , both basis sets are complete and converge rapidly to the same solution. The solution is found by exact diagonalization of Eq. (4) for $`N=10`$. The eigenvalues coincides with those of Linder et. al. Linder  for the case of zero quadratic coupling.

The vibrational frequencies on the neutral molecule $`\omega _1=581`$ cm-1 and $`\omega _2=1644`$ cm-1 become (for the benzene cation) 0.54$`\omega _1`$ and 0.7$`\omega _2`$ in the uncoupled-mode approximation. To take into account the interaction between the two $`E_{2g}`$ vibrational modes (when both $`G_10`$ and $`G_20`$) one has to use a trial wavefunction similar to Eq. (7), but including all four vibrational modes. The size of the matrix grows as $`2\times C_{N+4}^4(N+2.5)^4/12`$. Convergence was reached for $`N=10`$. The lowest eigenvalues as a function of parameter $`\alpha `$ are shown on Fig. 3. The coupling constants are proportional to $`\alpha `$ and at $`\alpha =1`$ they become $`\kappa _1=1.18`$ and $`\kappa _2=0.8`$ . The frequency shift of the ring bending mode $`\omega _10.55\omega _1`$ is essentially the same as in the noninteracting case. The interaction of the bond stretching mode with the ring bending overtones results in the level repulsion, such that $`\omega _20.84\omega _2`$ for $`\kappa _2=0.8`$. The predicted vibrational spectrum corresponds to $`\alpha =1`$ on Fig. 3.

On the anion, a $`D_{2h}`$ distortion splits the $`e_{2u}`$ LUMO into two $`b_{1u}`$ and $`a_u`$ orbitals, which can be obtained from Eq. (2) by changing the sign in front of the $`|2>`$, $`|4>`$, $`|6>`$ molecular orbitals. Projecting the Hamiltonian Eq. (1) into the $`\{b_{1u},a_u\}`$ manifold leads to the same Hamiltonian as (4) with a sign change of coupling constant $`g_1g_1`$. The vibrational excitation spectra on the anion $`C_6H_6^{}`$ is described by Eq. (4), with coupling constants $`G_1^{}=T_1g_1/6+T_2g_2/2R_0=0.17`$ eV/Å and $`G_2^{}=T_3g_1/6T_4g_2/2R_0=5.48`$ eV/Å. Since the $`H_0`$ part of the projected Hamiltonian is the same as for the cation, the values for $`T_{\mathrm{1..4}}`$ are unchanged. The JT energy lowering on the anion is the same as for the cation $`G_1^2/M\omega _1^2+G_2^2/M\omega _2^2=0.234`$ eV, but the effective couplings to the ring bending and C-C bond stretching modes are now different; $`\kappa _1^{}=0.16`$ and $`\kappa _2^{}=1.06`$ respectively. This means that the frequency of the ring bending $`E_{2g}`$ mode is shifted by less then 2% from the neutral benzene value, whereas the bond-stretching $`E_{2g}`$ mode becomes 59% of the neutral molecule value 1644 cm-1.

## VI Summary

Using the model Hamiltonian Eq. (1) with DFT-calculated parameters, we predict the JT stabilization energy of 944 cm-1 for both the benzene cation and anion. The bond-stretching mode 1644 cm-1 on neutral benzene experiences a large shift on the anion and becomes 970 cm-1, which is very close in energy to the $`a_{1g}`$ breathing mode $`992`$cm-1. On the other hand, the ring-bending mode is essentially unaffected. To the contrary, on the cation both $`E_{2g}`$ JT active modes experience the sizable shifts by 45% and 16% from their neutral benzene values. Experimentally Linder ; Goode  the ring-bending mode on the benzene cation was measured to reduce from $`536`$cm-1 to $`350`$cm-1 (or by 35%). This measurements led Linder et al. Linder  to deduce a JT energy stabilization of 208 cm-1. A more detailed analysis, including quadratic JT coupling, led to the conclusion that the acute $`D_{2h}`$ distorted geometry is the global minimum, lower by 8 cm-1 than the obtuse local minimum. Our Hamiltonian (4) predicts a larger relative shift of the ring bending mode by 10% with respect to the experimental shift. The amount of the shift is sensitive to the choice of normal modes determined by the term $`_0`$ (Eq. 4), a slightly oversimplified model. The main result of our new solution is that there are two contributions to the JT energy lowering. To determine the JT energy lowering on the cation two vibrational $`E_{2g}`$ frequencies have to be measured. The model Hamiltonian (1) contains quadratic couplings, which predict an acute global minimum, while the accuracy of the true DFT answer is insufficient to make such a prediction Muller .

The benzene anion is not stable, which makes it difficult to measure the vibrational spectrum. Electron transmission techniques Burrow  give an opportunity to measure the vibrational sidebands in the resonant electron cross section at negative electron affinity energy 1.1 eV Burrow . The spectrum shows vibrational peaks separated by 123 meV (or 992 cm-1), and were attributed to $`a_{1g}`$ vibrational quanta. The higher frequency JT-active $`e_{2g}`$ mode has not been resolved. Our results, however, suggest that since both breathing and C-C bond stretching modes are coupled to the LUMO, a mixture of the two is expected to be present in the spectrum. Since the $`e_{2g}`$ modes becomes very close in energy to the breathing $`a_{1g}`$ mode, it is difficult to distinguish experimentally between the two.

In conclusion we derived a new model Hamiltonian for the JT active benzene cation and anion, and obtained all parameters from DFT calculations. This model Hamiltonian predicts a JT stabilization energy of $`970`$ cm-1. This value, similar to other first-principles results, is 4.5 times larger than the value deduced experimentally by Linder et al. Linder . However, our model gives the result that two $`E_{2g}`$ modes are JT-active, coupling to the electronic HOMO and LUMO states. Only one of them was measured Linder , and our results are reasonably consistent with that measurement. However, both modes are needed to obtain the JT stabilization energy from spectroscopic data. We conclude that there is no contradiction between theory and experiment, and predict the relevant frequency shifts that can be used to test theory more completely.

###### Acknowledgements.

We are grateful to Prof. Philip M. Johnson for useful discussions. This work was supported in part by DOE Grant No. DE-AC-02-98CH10886, and in part by NSF Grant No. DMR-0089492.


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# Fundamental Limits for Coherent Manipulation on Atom Chips

## 1 Atom chip ‘building block’: the side guide

In the 1930’s, Frisch and Segré realized that when a homogeneous magnetic field (‘bias field’) is superimposed with the field of a straight wire current, the magnetic field vanishes on a line parallel to the current (see figure 1) Frisch33 . In the vicinity of this line, the field increases in a quadrupolar fashion. The height of the field zero is given by

$$h=\frac{\mu _0}{2\pi }\frac{I}{B_b},$$
(1)
where $`\mu _0=4\pi \mathrm{mm}\mathrm{G}/\mathrm{A}`$ is the vacuum permeability, $`I`$ the wire current and $`B_b`$ the bias field magnitude. (This expression applies to finite size wires provided their diameter $`h`$.) This ‘side guide’ can be implemented on an atom chip using a lithographically etched wire on the chip surface. The setup is ideal for miniaturization since the guide height is reduced using smaller currents (with less ohmic dissipation).

Atoms with a nonzero magnetic moment $`𝝁`$ are trapped around the magnetic field minimum provided $`𝝁`$ keeps an antiparallel orientation with respect to the local magnetic field (adiabatic approximation). These ‘weak field seekers’ are attracted to the field zero and get trapped in a potential, $`\mu _{}|𝐁_0(𝐱)|`$, proportional to the magnitude of the magnetic field. (The subscript 0 distinguishes the static trapping field from the field fluctuations discussed later.) It is particularly interesting to introduce a longitudinal magnetic field (along the wire) so that the field magnitude never reaches zero: this helps satisfying the adiabatic approximation everywhere and reduces so-called ‘Majorana flips’ into untrapped magnetic sublevels. The trapping potential is then a harmonic well instead of a linear one around the guide center. This is the guide geometry we focus on in the following. The relevant parameters are the trap height $`h`$ (Eq.1), the oscillation frequency $`\mathrm{\Omega }/2\pi `$ in the harmonic well, and the Larmor frequency $`\omega _\mathrm{L}=\mu _{}|𝐁_0(𝐫)|/\mathrm{}`$ where $`𝐁_0(𝐫)`$ is the field at the trap center and $`\mu _{}`$ is the magnetic moment along the center field Reichel01c ; Folman02 . For the lowest quantum states in the potential well, the magnetic field is predominantly longitudinal, and the single-particle wave functions are approximately harmonic oscillator states for quantum numbers up to $`n\omega _\mathrm{L}/\mathrm{\Omega }`$.

The validity of the adiabatic approximation is also determined by the ratio $`\omega _\mathrm{L}/\mathrm{\Omega }`$: it has been estimated that nonadiabatic losses are exponentially suppressed when this ratio is large Sukumar97  (see also Eberlein00a ). Similarly, tunnelling losses down to the chip surface can be made exponentially small with a sufficiently high and ‘thick’ potential barrier. The main loss channel is then provided by the uncontrollable coupling to the surface via magnetic noise.

## 2 Interaction with magnetic noise

### 2.1 Noise spectrum and spin flip rate

The coupling of the atomic magnetic moment to fluctuating magnetic fields gives rise to both spin flips and changes in the center-of-mass motion (scattering). The rate of these processes is given by Fermi’s Golden Rule. We recall here that it can be conveniently expressed in terms of the noise spectrum of the magnetic field fluctuations. (See Sipe84  for a similar approach and Chap. IV of CDG2  for the derivation of a full master equation.)

If we write $`|\mathrm{i}`$ and $`|\mathrm{f}`$ for the atomic states before and after the transition, the transition rate is

$$\mathrm{\Gamma }_{\mathrm{i}\mathrm{f}}=\frac{2\pi }{\mathrm{}}\underset{\mathrm{F},\mathrm{I}}{}p(\mathrm{I})\left|\mathrm{F},\mathrm{f}|H_{\mathrm{int}}|\mathrm{I},\mathrm{i}\right|^2\delta (E_\mathrm{F}+E_\mathrm{f}E_\mathrm{I}E_\mathrm{i}),$$
(2)
where $`|\mathrm{I}`$ and $`|\mathrm{F}`$ are initial and final states for the field, the summation being an average over the initial field states (with probabilities $`p(\mathrm{I})`$) and a trace over the final field states. The interaction Hamiltonian is given by $`H_{\mathrm{int}}=𝝁𝐁(𝐱)`$.

Consider first the rate for spin flips. Since only a subset of magnetic sublevels $`|m_\mathrm{i}`$ are weak field seekers, spin flips $`|m_\mathrm{i}|m_\mathrm{f}`$ are responsible for trap loss. The magnetic field is evaluated at the position $`𝐫`$ of the trap center. (An average over the atomic position distribution would be more accurate.) We write the $`\delta `$-function for energy conservation as a time integral over $`\mathrm{e}^{\mathrm{i}(E_\mathrm{I}E_\mathrm{F}\mathrm{}\omega _{\mathrm{fi}})t/\mathrm{}}`$ where $`\mathrm{}\omega _{\mathrm{fi}}=E_\mathrm{f}E_\mathrm{i}`$. The exponential $`\mathrm{e}^{\mathrm{i}(E_\mathrm{I}E_\mathrm{F})t/\mathrm{}}`$ can be removed by introducing the field operators in the Heisenberg picture

$$𝐁(𝐫,t)=\mathrm{e}^{\mathrm{i}H_0t/\mathrm{}}𝐁(𝐫)\mathrm{e}^{\mathrm{i}H_0t/\mathrm{}}$$
(3)
(here, $`H_0`$ is the free field Hamiltonian) and taking matrix elements of this operator between the initial and final field states. This gives

$$\mathrm{e}^{\mathrm{i}(E_\mathrm{I}E_\mathrm{F})t/\mathrm{}}\mathrm{I}|𝐁(𝐫)|\mathrm{F}=\mathrm{I}|𝐁(𝐫,t)|\mathrm{F}.$$
(4)
The sum over the final states $`|\mathrm{F}`$ now reduces to a completeness relation and we get ($`\alpha ,\beta `$ denote field components)

$`2\pi \mathrm{}{\displaystyle \underset{\mathrm{F},\mathrm{I}}{}}p(\mathrm{I})\mathrm{I}|B_\alpha (𝐫)|\mathrm{F}\mathrm{F}|B_\beta (𝐫)|\mathrm{I}\delta (E_\mathrm{F}E_\mathrm{I}\mathrm{}\omega )`$
$`={\displaystyle \underset{\mathrm{}}{\overset{\mathrm{}}{}}}dt\mathrm{e}^{\mathrm{i}\omega t}{\displaystyle \underset{\mathrm{I}}{}}p(\mathrm{I})\mathrm{I}|B_\alpha (𝐫,t)B_\beta (𝐫,0)|\mathrm{I}`$
$`=S_{\alpha \beta }(𝐫;\omega ).`$ (5)
In the last line, we have defined the magnetic noise spectrum which is the Fourier transform of the field’s autocorrelation function. The rate for spin flips can now be written as

$$\mathrm{\Gamma }_{\mathrm{i}\mathrm{f}}=\frac{1}{\mathrm{}^2}\underset{\alpha ,\beta =x,y,z}{}m_\mathrm{i}|\mu _\alpha |m_\mathrm{f}m_\mathrm{f}|\mu _\beta |m_\mathrm{i}S_{\alpha \beta }(𝐫,\omega _{\mathrm{fi}}).$$
(6)
Since $`m_\mathrm{f}m_\mathrm{i}`$, the matrix elements of $`\mu _\alpha `$ are only nonzero for directions perpendicular to the magnetic field at the trap center. We also recover the selection rule $`m_\mathrm{f}m_\mathrm{i}=\pm 1`$ so that the relevant transition frequency is the Larmor frequency $`|\omega _{\mathrm{fi}}|=\omega _\mathrm{L}`$. The spin flip rate gives the order of magnitude of trap loss even if more than one weak-field seeking Zeeman states, $`m_\mathrm{i}=+2,+1`$, say, are trapped (possible with many of the alkali atoms). This is because the matrix elements between adjacent sublevels do not significantly differ in magnitude so that the atoms reach the non-trapped sublevel $`m_\mathrm{f}=0`$ after a time $`2/\mathrm{\Gamma }_{+2+1}`$.

We finally note that as long as the behaviour of the ‘environment’ (the field) is ignored in the description of the atom’s dynamics, the noise spectrum is the only quantity needed to characterize the environment. It is also an experimentally measurable quantity: for example, the rms magnetic noise $`B_x^2(𝐫)^{1/2}`$ measured by a spectrum analyzer in a given frequency band $`\mathrm{\Delta }\omega /2\pi `$ around $`\omega `$ is $`(2S_{xx}(𝐫,\omega )\mathrm{\Delta }\omega /2\pi )^{1/2}`$, the factor $`2`$ accounting for the sum over positive and negative frequencies. The atomic spin flip rate may be regarded as an alternative way to measure the noise spectrum. In order of magnitude, the magnetic moment is comparable to the Bohr magneton, $`\mu _\mathrm{B}`$ ($`\mu _\mathrm{B}/2\pi \mathrm{}=1.4`$MHz/G), and we get

$$\mathrm{\Gamma }_{\mathrm{i}\mathrm{f}}(𝐫)0.01\mathrm{s}^1(\mu /\mu _\mathrm{B})^2\frac{S_{\alpha \beta }(𝐫,\omega _\mathrm{L})}{\mathrm{pT}^2/\mathrm{Hz}}.$$
(7)
Note that current SQUID magnetometers are able to detect magnetic field noise even on the $`10\mathrm{fT}/\sqrt{\mathrm{Hz}}`$ scale Varpula84 .

### 2.2 Near field noise

The magnetic noise spectrum close to a solid substrate shows dramatic differences with respect to the well-known blackbody spectrum. This is because thermally excited currents in the substrate (Johnson-Nyquist noise) generate electromagnetic fields with substantial nonpropagating components. As an illustration, figure 2 shows the noise spectrum at a fixed distance ($`h=1\mu `$m) above a metallic half-space, calculated along the lines of Henkel99c . One gets an increase of several orders of magnitude for low frequencies (wavelength $`\lambda `$ much larger than $`h`$). In addition, the spectrum is rather flat in this range. Only at high frequencies ($`\lambda <h`$), the Planck spectrum is recovered because the detector then enters the far field of the source.

In the low-frequency range, the magnetic near field noise above a planar substrate is approximately characterized by the spectrum Henkel99c

$$\frac{\omega h}{c}1:S_{\alpha \beta }(𝐫,\omega )=\frac{\mu _0^2k_BT}{16\pi \varrho }\frac{s_{\alpha \beta }}{h}[1+\frac{2h^3}{3\delta (|\omega |)^3}]^1,$$
(8)
where $`T,\varrho `$ are the substrate temperature and resistivity, respectively, $`h`$ is the observation distance, $`s_{\alpha \beta }=\mathrm{diag}(\frac{1}{2},1,\frac{1}{2})`$ is a diagonal tensor (the distinguished axis is along the surface normal), and $`\delta (\omega )=\sqrt{2\varrho /\mu _0\omega }`$ is the skin depth. In order of magnitude, the corresponding spin flip rate is surprisingly large for traps at a micrometer distance:

$$h\delta (\omega _\mathrm{L}):\mathrm{\Gamma }_{\mathrm{i}\mathrm{f}}100\mathrm{s}^1\frac{(\mu /\mu _\mathrm{B})^2(T/300\mathrm{K})}{(\varrho /\varrho _{\mathrm{Cu}})(h/\mu \mathrm{m})},$$
(9)
where $`\varrho _{\mathrm{Cu}}=1.7\times 10^6\mathrm{\Omega }\mathrm{cm}`$ is the copper resistivity. The flip rate is plotted as a function of distance in figure 3. A larger Larmor frequency (longitudinal bias field) only helps reducing spin flips when $`h>\delta (\omega _\mathrm{L})`$, giving a scaling $`\mathrm{\Gamma }_{\mathrm{i}\mathrm{f}}\omega _\mathrm{L}^{3/2}`$. Finally, there are many plausible reasons to expect that the linear dependence on $`T`$ of the flip rate (9) does not continue down to very low temperatures: the full Bose-Einstein occupation number has to be used, $`k_\mathrm{B}T\mathrm{}\omega _\mathrm{L}(1\mathrm{e}^{\mathrm{}\omega _\mathrm{L}/k_\mathrm{B}T})^1`$, and other sources of magnetic fields may come into play like spin waves, lattice vibrations etc. One thus probably gets lifetimes (and coherence times, see the following) shorter than predicted by (9).

At room temperature, the estimate (9) describes a worst case because most materials have a resistivity larger than copper. A structured substrate like a thin metallic layer or a wire also helps: the magnetic noise then decreases more rapidly with distance $`h`$ Folman02 ; Henkel01a . As a general rule, the smaller the amount of metallic material, the lower the magnetic noise. This can be understood from a simple model where thermally excited currents in each volume element of the conducting substrate contribute to the total magnetic noise above (a similar approach has been used in Varpula84 ; Turchette00a ). For distances $`h\delta (\omega )`$, one obtains a noise spectrum accurate within a factor of two from an incoherent addition of magnetostatic fields, neglecting the influence of the material on the field propagation. For example, at a distance $`h`$ from a single, thin wire with radius $`ah`$, the theory of Ref.Henkel01a  yields a magnetic noise tensor given by Eq.(8) with the replacement $`s_{\alpha \beta }/h(\pi a^2/h^3)\mathrm{diag}(2,\frac{1}{2},\frac{3}{2})`$, showing a similar weak anisotropy. The components specify the azimuthal, radial and longitudinal directions in cylindrical coordinates, respectively. The correction involving the skin depth $`\delta (\omega )`$ cannot be obtained in the magnetostatic approximation.

Experimental data Reichel01b ; Zimmermann01 ; Zimmermann02a  indicate that trap lifetimes as long as or even longer than estimated by (9) (several $`100`$ms to $`100`$s) are achievable: these traps were built close to thin wires ($`3`$ to $`90\mu `$m width) or semiconductor substrates covered with thin metallic layers (thickness $`h`$), at distances between $`20\mu `$m and $`2`$mm. It should be noted that the distance dependence of the trap lifetime measured in Zimmermann02a  only agrees qualitatively with our theory, and more detailed investigations are required.

### 2.3 Current noise

The electric currents that generate the side guide fields are also subject to fluctuations that drive spin flips and deform the trapping fields. The impact of technical noise can be reduced using electronic filtering, “quiet” drivers, by correlating the currents for the wire and the bias field etc. This works down to the most fundamental level where the noise due to the discrete value of the electron charge comes into play (‘shot noise’). For a current $`I`$ in free space, shot noise has a frequency-independent spectrum given by

$$SN_I=eI0.16\mathrm{nA}^2/\mathrm{Hz}\frac{I}{\mathrm{A}},$$
(10)
where $`e`$ is the charge quantum. Note that currents in a solid wire can have fluctuations below the shot noise limit because the Coulomb interaction correlates the electrons. In the following, we use $`SN_I`$ as a convenient reference value.

If the wire current in a side guide has a noise spectrum $`S_I(\omega )`$, it creates a magnetic field with

$$S_B(𝐫,\omega )=\frac{\mu _0^2eI}{4\pi ^2h^2}\frac{S_I(\omega )}{SN_I}.$$
(11)
This scalar quantity gives one component of the noise tensor. The spin flip rate is then of the order of

$$\mathrm{\Gamma }_{\mathrm{i}\mathrm{f}}1\mathrm{s}^1\frac{(\mu /\mu _B)^2}{(h/\mu \mathrm{m})^2}\frac{S_I(\omega _L)}{SN_I}\frac{I}{\mathrm{A}}.$$
(12)
We conclude that miniaturization beyond the micrometer scale requires extremely low current noise to achieve trap lifetimes longer than seconds. It may well turn out that very large scale atom chip integration is only possible with static magnetic fields, generated by magnetized nanostructures Hinds99b . Experimental trap lifetime data Reichel01b ; Zimmermann02a  show that currently used power supplies are quiet enough not to reduce lifetimes at distances above $`10\mu `$m.

## 3 Spin coherence

Coherent manipulation on atom chips requires both that atoms stay trapped and that their quantum state be preserved. Here, we focus on the influence of magnetic noise on the internal (spin) states. For example, different magnetic sublevels or hyperfine states are interesting candidates to implement a bit of quantum information (qubit). Noise-induced transitions between sublevels erase the qubit, and this occurs on the same timescale as the spin flips discussed in the previous section. But the information contained in quantum superpositions can also be lost by pure ‘dephasing’, without changing sublevel populations Stern90 . For this process, which opens an additional channel for decoherence, longitudinal magnetic fields, i.e. polarized along the static trapping field (‘phase noise’), come into play.

Consider two magnetic sublevels $`|m_1`$ and $`|m_2`$ that are simultaneously trapped. A magnetic field fluctuation parallel to the static trapping field changes the energy difference between the two qubit states by

$$\mathrm{\Delta }E(t)=\mathrm{\Delta }\mu _{}B_{}(𝐫,t),$$
(13)
where $`B_{}`$ is the longitudinal magnetic field and $`\mathrm{\Delta }\mu _{}=m_2|\mu _{}|m_2m_1|\mu _{}|m_1`$ the differential magnetic moment. (This difference can be substantially reduced in alkalis by choosing hyperfine states that only differ in the nuclear spin state.) Let us now expose a superposition of $`|m_1`$ and $`|m_2`$ to pure magnetic phase noise during an interaction time $`t`$. The off-diagonal element of the corresponding $`2\times 2`$ density matrix is then proportional to Stern90

$$\mathrm{exp}\frac{\mathrm{i}}{\mathrm{}}\underset{0}{\overset{t}{}}dt^{}\mathrm{\Delta }E(t^{})=\mathrm{exp}\left[\frac{\mathrm{\Delta }\mu _{}^2t}{2\mathrm{}^2}S_{}(𝐫;0)\right],$$
(14)
where $`S_{}(𝐫;0)`$ is the low-frequency limit of the magnetic noise spectrum. (More precisely, one needs the spectrum averaged over the frequency range $`0\mathrm{}1/t`$. We neglect this complication since the relevant spectra are flat in this range.)

From Eq.(14), we conclude that dephasing leads to exponential decoherence of qubit superpositions with a rate similar to the spin flip rate (*cf.* Eq.(6)). The decoherence rate gets smaller when the logical states have the same magnetic moment (reducing $`\mathrm{\Delta }\mu _{}`$), or when the magnetic field component $`B_{}`$ shows much less noise.

Near field noise is rather isotropic, as shown by the spectrum (8), and therefore contributes equally to spin flips and phase noise. Noise in the wire current gives only fluctuations perpendicular to the guide axis so that dephasing is suppressed close to the guide center. Note that this suppression is not complete because of the finite, transverse width of the trapped wave function. In addition, gravity can displace the actual trap center with respect to the magnetic field minimum (the ‘gravitational sag’ familiar from Bose condensates in magnetic traps, see also Ketterle02a ). In the harmonic approximation, a simple calculation leads to a reduction of the dephasing rate by a factor $`(Mg/\mu _{}b)^2`$ where in order of magnitude

$$\frac{Mg}{\mu _{}b}0.1\frac{(M/\mathrm{amu})[g/(10\mathrm{m}/\mathrm{s}^2)]}{(\mu _{}/\mu _\mathrm{B})[b/(\mathrm{G}/\mathrm{cm})]}.$$
(15)
This ratio can be made quite small ($`<10^6`$) using typical magnetic gradients $`b=B_b/h`$ achievable with the side guide. Magnetic near fields thus remain as the main source of dephasing noise, with a rate basically scaling like the spin flip rate.

## 4 Vibrational coherence

In this section, we turn to scattering processes that leave the atoms in the magnetic trap, but perturb their center-of-mass motion. This occurs whenever the magnetic noise is not spatially homogeneous. A simple model is suggested showing that the typical length scale for magnetic inhomogeneities is of the order of the trap height $`h`$ for both near field noise and current noise at the shot noise level. We discuss the relation between random changes in the atoms’ momentum and the decoherence of their density matrix in position space.

### 4.1 Scattering rate

We again use Fermi’s Golden Rule (2), but now the initial and final states are given by wave functions $`\psi _{\mathrm{i},\mathrm{f}}(𝐱)`$. In the following, we retain only a single trapped magnetic sublevel $`|m_\mathrm{f}=|m_\mathrm{i}`$ and assume that the magnetic moment has the same orientation for all relevant center-of-mass states. Its matrix elements then reduce to $`\mu _{}`$ (the component along the trapping field). Writing out the overlap integral between wave functions, the transition rate (2) becomes

$$\mathrm{\Gamma }_{\mathrm{i}\mathrm{f}}=\frac{\mu _{}^2}{\mathrm{}^2}\mathrm{d}^3x\mathrm{d}^3x^{}M_{\mathrm{fi}}^{}(𝐱)M_{\mathrm{fi}}(𝐱^{})S_{}(𝐱,𝐱^{};\omega _{\mathrm{fi}}),$$
(16)
where the wavefunction overlap is given by

$$M_{\mathrm{fi}}(𝐱)=\psi _\mathrm{f}^{}(𝐱)\psi _\mathrm{i}(𝐱),$$
(17)
the transition energy $`\mathrm{}\omega _{\mathrm{fi}}`$ is the difference between the center of mass levels, and the field correlation spectrum is the generalization of the noise spectrum (5):

$$S_{}(𝐱,𝐱^{};\omega )=\underset{\mathrm{}}{\overset{\mathrm{}}{}}dt\mathrm{e}^{\mathrm{i}\omega t}\underset{\mathrm{I}}{}p(\mathrm{I})\mathrm{I}|B_{}(𝐱,t)B_{}(𝐱^{},0)|\mathrm{I}.$$
(18)
A useful figure that can be extracted from this function is the correlation length $`l_\mathrm{c}`$ that governs the variation of (18) as a function of distance $`𝐬=𝐱𝐱^{}`$. As a general rule, one has $`S_{}(𝐱,𝐱^{};\omega )0`$ if $`sl_\mathrm{c}`$ because the fields $`B_{}(𝐱,t)`$ and $`B_{}(𝐱^{},t)`$ become decorrelated. More quantitatively, we define here $`l_\mathrm{c}`$ by the following expansion for small deviations from the trap center $`𝐫`$

$`S_{}(𝐱,𝐱^{};\omega )S_{}(𝐫;\omega )\left[1{\displaystyle \frac{(𝐱𝐱^{})^2}{l_\mathrm{c}^2}}\right]`$ (19)
$`\text{provided }|𝐱𝐫|,|𝐱^{}𝐫|l_\mathrm{c}.`$
In Sec.6, we show that the correlation length $`l_\mathrm{c}`$ is comparable to the trap height $`h`$, for both near field and current noise.

### 4.2 Heating

Consider the vibrational motion along one transverse direction (the $`x`$-axis, say) in the harmonic region of the side guide. Magnetic noise can induce transitions between different quantum states in the trap (‘heating’). The transition $`01`$ between the ground and first excited states is particularly interesting and involves the overlap integral ($`\omega _{\mathrm{fi}}=\mathrm{\Omega }`$)

$$dxdx^{}M_{\mathrm{fi}}^{}(x)M_{\mathrm{fi}}(x^{})S_{}(𝐱,𝐱^{};\mathrm{\Omega })\frac{a^2}{l_\mathrm{c}^2}S_{}(𝐫;\mathrm{\Omega })$$
(20)
where $`a=(\mathrm{}/2M\mathrm{\Omega })^{1/2}`$ is the (rms) size of the trap ground state ($`M`$ is the atomic mass) and the noise spectrum is evaluated at the trap center $`𝐫`$. Eq.(20) is derived in the limit of strong confinement ($`a`$ much smaller than the correlation length $`l_\mathrm{c}`$), using the expansion (19).

Comparing (20) to (6), we conclude that heating in tight traps is suppressed relative to spin flips, due to the small ratio $`(a/l_\mathrm{c})^21`$. We stress that this is not due to the increase in the trap frequency (because the noise is essentially white), but due to the small size of the trap ground state. Since $`l_\mathrm{c}h`$, the excitation rate $`\mathrm{\Gamma }_{01}`$ follows power laws $`1/h^3`$, $`1/h^4`$, instead of the flip rates (9, 12), depending on the noise source. For example, the rate due to near field noise above a metallic half-space scales like Folman02

$$\mathrm{\Gamma }_{01}\frac{1\mathrm{s}^1(\mu /\mu _B)^2(T_s/300\mathrm{K})}{(M/\mathrm{amu})(\mathrm{\Omega }/2\pi \mathrm{\hspace{0.17em}100}\mathrm{kHz})(\varrho /\varrho _{\mathrm{Cu}})(h/\mu \mathrm{m})^3}.$$
(21)
Heating is also relevant for the decoherence of qubits implemented in different vibrational levels. One can derive a master equation for the density matrix in the harmonic well that shows that the corresponding off-diagonal elements decay at a rate comparable to $`\mathrm{\Gamma }_{01}`$. For details, see Henkel99c ; Turchette00a .

Finally, we note that even spatially homogeneous magnetic fluctuations can induce heating when they change the trap position or curvature. Displacing the trap is equivalent to a force and drives the transition $`01`$ with a rate Folman02 ; Savard97 ; Gehm98 :

$$\mathrm{\Gamma }_{01}=\frac{M\mathrm{\Omega }^3}{2\mathrm{}}S_h(\mathrm{\Omega })$$
(22)
where $`M`$ is the atomic mass and $`S_h(\omega )`$ is the spectrum of the trap height fluctuations. Taking into account only field fluctuations caused by the wire current, we get in order of magnitude

$`\mathrm{\Gamma }_{01}`$ $``$ $`3\mathrm{s}^1(M/\mathrm{amu})(\mathrm{\Omega }/2\pi \mathrm{\hspace{0.17em}100}\mathrm{kHz})^3`$ (23)
$`\times {\displaystyle \frac{I/\mathrm{A}}{(B_b/\mathrm{G})^2}}{\displaystyle \frac{S_I(\mathrm{\Omega })}{SN_I}}.`$
This rate is still reasonably small for sufficiently large bias fields $`B_b>50`$G. Note, however, that a very strong confinement may not be possible due to the increase with the trap frequency $`\mathrm{\Omega }`$: this occurs because a larger spring constant $`M\mathrm{\Omega }^2`$ translates position fluctuations into larger forces.

Fluctuations in the trap position due to technical noise can be reduced by correlating the currents in the wire with those procuding the bias fields. The trap curvature, however, then still fluctuates and changes the oscillation frequency $`\mathrm{\Omega }`$. This gives a parametric resonance on the $`02`$ transition with a rate Folman02 ; Savard97 ; Gehm98 :

$`\mathrm{\Gamma }_{02}`$ $`=`$ $`{\displaystyle \frac{1}{2}}S_\mathrm{\Omega }(2\mathrm{\Omega })`$ (24)
$``$ $`3\times 10^8\mathrm{s}^1{\displaystyle \frac{(\mathrm{\Omega }/2\pi \mathrm{\hspace{0.17em}100}\mathrm{kHz})^2}{I/\mathrm{A}}}{\displaystyle \frac{S_I(2\mathrm{\Omega })}{SN_I}},`$ (25)
which is substantially smaller than the rate (23). Fluctuations in $`\mathrm{\Omega }`$ also induce phase noise on the quantum states in the harmonic trap because their energy difference is $`\mathrm{}\mathrm{\Omega }`$. Arguing as in Sec.3, one finds a dephasing rate comparable to $`\mathrm{\Gamma }_{02}`$.

In experiments with trapped atoms, it is relatively simple to observe the rate of temperature increase, $`\dot{T}`$. In the harmonic approximation, one finds a ‘heating rate’ $`k_B\dot{T}=\mathrm{}\mathrm{\Omega }\mathrm{\Gamma }_{01}`$ for noise driving the transitions $`nn\pm 1`$ Savard97 ; Gehm98 . Currently observed values are in the range of $`0.051\mu `$K/s Reichel01b ; Zimmermann02a . This is orders of magnitude larger than predicted by (21) and excludes an origin dominated by near field noise. Heating can probably be attributed to current fluctuations, as given by (23), assuming typical power supply noise spectra (above shot noise). Ambient electromagnetic noise (‘electrosmog’) may also play a role and is currently under investigation.

## 5 Spatial coherence

### 5.1 Scattering ‘cross section’

We now consider the quasi-free motion along the side guide axis $`Oz`$, the transverse motion is assumed to be ‘frozen out’. Noise induces scattering $`p_\mathrm{i}p_\mathrm{f}`$ between different momentum states, where the wavefunction overlap $`M_{\mathrm{fi}}(z)=L^1\mathrm{exp}(\mathrm{i}q_{\mathrm{fi}}z)`$ involves the wavevector transfer $`\mathrm{}q_{\mathrm{fi}}=p_\mathrm{f}p_\mathrm{i}`$ ($`L`$ is a normalization length). The transition frequency is $`\omega _{\mathrm{fi}}=q_{\mathrm{fi}}p_\mathrm{i}/M+\mathrm{}q_{\mathrm{fi}}^2/2M`$. We end up with the spatial Fourier transform of the correlation function (the vectors $`𝐱`$, $`𝐱^{}`$ only differ in their $`z`$-components)

$`\mathrm{\Gamma }_{\mathrm{i}\mathrm{f}}`$ $`=`$ $`{\displaystyle \frac{\mu _{}^2}{\mathrm{}^2}}{\displaystyle \frac{\mathrm{d}z\mathrm{d}z^{}}{L^2}\mathrm{e}^{\mathrm{i}q_{\mathrm{fi}}(zz^{})}S_{}(𝐱,𝐱^{};\omega _{\mathrm{fi}})}`$ (26)
$``$ $`{\displaystyle \frac{\mu _{}^2}{\mathrm{}^2}}S_{}(𝐫;\omega _{\mathrm{fi}}){\displaystyle \frac{\mathrm{d}s}{L}\mathrm{e}^{\mathrm{i}q_{\mathrm{fi}}s}C(s;\omega _{\mathrm{fi}})}.`$
To perform the last step, we have assumed that the correlations involve only the distance $`s=zz^{}`$ (statistically homogeneous noise) and used the normalized correlation function ($`C(0;\omega )1`$):

$$C(zz^{};\omega )=\frac{S_{}(𝐱,𝐱^{};\omega )}{S_{}(𝐫;\omega )}.$$
(27)
Finally, we get a transition rate per wavevector transfer $`\mathrm{d}\mathrm{\Gamma }/\mathrm{d}q`$ by dividing by the wavevector spacing $`\mathrm{d}q=2\pi /L`$ in the quantization volume:

$$\frac{\mathrm{d}\mathrm{\Gamma }_{\mathrm{i}\mathrm{f}}}{\mathrm{d}q}=\gamma \frac{\mathrm{d}s}{2\pi }\mathrm{e}^{\mathrm{i}q_{\mathrm{fi}}s}C(s;\omega _{\mathrm{fi}}),$$
(28)
where the rate $`\gamma `$ is the prefactor of the integral in Eq.(26). If the elements of the magnetic noise tensor are of comparable magnitude, this rate is of the same order as the spin flip rate (6). As mentioned at the end of Sec.3, this is the case for near field noise and to a some extent also for fluctuations due to current noise.

We conclude from the differential scattering rate (28) that typical momenta exchanged with the noise field have a magnitude $`q_{\mathrm{fi}}\mathrm{}/l_\mathrm{c}`$ given by the inverse noise correlation length.

### 5.2 Decoherence

The relation to spatial decoherence of the atoms has been made more quantitative in Henkel01a , where the following master equation for the density matrix $`W(z,p)`$ in the Wigner representation is derived

$`\left(_t+{\displaystyle \frac{p}{M}}_z\right)W(z,p)`$
$`={\displaystyle dq\frac{\mathrm{d}\mathrm{\Gamma }}{\mathrm{d}q}\left(W(z,p+\mathrm{}q)W(z,p)\right)}.`$ (29)
The scattering integral on the right hand side describes processes $`pp+\mathrm{}q`$, while the left hand side gives the free ballistic motion along the guide axis.

The master equation (29) can be solved exactly using the fact that the ‘scattering cross section’ (28) is essentially independent of the transition frequency $`\omega _{\mathrm{fi}}`$ for the relevant magnetic field fluctuations. One finds the following expression for the spatially averaged coherence function of the atoms Henkel01a

$`\rho (s,t)`$ $``$ $`{\displaystyle dz\psi ^{}(z+s,t)\psi (z,t)}`$ (30)
$`=`$ $`\rho (s,0)\mathrm{exp}\left(\gamma t[1C(s;0)]\right),`$ (31)
where the brackets denote the average with respect to the noise and $`C(s;0)`$ is the low-frequency limit of the noise correlation function.

From the coherence function (31), we identify $`\gamma [1C(s;0)]`$ as the decoherence rate for spatially separated superposition states: for a splitting greater than the correlation length, $`sl_\mathrm{c}`$, the correlation function $`C(s;0)`$ is zero and the superposition decays into a statistical mixture on a time scale given by $`1/\gamma `$, comparable to the spin lifetime. Superpositions with smaller splitting $`s`$ decay more slowly, with a rate scaling like $`[1C(s;0)]\gamma (s/l_\mathrm{c})^2\gamma \gamma `$, using the expansion (19). This behaviour was also found in a decoherence model by W. H. Zurek Zurek91  who used a master equation in Fokker-Planck form instead of our Eq.(29).

We note that the decoherence rate just found also describes the dephasing between the arms of a guided matter wave interferometer Folman02 ; Hinds01a ; Andersson02 . This follows from an argument similar to that used in Eq.(14). In this context, $`s`$ is the (transverse) separation between the arms of the interferometer. For more details, we refer to Folman02 .

### 5.3 Decoherence of a condensate

We now discuss the extension of the previous results to the case of a Bose condensate in a linear waveguide (see Reichel02a  for a review of experiments). The single-particle wave functions then have to be replaced by collective modes, and the effective potential is changed due to atom-atom interactions. For example, the (transverse) ground state has a larger width compared to the single-particle wave function so that the atomic spins are no longer aligned along the guide axis. We present here preliminary results for the decoherence of a Bose condensate focussing on a quasi-1D regime Olshanii98 ; Ketterle01b ; Dettmer01 ; Petrov01 . Adopting a mean-field description, we have performed Monte-Carlo simulations of the one-dimensional Gross-Pitaevski equation

$$\mathrm{i}\mathrm{}\frac{\psi }{t}=\frac{\mathrm{}^2}{2M}\frac{^2\psi }{z^2}+V(z,t)\psi +g|\psi (z)|^2\psi $$
(32)
where the coupling constant $`g=2\mathrm{}\mathrm{\Omega }a_\mathrm{s}`$ is proportional to the (transverse) trap frequency and the s-wave scattering length $`a_\mathrm{s}>0`$ (repulsive interactions). The random potential $`V(z,t)`$ is chosen in accordance with the correlation functions relevant for atom chip traps (white noise and lorentzian spatial correlations). The initial situation is a condensate in the ground state of a harmonic trap superimposed on the waveguide potential. Quantum (phase) fluctuations Dettmer01 ; Petrov01  are ignored assuming effectively $`T_{\mathrm{at}}=0`$. The harmonic confinement is instantaneously released at $`t=0`$, and the cloud expands along the waveguide axis.

The simulation results given in figure 4 show the spatially averaged coherence function of the condensate, Eq.(30), as a function of the separation $`s`$ for different expansion times $`t`$. One observes that in the presence of noise (scattering rate $`\gamma 0`$), the coherence length (the width of $`\rho (s,t)`$) is reduced as time increases — the cloud breaks apart in mutually incoherent patches that have ‘seen’ different noise potentials. The dotted lines in the upper left figure give the prediction (31) of the master equation for noninteracting atoms, and we note a very good agreement between the analytics and the numerical data.

We find that the decoherence scenario is not qualitatively changed by a moderate self-interaction, as a comparison of the panels for $`g=0`$ and $`g=10`$ shows. Only for short times is the coherence length of an interacting cloud larger because the ground state is broadened by the interactions. A more detailed investigation of condensate decoherence, including analytical approximations and the limit of strong interactions, will be presented elsewhere Henkel02c .

## 6 Noise correlation length

We finally show that magnetic noise involved in atom chips has a correlation length $`l_\mathrm{c}h`$, for both near field and current noise.

### 6.1 Near field noise

The spatial correlation function for the electric near field above a thermal, planar substrate was studied in Henkel00b . A similar calculation yields for the magnetic near field the following normalized correlation function:

$$C(s;0)=\frac{8h^2}{(2h+\sqrt{s^2+4h^2})\sqrt{s^2+4h^2}}\frac{16h^2/3}{s^2+16h^2/3}$$
(33)
This gives the correlation for the magnetic field component $`B_{}`$, taken at positions $`z`$, $`z^{}`$ on the side guide axis with a separation $`s`$. We have assumed that the field wavelength (fixed by the transition frequency $`\omega _{\mathrm{fi}}`$) is much larger than the relevant distances $`s,h`$. The lorentzian form in Eq.(33) is a good approximation for all distances where $`C(s;0)`$ is sensibly nonzero and shows even more explicitly that the correlation length is of the order of the guide height $`h`$. This is because the noise fields radiated by each volume element of the substrate are quasi-static in the near field and decay algebraically (no retardation).

### 6.2 Shot noise correlations

One might think at first sight that magnetic noise due to current fluctuations should have a large correlation length because the relevant electromagnetic frequencies (kHz to MHz range) propagate with a large wavelength along the wire. The analysis of near field fluctuations has shown, however, that the wavelength is not really the relevant scale as soon as one is sensitive to non-propagating fields generated by nearby sources. For this reason, we suggest a simple toy model for the flow of electrons through a thin wire that allows to recover both the noise spectrum of the magnetic field and its spatial correlations.

The ingredients of the model are sketched in figure 5 and details are given in Appendix A. The electrons are assumed to move independently and ballistically (the Drude electron gas model), their transverse position in the wire is neglected compared to the guide distance $`h`$. It is beyond the scope of this model to describe correlations between the electrons that could lead to lower current fluctuations. Neither does the model describe diffusive electron transport, we comment on that below.

The result of the model is the magnetic noise spectrum (41) given in the Appendix. We recover the previous spectrum (11) (with current noise at the shot noise level, $`S_I(\omega )=SN_I`$) in the low-frequency limit where $`\omega hv`$ for all relevant electron velocities $`v`$. At high frequencies, the noise is reduced because one needs fast electrons to produce magnetic field ‘pulses’ with short duration $`h/v`$. This is visible in Figure 6 where the spectrum (41), for fixed $`h=1\mu `$m, is shown as a function of frequency, normalized to its low-frequency limit. The high-frequency cutoff occurs at $`\omega hv_\mathrm{F}`$ where $`v_\mathrm{F}`$ is the Fermi velocity when the Fermi-Dirac distribution is taken for $`P(v)`$. A Maxwellian distribution gives a similar behavior with a lower cutoff, as shown in the figure. Note again that at most frequencies relevant for atom chip traps, the noise spectrum can be assumed flat.

The characteristic length scale $`l_\mathrm{c}`$ for the spatial correlation of the shot noise fields can also be read off from Eq.(41). In the directions perpendicular to the guide axis, it is given by the guide height $`h`$, and we recover the same correlation length as for near field fluctuations. For the motion along the guide axis, the simplest way is compute the differential scattering rate (28). For a process $`p_\mathrm{i}p_\mathrm{i}+\mathrm{}q`$, we get

$$\frac{\mathrm{d}\mathrm{\Gamma }_{\mathrm{i}\mathrm{f}}}{\mathrm{d}q}=\gamma _{\mathrm{SN}}\frac{p_\mathrm{i}}{Mq}P(p_\mathrm{i}/M)\left[qhK_1(qh)\right]^2,$$
(34)
where we have neglected the recoil shift $`\mathrm{}q^2/2M`$ compared to the Doppler shift $`qp_\mathrm{i}/M`$. The scattering rate is

$$\gamma _{\mathrm{SN}}=\frac{\mu _{}^2\mathrm{cos}^2\alpha }{\mathrm{}^2}\frac{\mu _0^2eI}{4\pi ^2h^2},$$
(35)
where $`\alpha `$ is the angle between the atomic spin and the wire field. If the harmonic approximation for the transverse motion is not valid, $`\mathrm{cos}\alpha `$ is not small and (35) is comparable to the spin flip rate (*cf.* Eq.11), typically a few $`1\mathrm{s}^1`$. $`K_1`$ in Eq.(34) is the modified Bessel function of the second kind, and $`P(v)`$ is the electrons’ velocity distribution, taken at the atomic velocity $`p_\mathrm{i}/M`$. It is interesting that the scattering involves a class of electrons co-moving with the atom: this suggests that the atomic wave in the linear guide is diffracted by the spatially confined field pulse. The divergence of the cross-section (34) for forward scattering ($`q0`$) is related to the long range behavior of the field pulse; this behavior also occurs for the Coulomb potential where the Rutherford cross section diverges in the forward direction.

We can now conclude that also the longitudinal scattering is limited to momentum transfers $`\mathrm{}q\mathrm{}/h`$. This is due to the large-argument asymptotics of the Bessel function in the result (34)

$$qh1:qhK_1(qh)\sqrt{\frac{\pi qh}{2}}\mathrm{e}^{qh},$$
(36)
giving an exponential suppression for large $`qh`$. The shot noise field is thus also ‘rough’ on a scale $`l_\mathrm{c}h`$, and does not behave qualitatively different compared to the thermal magnetic near field.

We finally comment on our neglect of the diffusive electron motion in the wire. Since this effect gives rise to the nonzero resistivity of the wire, it is in fact included in the Johnson noise approach for the metallic substrate. The finite drift velocity of the electrons, which makes the distribution $`P(v)`$ asymmetric, does not change our conclusions either because it is typically much smaller than the width of $`P(v)`$. The electron drift is taken into account in the spectrum shown in figure 6.

## 7 Perspectives

We have reviewed in this paper loss, heating and decoherence mechanisms for wire-based atom chips and their scaling with the microtrap geometry and the substrate material properties. The importance of the shot noise level for current noise has been highlighted. Using a simple model, we have shown that the spatial correlation length of magnetic fields due to shot noise is fixed by the distance between microtrap and chip wire.

The extreme miniaturization of atom chip traps below the $`1\mu `$m scale may not be possible with “conventional”, conducting nanostructures, because magnetic field fluctuations due to thermal and technical current fluctuations become quite strong. The key process is a noise-induced change of the atomic sublevel $`|m`$ (‘spin flip’). Its rate, which can be related to the trap lifetime, also dictates the order of magnitude of more subtle processes involving heating of the center-of-mass motion or qubit dephasing. The timescale for useful coherent manipulations is thus at least limited to a few 100 ms at a height of a few $`\mu `$m. Depending on the gate time of 2-qubit operations, this time scale may be sufficient.

Several strategies leading to more robust atom chips can be imagined. Cooled substrates reduce thermal near field noise, with a gain in lifetime inversely proportional to the temperature. Quiet current drivers and/or superconducting wires are an option to reduce current noise, possibly below the shot noise level. Substrates with a permanent magnetization may also provide the required low-noise environment.

The theory of magnetic noise close to complex, magnetized structures can be developed starting from a description of the material in terms of its electric and magnetic susceptibilities. According to the fluctuation-dissipation theorem Varpula84 ; Agarwal75a , the imaginary parts of these fix the magnitude of the noise current and magnetization that generate thermal noise fields. This scheme can be used at low frequencies (high temperatures), which is the typical situation in atom chip traps, but can also be extended to high frequencies where the noise reduces to vacuum fluctuations, modified by the boundary conditions set by the substrate (see e.g. Scheel00b  for a review). This kind of approach can be used to compute atom-atom interactions mediated by virtual photon exchange.

Another theoretical task is to estimate the coupling between higher atomic levels and the electric and magnetic fields originating from the surface. For example, it has been proposed to make use of the electric dipole-dipole interaction to realize controlled two-qubit gates on atom chip traps Calarco00 ; Brennen00 . The gate operation is sped up when the atoms are excited to high-lying Rydberg states, but these states also interact strongly with the chip substrate due to their large dipole moments, hence the need for a review of their coherence times.

Finally, the understanding of the impact of the surface on the fidelity of qubit operations needs to be studied in order to optimize the construction of an atom chip quantum processor.

Acknowledgments. C.H. took a great benefit from a discussion with Marc-André Dupertuis, and thanks Sierk Pötting for his collaboration in earlier stages and for providing figure 1. Thanks to Johannes Hecker Denschlag for being a critical co-author in previous work. The help of Simon A. Gardiner with the numerical simulations of figure 4 is gratefully acknowledged. We also thank an anonymous referee for carefully reading the manuscript. This work has been supported by the Deutsche Forschungsgemeinschaft via the ‘Schwerpunktprogramm Quanten-Informationsverarbeitung’ and by the European Union via the ACQUIRE network (contract number IST-1999-11055).

## Appendix A Correlation of magnetic fields generated by shot noise

Each electron (charge $`e`$), during its passage with velocity $`v`$ below the trapped atom, gives an electromagnetic ‘pulse’ whose vector potential is given by

$`𝐀(𝐱,t)`$ $`=`$ $`𝐞_zek(𝐱,tt_0;v)`$ (37)
$`=`$ $`{\displaystyle \frac{𝐞_z\mu _0ev/4\pi }{\left[x^2+y^2+(zv(tt_0))^2\right]^{1/2}}},`$
where the coordinates are chosen as shown in figure 5. The atom actually experiences an average vector potential that is due to the flow of many electrons, passing below the atom at random instants $`t_0`$. With the assumption of a stationary electron flow, we find

$$𝐀(𝐱,t)=𝐞_z\frac{\mu _0}{4\pi }I\mathrm{log}(x^2+y^2)+\text{const.}$$
(38)
where the average current is $`I=en/\mathrm{\Delta }t`$ with $`n`$ the number of electrons flowing during the interval $`\mathrm{\Delta }t`$. This average vector potential is time-independent and gives the static magnetic field generated by the current. Note that it does not involve the velocity distribution of the electrons. (The calculation is analogous to the calculation of a photodetector current, as outlined in chapter 9.8 of MandelWolf .)

We are interested in the correlation function of the vector potential (from which the magnetic field correlations follow via differentiation). Subtracting the average value and performing again the average over the flowing electrons, we find using the approximation of independent electrons

$`A_z(𝐱,t+\tau )A_z(𝐱^{},t)A_z(𝐱,t+\tau )A_z(𝐱^{},t)`$
$`={\displaystyle \frac{e^2n}{\mathrm{\Delta }t}}{\displaystyle dt^{}dvP(v)k(𝐱,t^{}+\tau ;v)k(𝐱^{},t^{};v)},`$ (39)
where the ‘pulse function’ $`k(\mathrm{},t;\mathrm{})`$ is defined in Eq.(37). The prefactor $`e^2n/\mathrm{\Delta }t=eI`$ is the shot noise spectrum $`SN_I`$ (Eq.10). The Fourier integral with respect to the time difference $`\tau `$ gives the squared Fourier transform of the pulse function that can be evaluated analytically. We do not give this formula here, but proceed directly to the magnetic field correlation tensor. After differentiation, one needs the Fourier transform

$$dt\frac{v\mathrm{e}^{\mathrm{i}\omega t}}{\left[r^2+(zvt)^2\right]^{3/2}}=\frac{2\mathrm{e}^{\mathrm{i}\omega z/v}|\omega /v|}{r}K_1(r|\omega /v|),$$
(40)
where $`r^2=x^2+y^2`$ and $`K_1`$ is a Bessel function. The magnetic noise field has the same orientation (azimuthal) as the static field so that in cylindrical coordinates, the correlation tensor has a single nonzero element given by

$`S_{\phi \phi ^{}}(𝐱,𝐱^{};\omega )={\displaystyle \frac{\mu _0^2SN_I}{4\pi ^2rr^{}}}{\displaystyle dvP(v)\mathrm{e}^{\mathrm{i}(zz^{})\omega /v}}`$
$`\times {\displaystyle \frac{rr^{}\omega ^2}{v^2}}K_1(r|\omega /v|)K_1(r^{}|\omega /v|).`$ (41)
In the low-frequency limit where $`\omega h,\omega rv`$, one gets $`(r\omega /v)K_1(r\omega /v)1+𝒪((r\omega /v)^2)`$. At the guide center $`r=r^{}=h,z=z^{}`$, we then recover the magnetic noise spectrum (11) with $`S_I(\omega )=SN_I`$.

The scattering cross section (28) involves the Fourier transform of the correlation function (41) with respect to the distance $`s=zz^{}`$. This gives a $`\delta `$-function that permits us to perform the integral over the electron velocities. At $`r=r^{}=h`$, we get

$`{\displaystyle dvP(v)\delta \left(\frac{\omega }{v}+q\right)\left[\frac{h\omega }{v}K_1(h|\omega /v|)\right]^2}`$ (42)
$`={\displaystyle \frac{|\omega |}{q^2}}P(\omega /q)[qhK_1(qh)]^2.`$ (43)
For the scattering process $`p_\mathrm{i}p_\mathrm{i}+\mathrm{}q`$, $`\omega =\omega _{\mathrm{fi}}`$ is the negative kinetic energy difference (see Eq.26), so that

$$\frac{\omega }{q}=\frac{qp_\mathrm{i}+\mathrm{}q^2/2}{Mq}\frac{p_\mathrm{i}}{M},$$
(44)
neglecting the recoil shift compared to the Doppler shift. This approximation yields the scattering probability (34).


text:
# TOWARDS DEEP-INELASTIC STRUCTURE FUNCTIONS AT THREE LOOPS

## 1 Introduction

Today, structure functions in inclusive deep-inelastic scattering are extremely well measured quantities. As a consequence, they offer the possibility for very precise determinations of the strong coupling $`\alpha _s`$ and the parton distribution functions. The high statistical accuracy of the present and upcoming experimental measurements demands analyses to next-to-next-to leading order (NNLO) of perturbative QCD for the structure functions $`F_2,F_3`$ and $`F_L`$.

However, the complete NNLO corrections are not fully available yet. The two-loop coefficient functions of $`F_2,F_3`$ and $`F_L`$ have been calculated . For the three-loop anomalous dimensions only a finite number of fixed Mellin moments  are presently available. In addition, some information about leading fermionic contributions  and the small-$`x`$ limit  exists.

In the following, we briefly report on the status of the calculation of the coefficient functions and the anomalous dimensions to three loops in perturbative QCD. Furthermore, we present results for the leading fermionic contributions to the non-singlet structure function $`F_2`$.

## 2 Method

We employ the optical theorem and the operator product expansion (OPE) to calculate the deep-inelastic structure functions in Mellin space analytically  as general functions of $`N`$. For the $`N`$-th Mellin moment of $`F_2`$ we can write

$`F_2^N(Q^2)={\displaystyle \underset{0}{\overset{1}{}}}𝑑xx^{N2}F_2(x,Q^2)={\displaystyle \underset{j=\alpha ,\mathrm{q},\mathrm{g}}{}}C_{2,j}^N({\displaystyle \frac{Q^2}{\mu ^2}},\alpha _s)A_{\mathrm{P},N}^j\left(\mu ^2\right),`$ (1)
where $`C_{2,j}^N`$ denote the coefficient functions and $`A_{\mathrm{P},N}^j`$ the spin averaged hadronic matrix elements of singlet operators $`O^\mathrm{q}`$, $`O^\mathrm{g}`$ and non-singlet operators $`O^\alpha `$, $`\alpha =1,2,\mathrm{},(n_f^21),`$ of leading twist. Both, the coefficient functions and the renormalized operator matrix elements in eq.(1) satisfy renormalization group equations governed by the same anomalous dimensions $`\gamma _{jk}`$. The anomalous dimensions determine the scale evolution of deep-inelastic structure functions.

The calculation of the coefficient functions $`C_{2,j}^N`$ and anomalous dimensions $`\gamma _{jk}`$ at a given order in perturbation theory amounts to the determination of the $`N`$-th moment of all contributing Feynman diagrams with external partons of momentum $`p`$ with $`p^2=0`$ and photons of momentum $`q`$ with $`q^2=Q^2`$. To achieve this task, we apply the following strategy . We set up a hierarchy among all diagrams depending on the number of $`p`$-dependent propagators. We define basic building blocks (BBB) as diagrams in which the parton momentum $`p`$ flows only through a single line in the diagram, while composite building blocks (CBB) denote all diagrams with more than one $`p`$-dependent propagator.

Then, with the help of integration-by-parts  and scaling identities  we determine reduction schemes that map the CBB’s of a given topology to the BBB’s of the same topology or to the CBB’s of a simpler topology. Subsequently, we use reduction identities that express the BBB’s of a given topology in terms of simpler topologies. Working in Mellin space, the reduction equations often involve explicitly the parameter $`N`$ of the Mellin moment. Sometimes, one encounters difference equations in $`N`$ for the $`N`$-th moment $`F(N)`$ of a diagram,

$`a_0(N)F(N)+a_1(N)F(N1)+`$ (2)
$`\mathrm{}+a_n(N)F(Nn)+G(N)`$ $`=`$ $`0,`$
where $`G(N)`$ denotes the $`N`$-th Mellin moment of simpler diagrams. First order difference equations can be solved at the cost of one sum over $`\mathrm{\Gamma }`$-functions in dimensional regularization. We use $`D=42ϵ`$. The $`\mathrm{\Gamma }`$-functions can be expanded in $`ϵ`$ and the sum can be solved to any order in $`ϵ`$ in terms of harmonic sums . Higher order difference equations could be solved constructively. On the mathematical side, the approach to calculate Mellin moments of structure functions relies on particular mathematical concepts , such as harmonic sums  and our ability to set up and solve the difference equations as nested sums in $`N`$.

## 3 Leading fermionic contributions

To illustrate the method, we discuss the leading fermionic contributions to the non-singlet structure function. At three loops, they are proportional to $`n_f^2`$, with $`n_f`$ being the number of massless fermions. These contributions form a gauge-invariant subset, but do not involve yet any genuine three-loop topologies. Therefore, in the sense of the reduction strategy sketched above, the $`n_f^2`$-terms are easier to calculate.

The result for the $`n_f^2`$-contribution to the non-singlet anomalous dimension $`g_{\mathrm{qq}}^{(2),\mathrm{ns}}`$ at three loops is known from the work of Gracey . It is given by,

$`g_{\mathrm{qq}}^{(2),\mathrm{ns}}`$ $`=`$ $`C_Fn_f^2({\displaystyle \frac{17}{9}}+{\displaystyle \frac{32}{9}}{\displaystyle \frac{1}{N+1}}{\displaystyle \frac{88}{27}}{\displaystyle \frac{1}{(N+1)^2}}+{\displaystyle \frac{8}{9}}{\displaystyle \frac{1}{(N+1)^3}}{\displaystyle \frac{32}{9}}{\displaystyle \frac{1}{N}}`$ (3)
$`+{\displaystyle \frac{88}{27}}{\displaystyle \frac{1}{N^2}}{\displaystyle \frac{8}{9}}{\displaystyle \frac{1}{N^3}}{\displaystyle \frac{16}{27}}S_1(N){\displaystyle \frac{80}{27}}S_2(N)+{\displaystyle \frac{16}{9}}S_3(N)),`$
with $`C_F=(N^21)/(2N)`$, which is $`4/3`$ for QCD.

As a new result, we give here the $`n_f^2`$-contribution to the non-singlet coefficient function $`c_{2,\mathrm{qq}}^{(3),\mathrm{ns}}`$ at three loops for the flavour class, where both photons couple to the external quark. Strictly speaking, the three-loop coefficient functions contribute in a perturbative expansion only at next-to-next-to-next-to-leading order (NNNLO). However, the result illustrates nicely that our method will not only provide the anomalous dimensions, which are proportional to the single pole in $`ϵ`$ in dimensional regularization, but also the coefficient functions which are determined by the finite terms, since our approach is (at least in principle) not limitated to a given order in $`ϵ`$.

In terms of harmonic sums up to weight four, our result for the $`n_f^2`$-contribution to $`c_{2,\mathrm{qq}}^{(3),\mathrm{ns}}`$ reads

$`c_{2,\mathrm{qq}}^{(3),\mathrm{ns}}=`$ (4)
$`C_Fn_f^2({\displaystyle \frac{9517}{486}}{\displaystyle \frac{8}{9}}\zeta _3+{\displaystyle \frac{36748}{729}}{\displaystyle \frac{1}{N+1}}+{\displaystyle \frac{16}{27}}{\displaystyle \frac{\zeta _3}{N+1}}{\displaystyle \frac{4384}{81}}{\displaystyle \frac{1}{(N+1)^2}}`$
$`+{\displaystyle \frac{2360}{81}}{\displaystyle \frac{1}{(N+1)^3}}{\displaystyle \frac{184}{27}}{\displaystyle \frac{1}{(N+1)^4}}+{\displaystyle \frac{16}{3}}{\displaystyle \frac{S_1(N+1)}{(N+1)^3}}{\displaystyle \frac{544}{27}}{\displaystyle \frac{S_1(N+1)}{(N+1)^2}}`$
$`{\displaystyle \frac{32}{9}}{\displaystyle \frac{S_{1,1}(N+1)}{(N+1)^2}}+{\displaystyle \frac{32}{9}}{\displaystyle \frac{S_2(N+1)}{(N+1)^2}}+{\displaystyle \frac{2240}{81}}{\displaystyle \frac{S_1(N+1)}{N+1}}+{\displaystyle \frac{272}{27}}{\displaystyle \frac{S_{1,1}(N+1)}{N+1}}`$
$`+{\displaystyle \frac{16}{9}}{\displaystyle \frac{S_{1,1,1}(N+1)}{N+1}}{\displaystyle \frac{16}{9}}{\displaystyle \frac{S_{1,2}(N+1)}{N+1}}{\displaystyle \frac{272}{27}}{\displaystyle \frac{S_2(N+1)}{N+1}}{\displaystyle \frac{16}{9}}{\displaystyle \frac{S_{2,1}(N+1)}{N+1}}`$
$`+{\displaystyle \frac{16}{9}}{\displaystyle \frac{S_3(N+1)}{N+1}}{\displaystyle \frac{11170}{729}}{\displaystyle \frac{1}{N}}{\displaystyle \frac{16}{27}}{\displaystyle \frac{\zeta _3}{N}}+{\displaystyle \frac{1204}{81}}{\displaystyle \frac{1}{N^2}}{\displaystyle \frac{992}{81}}{\displaystyle \frac{1}{N^3}}+{\displaystyle \frac{184}{27}}{\displaystyle \frac{1}{N^4}}`$
$`{\displaystyle \frac{16}{3}}{\displaystyle \frac{S_1(N)}{N^3}}+{\displaystyle \frac{232}{27}}{\displaystyle \frac{S_1(N)}{N^2}}+{\displaystyle \frac{32}{9}}{\displaystyle \frac{S_{1,1}(N)}{N^2}}{\displaystyle \frac{32}{9}}{\displaystyle \frac{S_2(N)}{N^2}}{\displaystyle \frac{644}{81}}{\displaystyle \frac{S_1(N)}{N}}`$
$`{\displaystyle \frac{104}{27}}{\displaystyle \frac{S_{1,1}(N)}{N}}{\displaystyle \frac{16}{9}}{\displaystyle \frac{S_{1,1,1}(N)}{N}}+{\displaystyle \frac{16}{9}}{\displaystyle \frac{S_{1,2}(N)}{N}}+{\displaystyle \frac{104}{27}}{\displaystyle \frac{S_2(N)}{N}}`$
$`+{\displaystyle \frac{16}{9}}{\displaystyle \frac{S_{2,1}(N)}{N}}{\displaystyle \frac{16}{9}}{\displaystyle \frac{S_3(N)}{N}}+{\displaystyle \frac{8714}{729}}S_1(N)+{\displaystyle \frac{32}{27}}S_1(N)\zeta _3+{\displaystyle \frac{940}{81}}S_{1,1}(N)`$
$`+{\displaystyle \frac{232}{27}}S_{1,1,1}(N)+{\displaystyle \frac{32}{9}}S_{1,1,1,1}(N){\displaystyle \frac{32}{9}}S_{1,1,2}(N){\displaystyle \frac{232}{27}}S_{1,2}(N)`$
$`{\displaystyle \frac{32}{9}}S_{1,2,1}(N)+{\displaystyle \frac{32}{9}}S_{1,3}(N){\displaystyle \frac{860}{27}}S_2(N){\displaystyle \frac{536}{27}}S_{2,1}(N){\displaystyle \frac{64}{9}}S_{2,1,1}(N)`$
$`+{\displaystyle \frac{64}{9}}S_{2,2}(N)+{\displaystyle \frac{2440}{81}}S_3(N)+{\displaystyle \frac{32}{3}}S_{3,1}(N){\displaystyle \frac{368}{27}}S_4(N)).`$
This result agrees with the one of the fixed Mellin moment calculation  for $`N=2,\mathrm{},14`$. It may be used to improve approximations  to the full functional form of $`c_{2,\mathrm{qq}}^{(3),\mathrm{ns}}`$, although the $`n_f^2`$-terms are numerically not the most dominant contribution.

## 4 Conclusions

The present approach based on the OPE, to calculate the Mellin moments of structure functions allows for the calculation of the complete coefficient functions and the anomalous dimensions at three loops.

As a next step, one can consider the subleading fermionic contributions at three loops proportional to $`n_f`$. The determination of these terms already relies on major parts of the complete reduction scheme as it requires the calculation of several genuine three-loop topologies of the Benz type as well as the calculation of two-loop topologies with a self-energy insertion. The results for the $`n_f`$-contribution to the non-singlet anomalous dimension will be presented elsewhere.