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# Two-Pulse Atomic Coherent Control (2PACC) Spectroscopy of Eley-Rideal Reactions. An Application of an Atom Laser.

## I Introduction

Controlling the outcome of a chemical reaction has been the ultimate goal of chemistry. Coherent control, a new addition to the quest, is based on exploitation of quantum interferences of matter-waves to build a constructive interference in the desired channel and a destructive interference in all other channels. To carry out such a task the molecular matter-wave has to exhibit a coherent property. To date, all experimental applications of coherent control have been based on imprinting the coherent properties of a light/optical source onto the matter to be controlledRice (2001); Gordon and Rice (1997). With the experimental realization of Bose-Einstein condensationAnderson et al. (1995); Davis et al. (1995); Bradley et al. (1995, 1997), a new source of coherent matter-waves has become potentially available. The present paper explores the direct employment of a matter-wave coherent source to achieve the goal of coherent control of a chemical reaction.

The utilization of a matter-wave source depends on the experimental ability to direct and shape the matter-waves from a Bose-Einstein condensation (BEC). The waves in a BEC trap constitute a single many-body matter-wave function which is an analogue of a photon field in an optical cavity. An output coupler termed atom laser transforms the condensate into a source of either pulsed or continuous coherent matterMewes et al. (1997); Anderson and Kasevich (1998); Hagley et al. (1999); Bloch et al. (1999); Coq et al. (2001); Köhl et al. (2002); Chikkatur et al. (2002). We propose to employ this matter-wave for a surface mediated chemical reaction carried out by a two-pulse atomic coherent control (2PACC) spectroscopy. The present paper elaborates on previous preliminary studies (See Refs. Jørgensen and Kosloff, 2003, 2002).

BEC has been accomplished for a growing list of atoms $`\{`$$`{}_{}{}^{133}\mathrm{𝐂𝐬}`$ (Ref. Weber et al., 2003), $`{}_{}{}^{87}\mathrm{𝐑𝐛}`$ (Ref. Anderson et al., 1995), $`{}_{}{}^{85}\mathrm{𝐑𝐛}`$ (Ref. Cornish et al., 2000), $`{}_{}{}^{23}\mathrm{𝐍𝐚}`$ (Ref. Davis et al., 1995), $`{}_{}{}^{7}\mathrm{𝐋𝐢}`$ (Refs. Bradley et al., 1995, 1997; Schreck et al., 2001), $`{}_{}{}^{6}\mathrm{𝐋𝐢}`$ (Ref. Schreck et al., 2001), $`𝐊`$ (Ref. Modugnu et al., 2001), $`𝐇`$ (Ref. Fried et al., 1998) and meta-stable $`\mathrm{𝐇𝐞}`$ (Refs. Santos et al., 2001; Robert et al., 2001)$`\}`$. All of the above condensates and additional systems to be prepared, are candidates for a source for a coherently matter-wave.

The principle of interfering optical waves in a molecular framework has neatly been demonstrated by Scherer et al.Scherer et al. (1990, 1991). Using a sequence of two optical pulses, population is transferred from the ground to the excited electronic state in the iodine molecule. The first pulse promotes a portion of the wave function to the excited state, which then evolves in time. The second pulse, which is phase-locked relative to the first one, excites an additional wave packet to the excited state.. The intramolecular superposition of the two wave packets is subject to quantum interferences, either constructive or destructive. This gives rise to larger or smaller population on the excited state for a given time-delay between the pulses. The outcome is then controlled by the optical phase difference between the two pulses and the evolution of the initial wave packetScherer et al. (1990, 1991); Kosloff et al. (1992); Bartana et al. (1993).

The objective of the study is to control a bimolecular surface reaction using a coherent source of matter-waves shaped as two phase-locked pulses. The target substrate is a stationary atom adsorbed on a surface. The outcome of the reaction is a desorbed molecule in the gas phase composed from one atom from the matter-wave pulse and one surface atom. The method is therefore termed two-pulse atomic coherent control (2PACC) spectroscopy. The yield of the reaction is controlled by the time delay between the two atomic pulses and the relative phase between them.

The majority of studies in coherent control have concentrated on unimolecular processes. An exception is the study by Abrashkevish et al Abrashkevich et al. (1998) which theoretically considered a 3D-atom-diatom reactive scattering process. The 2PACC spectroscopy is aimed at the more difficult task of controlling a bimolecular reaction described by $`A+BC`$.

In contrast to a two-pulse photon field the matter waves are dispersive. This means that the source of the matter-waves, the BEC condensate, has to be positioned very close to the target surface. Such a device is realized in the so-called atom chipsJones et al. (2003); Folman et al. (2002); Hänsel et al. (2001) or surface micro-trapsLeanhardt et al. (2002); Ott et al. (2001). In the atom chips for example the BEC has been placed a few hundred microns above a metal surfaceFolman et al. (2002). The additional step required to realize the current proposal is a two-pulsed output coupler directing a coherent pulse of atoms toward the surface.

A coherent optical spectroscopy employed in surface science is two-photo emission (2PPE) which has served as the inspiration for the present proposed 2PACC. In 2PPE, two photons from a laser are applied to a surface with or without adsorbates. In 2PPE, the first optical pulse excites a surface electron to an intermediate level of either an image potential state or an unoccupied molecular orbital of the adsorbate. The second photon exploits this excitation to create a measurable outcome. The method has been used to characterize the energetics and dynamics of electrons, atoms and molecules on surfacesGeisen et al. (1985); Fauster and Steinmann (1995); Harris et al. (1997); Petek and Ogawa (2002); Shumay et al. (1998); Vondrak et al. (2000); Gahl et al. (2000). The application of two laser pulses allows for probing the nuclear dynamics of the electronic states which could not be studied if only one pulse was applied. Recently, Petek et alPetek and Ogawa (2002) have demonstrated that applying a sequence of phase-locked optical pulses coherently controls the motion of an alkali atom on the metal surface and thereby the desorption process.

The bimolecular surface mediated reaction to be controlled by the 2PACC spectroscopy is the Eley-Rideal reaction. The atomic pulses consist of a coherent atomic source of hydrogen or alkali atoms which collide with a hydrogen atom chemisorbed on a Cu(111)-surface. The outcome is an ejected molecule in the gas phase of either H2 or an alkali hydride. It will be shown that the application of a second atomic pulse induces the matter-wave interferences that enable enhancement or suppression of the desorbing flux of molecules relative to a single atomic beam experiment. The quantum interferences are controlled by the time delay and the relative phase between the two atomic pulses.

Theoretical studies of Eley-Rideal reactions have been performed by Jackson et al.Sha et al. (2002); Jackson and Lemoine (2001); Shalashilin et al. (1999); Jackson and Persson (1992) for an incident hydrogen atom beam interacting with various coated surfaces. They have observed that hot atom processes, where the impinging atom becomes trapped onto the surface, play an important role. The trapped atoms can react with the adsorbate or they can eventually dissipate enough energy through collisions with the adsorbates to become immobile. These dissipative forces cause decoherence and therefore will suppress the 2PACC control. In this paper the energy and charge transfer between the surface and the adsorbates are not included.

The dynamics of the 2PACC spectroscopy model is explored by solving the time dependent Schrödinger equation by a Newtonian propagation method Ashkenazi et al. (1995). The matter-wave pulses are presented by two phase related Gaussian-like wave-packets. The atomic and molecular as well as their interactions with the surface are described in a diabatic framework.

The methodology of the 2PACC spectroscopy is presented in Section II. In Section III the dynamics of 2PACC is presented. In Section IV two simulations of 2PACC spectroscopy are studied one with a hydrogen source and another with a lithium atom laser both impinging on a Cu-surface with chemisorbed hydrogen atoms. Conclusions and a general outlook are presented in Section V.

## II The model

The target of control is the Eley-Rideal reaction described by

$$𝐘+𝐇/\mathrm{𝐂𝐮}(111)\mathrm{𝐘𝐇}+\mathrm{𝐂𝐮}(111).$$
(1)
The atom Y is from the atom laser source, which in the present model consists of either hydrogen or alkali atoms. The matter-wave of Y is directed to a Cu(111)-surface with low coverage chemisorbed hydrogen atoms. When the wave function of Y overlaps with that of the adsorbed atom, interaction is expected, leading to a recombination that forms the YH molecule. If the newly formed molecule has sufficient energy it will eventually desorb from the surface to the gas phase. By shaping the wave function of Y, the yield of the desorbing molecules becomes controlled by constructive or destructive interference. The simplest controlled wave function is obtained by a sequence of two pulses where the time delay and relative phase are the control variables. It is anticipated that atom lasers will be able to produce such coherent matter-wave pulses by an output coupler of a coherent source - the Bose-Einstein condensate (BEC). For example a coherent atomic pulse can be realized by using an optical laser source to transfer the atom from a trapped (BEC) to an untrapped state (the atom laser). The relative phase between the two optical pulses can be utilized to phase-lock the two pulses of the atom matter-wave. A time delay between the two optical laser determines also the time delay between the two pulsed atomic laser. The coherent properties of interest are projected onto this wave function. In this study the wave function of an atom laser composed of a single atom is represented by two Gaussian wave functions with a well defined time-delay and phase.

The binding energy for a hydrogen atom on a Cu(111)-surface is roughly 2.4 eV. Since the bond energy of H2 is approximately twice this value, the reaction is very exothermic. For this reason the desorbing molecule is expected to be vibrationally hot due to the large exothermicity. As one proceeds through the list of atoms (Y$`=`$$`\{`$H,Li,Na,K,Rb,Cs$`\}`$) the reaction changes from exothermic to endothermic. If the Cu(111)-surface is replaced with an Al(110)-surface all the reactions become again exothermic since the binding energy of the hydrogen on this surface is only 1.8 eV Castro et al. (1996).

The present modeling of the Eley-Rideal reaction restricts the motion of the two atoms to a collinear configuration normal to the surface. We consider the reaction between an impinging atom of mass $`m_y`$ located at $`z_y`$ and a target atom of mass $`m_h`$ located at $`z_h`$ which is initially adsorbed on a flat static surface. The coordinate set ($`z_h,z_y`$) is transformed to a new set of coordinates ($`r,Z`$) where $`r=z_yz_h`$ is the intramolecular distance and $`Z=(m_hz_h+m_yz_y)/M`$ is the center of mass coordinate. The total and reduced mass of the system are denoted by $`M`$ and $`\mu `$, respectively. Effects arising from phonons and surface corrugations are not included in this model.

### II.1 Two-dimensional potential energy surfaces

To understand the dynamics of either a dissociation reaction of a diatomic or a recombination reaction of two atomic species on a surface, potential energy surfaces (PES) representing the physics of breaking and forming a chemical bond is required. A comprehensive overview of the historical development of potential energy surfaces is given in Ref. Darling and Holloway, 1995.

An electronic structure model for the dissociation/recombination of the H2/Cu system has been suggested by Holloway and co-workersHarris et al. (1988); Hand and Holloway (1989). Their model is based on a small complex of the form Cu2H2 in a planar $`C_{2v}`$ geometry. The intramolecular coordinates are $`r`$ which is the distance between the two hydrogen atoms, and $`Z`$ the distance between the midpoint of H-H and Cu-Cu. For large value of $`Z`$ there is no interaction between the two units, H-H and Cu-Cu, meaning that each unit has a separate set of fully occupied molecular orbitals. As $`Z`$ decreases the two units approach each other, the orbitals with similar symmetry with respect to the bond center mix, e.g. the parallel-bonding orbital of H-H and Cu-Cu interfere with the parallel anti-bonding of Cu-H. Due to these interactions the orbital energies shift. This causes a crossing between the ”parallel” and ”perpendicular” orbitals with the result that the H-Cu bonding becomes energetically favorable.

The PES of the reactant surface has been constructed from a Morse potential describing the hydrogen-hydrogen bond and a repulsive potential as the hydrogen molecule approaches the surface. In the product channel the two separated hydrogen atoms are chemisorbed on the surface, this bond is described by a Morse potential. The hydrogen-hydrogen repulsion on the surface is represented by an exponential repulsive potential.

In the diabatic representation, the potential is represented by a 2$`\times `$2 $`𝑽`$-matrix

$$𝑽(r,Z)=\left[\begin{array}{c}𝑽_{RR}(r,Z)𝑽_{RP}(r,Z)\\ 𝑽_{PR}(r,Z)𝑽_{PP}(r,Z)\end{array}\right].$$
(2)
The diagonal elements are the potential energy surfaces of the reactant and the product states and the off-diagonal elements is the non-adiabatic couplings between them. Upon diagonalization of the 2$`\times `$2 $`𝑽`$-matrix two new adiabatic PES are obtained. In the previous studies of Eley-Rideal reactions the adiabatic PES has been used. We will briefly discuss the idea behind them.

Jackson et al.Sha et al. (2002); Shalashilin et al. (1999); Persson et al. (1999) used the London-Eyring-Polanyi-Sato (LEPS) potential energy surface for modeling the Eley-Rideal reactions. The LEPS potential is given by

$$V=U_m+U_a+U_b\pm \sqrt{A_m^2+[A_a+A_b]^2A_m[A_aA_b]},$$
(3)
where $`U`$ and $`A`$ are the Coulomb and exchange contributions. The intramolecular contributions are denoted $`U_m`$ and $`A_m`$, whereas the other terms describe the atomic interactions with the surface. Here, only the lowest adiabatic PES are considered. The PES of the molecule as well as the interactions between the surface and a single atom have been calculated by Density Functional Theory (DFT). They have been fitted to the functional forms, $`U`$ and $`A`$, which are based on Morse-like attractive and repulsive terms which decay exponentially with increasing distances. Surface effects have been introduced through expanding the Morse parameters representing the surface in a Fourier series of the reciprocal lattice vectors.

The LEPS-potential is a member of a class of diatomic in molecules (DIM) potential forms. For surface reactions, an extension called embedded diatomic in molecules (EDIM) has been developed. The model was originally developed by Truong et al Truong et al. (1989) and recently used for the description of the motion of $`N_2`$ on a ruthenium-surfaceTully and Billing (2002). In the EDIM the intramolecular interactions are modeled by Morse and anti-Morse potentials which represent the singlet and triplet electronic state of the diatomic molecule in the gas phase. The interaction between the atoms in the gas phase and the surface is modeled by embedded atom model (EAM), in which the atom experiences an average charge density from the surface.

In the 2PACC spectroscopy the coherent properties of the encounter is intricate therefore the Born-Oppenheimer approximation in which the reaction takes place on a single potential energy surface has to be replaced with a non-adiabatic framework. In the 2PACC dynamics a diabatic frame is chosen consisting of two potential energy surfaces. Specifically, for the Eley-Rideal reaction the diabatic PES are constructed from two atomic or one molecular chemical species interacting with the surface. In the reactant channel the interaction between the stationary hydrogen atom and the surface is strong due to a chemical bond. We are using a semi-empirical functional form for the PES. The impinging atom experiences a repulsive force from the adsorbed atom as well as a long-range attraction from the surface due to polarization forces. In the product channel the newly formed molecule is attached to the surface by a weak bond induced by the polarization forces between the surface and the molecule. The PES for the reactant and product channels have the following functional forms

$`𝑽_{RR}(r,Z)`$ $`=`$ $`V_{HM}^R+V_{YM}^R+V_{YH}^R`$ (4)
$`𝑽_{PP}(r,Z)`$ $`=`$ $`V_{YHM}^P+V_{YH}^P,`$ (5)
where the index M represents the interactions with the surface. The last terms of Eqs.(4-5) represent the intramolecular interaction between the two gas phase atoms, H and Y. The other terms represent the interaction between an atom or a molecule with the surface. In the following section we will discuss each of the individual terms in the reactant and product PES.

#### II.1.1 Intramolecular interactions

Asymptotically, the intramolecular interaction potentials, $`V_{YH}^R`$ and $`V_{YH}^P`$ in the reactant and product channels become the triplet and singlet electronic states of the molecule, YH, when both atoms are far from the metal surface. The PES of the alkali hydride molecule was based on the intramolecular gas-phase singlet and triplet electronic states which have been evaluated by a multi-configuration self-consistent field calculation by Geum et al.Geum et al. (2001). These potentials have been fitted to a cubic spline interpolation function.

For the hydrogen molecule the singlet and triplet PES are given by a Morse and an anti-Morse potential

$`V_{HH}^P(r,Z)`$ $`=`$ $`D_{HH}([1e^{\{\alpha _{HH}(Z)(rr_{HH}^e(Z))\}}]^21)`$
$`V_{HH}^R(r,Z)`$ $`=`$ $`{\displaystyle \frac{1}{2}}{\displaystyle \frac{1\mathrm{\Delta }}{1+\mathrm{\Delta }}}D_{HH}([1+e^{\{\alpha _{HH}(Z)(rr_{HH}^e(Z))\}}]^21).`$
The dissociation energy of the hydrogen molecule is denoted $`D_{HH}`$ and $`(1\mathrm{\Delta })(1+\mathrm{\Delta })`$ is the Sato factor. The equilibrium distance between the two hydrogen atoms, $`r_{HH}^e`$, and the coupling strength, $`\alpha _{HH}`$, have been obtained as a function of $`Z`$ by an interpolation between values for the gas phase to ones for the adsorbate:

$`\alpha _{HH}(Z)`$ $`=`$ $`\alpha _{HH}^{ad}forZZ_e`$
$`\alpha _{HH}(Z)`$ $`=`$ $`\alpha _{HH}^g(\alpha _{HH}^g\alpha _{HH}^{ad})\mathrm{\Gamma }_4(Z,Z_e,2b_{HM})forZ>Z_e`$ (6)
and

$$r_{HH}^e(Z)=r_e^g(r_e^gr_e^{ad})\mathrm{\Gamma }_4(Z,Z_e,2b_{HM}).$$
(7)
The superscripts $`g`$ and $`ad`$ indicate the gas phase and the adsorbed state. Table 1 gives the parameters used for the PES for a Cu(111)-surface covered by a hydrogen atom adsorbed on the hollow site.

#### II.1.2 Surface interactions

In the product channel a molecule (YH) is formed and eventually transferred to the gas phase. The molecule is coupled to the surface by a weak bond induced by the polarization forces. The interaction potential, $`V_{YHM}^P`$, is represented as a sum of two terms - a short range repulsive term and a weak long-range attraction between the molecule and the surface

$$V_{YHM}^P=A_Me^{(b_MZ)}\frac{C_M}{Z^3}(1\mathrm{\Gamma }_4(Z,0,2b_M)).$$
(8)
The incomplete Gamma function which turns off the attraction as the Y-atom approaches the surface is given by:

$$\mathrm{\Gamma }_m(x,x_0,a)=\underset{k=0}{\overset{k=m}{}}\frac{a(xx_0)^k}{k!}e^{(a(xx_0))}.$$
(9)
The parameterization of the physisorption of the molecular interaction with the surface has been chosen such that the minimum energy e.g. the physisorption energy is observed at $`Z_e`$$`=`$$`(r_{HM}^e+m_yr_{YH}^e)/M`$. The location of the minimum energy is moved further away from the surface as the mass of the impinging atom increases. As Y becomes heavier, the polarization force between the surface and the alkali atom increases, thereby the binding energy of the physisorption bond becomes stronger. The amplitudes of the repulsion, $`A_M`$ and attraction, $`C_M`$ increase as one proceeds down the list of atoms, $`\{`$H,Li,Na,K,Rb,Cs$`\}`$. The coupling strength, $`b_M`$, is inversely proportional to $`Z_e`$. The parameters are constructed so that the physisorption energy of YH increases slightly as one proceeds down the list of atoms $`\{`$H,Li,Na,K,Rb,Cs$`\}`$. The physisorption potentials are shown in Figure 1 and the parameters are given in Table 1.

To model the interaction between the impinging atom in the reactant channel a physisorption potential has been used. The same set of parameters for the atomic interaction as for the molecular physisorption interactions have been chosen but the coordinate, $`Z`$, in Eq.(8) is replaced by the location of the impinging atom, $`z_y`$.

In the reactant channel the interaction between the chemisorbed atom and the surface is described by a Morse potential

$$V_{HM}^R=D_{HM}([1e^{(\alpha _{HM}(z_hz_{HM}^e))}]^21),$$
(10)
where $`D_{HM}`$ is the dissociation energy of the atom-metal bond and $`z_{HM}^e`$ is the equilibrium bond length. The parameters are given in Table 1 for a hydrogen atom adsorbed at the hollow site of a Cu(111)-surface.

### II.2 Wave function of the atomic pulse

Initially, when the impinging atom is far away from the surface and the adsorbed atom, the wave function representing the outcome of the total system is written as a product of a wave function on each atom,

$$\mathrm{\Psi }_{atom}(r,Z)=N\psi _h(z_h,z_y=z_s)\psi _y(z_y)e^{ik_yz_y};\psi _y(z_y)=e^{(z_yz_s)^2/\sigma _y}$$
(11)
where $`N`$ is a normalization factor. The wave function of the adsorbed atom, $`\psi _h`$, was chosen as the lowest energy eigenstate of the PES of the reactant channel along the one-dimensional path with a fixed distance, $`z_s`$, between the approaching atom and the surface. Considering only the lowest vibrational states would be sufficient since in a given experimental situation one would expect that the temperature of the surface is ultracold. The wave function of the approaching atom, $`\psi _y`$, is represented by a Gaussian wave function centered at $`z_y=z_s`$ and with a variance, $`\sigma _y`$. The momentum of the approaching atom is denoted by $`k_y=\pm \sqrt{2m_yE/\mathrm{}^2}`$ which is related to the energy $`E`$ of the propagating atom laser. The sign of the momentum operator determines the orientation of the atom laser: For negative momentum, the atom moves toward the surface. The variance is related to the dispersion of the atom laser.

## III 2PACC Dynamics

The 2PACC spectroscopy of an Eley-Rideal reaction consists of the dynamics on the coupled reactant and product potential energy surfaces. The wave function of the system is described by the vector

$$𝚿(r,Z,t)=\left(\begin{array}{c}𝚿_R(r,Z,t)\\ 𝚿_P(r,Z,t)\end{array}\right),$$
(12)
where the wave functions in the reactant and product channels are denoted by the index $`\{R,P\}`$. The Hamiltonian of the system is represented by

$`𝑯(r,Z)`$ $`=`$ $`𝑻(r,Z)+𝑽(r,Z)`$ (17)
$`=`$ $`\left[\begin{array}{c}𝑻_{RR}(r,Z)\mathbf{\hspace{0.33em}\hspace{0.33em}\hspace{0.33em}\hspace{0.33em}\hspace{0.33em}\hspace{0.33em}\hspace{0.33em}\hspace{0.33em}\hspace{0.33em}\hspace{0.33em}\hspace{0.33em}\hspace{0.33em}\hspace{0.33em}0}\\ \mathbf{\hspace{0.33em}\hspace{0.33em}\hspace{0.33em}\hspace{0.33em}0}𝑻_{PP}(r,Z)\end{array}\right]+\left[\begin{array}{c}𝑽_{RR}(r,Z)𝑽_{RP}(r,Z)\\ 𝑽_{PR}(r,Z)𝑽_{PP}(r,Z)\end{array}\right].`$
The diagonal elements of the Hamiltonian have the following form

$$𝑯_{ii}(r,Z)=𝑻_{ii}(r,Z)+𝑽_{ii}(r,Z)=\frac{\mathrm{}^2}{2M}\frac{^2}{Z^2}\frac{\mathrm{}^2}{2\mu }\frac{^2}{r^2}+𝑽_{ii}(r,Z)i=\{R,P\}$$
(18)
where the first two terms are the kinetic energy operator for the two degrees of freedoms ($`r`$ and $`Z`$) and the last term is the potential energy function which was described in Section II.1. The off-diagonal elements of the Hamiltonian represent the non-adiabatic coupling between the two channels which are described by

$$𝑽_{RP}(r,Z)=𝑽_{PR}(r,Z)=e^{(rr_{YH}^e)^2}e^{\beta Z},$$
(19)
where $`\beta `$ is the non-adiabatic coupling strength and $`r_{YH}^e`$ is the equilibrium distance between the two atoms in the singlet molecular PES. This representation ensures that the electron density of the metal decays exponentially outside the surface into the vacuum. It is important to note that the adiabatic PES of the Eley-Rideal reaction which have been used by Jackson et al.Sha et al. (2002); Jackson and Lemoine (2001); Shalashilin et al. (1999); Jackson and Persson (1992) can be obtained by diagonalization of this 2$`\times `$2 $`𝑽`$-matrix.

The dynamics of the 2PACC was followed by solving the time-dependent two-channel Schrödinger equation which is given by

$$i\mathrm{}\frac{𝚿}{t}=𝑯𝚿.$$
(20)
In the two-pulse atomic coherent control (2PACC) spectroscopy the first atom laser represented by the wave packet (Eq.(11)) is initialized at the reactant PES at a time $`t=0`$ e.g

$$𝚿(r,Z,0)=\left(\begin{array}{c}\mathrm{\Psi }_{atom}(r,Z)\\ 0\end{array}\right).$$
(21)
This initial wave packet evolves in time and after a time delay, $`\mathrm{\Delta }t`$, the second atom pulse is introduced given by

$$\mathrm{\Psi }_{atom,2}(r,Z)=\mathrm{\Psi }_{atom}(r,Z)\mathrm{exp}(i\theta )$$
(22)
where $`\theta [\pi ;\pi ]`$ is the relative phase between the two atomic pulses that describes the coherence between them. As the wave packet propagates population is transferred from the reactant to the product PES through the non-adiabatic coupling.

### III.1 Computational Method

The wave function is represented on a two-dimensional grid. First, the wave function of the chemisorbed hydrogen was calculated. Using an imaginary time propagationKosloff and Tal-Ezer (1986) the one-dimensional wave function of the hydrogen atom, $`\psi _H`$ along the line with a fixed distance between the approaching atom and the surface, $`z_y`$$`=`$6.8Å has been relaxed to its vibrational ground state. Representing the wave function of the impinging atom as a Gaussian wave function, the total wave packet Eq.(11) is then initialized.

The dynamics of the 2PACC is obtained by propagating the initial wave function by $`\mathrm{exp}(i𝑯t)\psi (0)`$, in which the time-evolution operator $`\mathrm{exp}(i𝑯t)`$ is expanded by Newtonian interpolation polynomials with Chebychev sampling pointsKosloff (1994). The kinetic energy operator has been evaluated using the fast Fourier transformation techniqueKosloff (1988, 1994). The parameters used in the wave packet propagation are displayed in Table 2.

The scattered wave function is removed at large values of $`r`$ and $`Z`$ by complex absorbing potentialsVibok and Balint-Kurti (1992) which prevent reflection and transmission at the end of the grid. The overall potential can be written as

$`V(r,Z)`$ $`=`$ $`V(r,Z)+V_{abs}(r)+V_{abs}(Z)ifr\mathrm{\Delta }_rrr_{max}andZ\mathrm{\Delta }_ZZZ_{max}`$ (23)
$`=`$ $`V(r,Z)+V_{abs}(r)ifr\mathrm{\Delta }_rrr_{max}andZZ\mathrm{\Delta }_Z`$
$`=`$ $`V(r,Z)+V_{abs}(Z)ifrr\mathrm{\Delta }_randZ\mathrm{\Delta }_ZZZ_{max}`$
$`=`$ $`V(r,Z)ifrr\mathrm{\Delta }_randZZ\mathrm{\Delta }_Z`$
where the complex potential is given by $`V_{abs}(r)=iv_0(r(r_{max}\mathrm{\Delta }_r))^2`$. The same functional form is used for $`Z`$. $`r_{max}`$ is the last grid point and $`\mathrm{\Delta }_r`$ is the interval where the complex potential is applied.

As the wave function is evolving from the entry/reactant channel, the non-adiabatic coupling term is responsible for transferring the amplitude between the two diabatic surfaces. Eventually the molecule desorbs from the metal surface. This leads to an outgoing flux in the exit/product channel. The probability of a YH-molecule to escape from the metal surface is obtained via a flux-resolved analysis carried out at an asymptotic value of $`Z`$$`=`$$`Z_{flux}`$$`=`$5.24Å. The total accumulated desorbing flux which is the predicted 2PACC signal is computed by

$`F`$ $`=`$ $`{\displaystyle \underset{i}{\overset{N_t}{}}}J(t_i)\delta t`$
$`=`$ $`{\displaystyle \frac{\delta t}{M}}{\displaystyle \underset{i}{\overset{N_t}{}}}Im\left[{\displaystyle 𝑑r𝚿_P^{}(r,Z_{flux},t_i)\frac{𝚿_P(r,Z,t_i)}{Z}}|_{Z=Z_{flux}}\right],`$
where the derivative is evaluated with a Fourier Transform. The integrated flux has been determined as a function of the time delay, $`\mathrm{\Delta }t`$, and the phase-relation, $`\theta `$, between the two atom laser pulses.

Furthermore, the accumulated flux current can be evaluated for each of the vibrational states along the dividing line

$`P_n`$ $`=`$ $`{\displaystyle \underset{i}{\overset{N_t}{}}}j_n(t_i)\delta t`$
$`=`$ $`{\displaystyle \frac{\delta t}{M}}{\displaystyle \underset{i}{\overset{N_t}{}}}Im\left[𝚿_n^{}(Z_{flux},t){\displaystyle \frac{𝚿_n(Z,t)}{Z}}|_{Z=Z_{flux}}\right],`$
where $`j_n`$ is the probability current for the wave packet to go into the n’th vibrational state.

Here, $`𝚿_n(Z,t)`$ is the projection of the wave function onto the vibrational eigenstates, $`\chi _n`$, along the dividing line

$$𝚿_n(Z,t)=𝑑r\chi _n^{}(r)𝚿_P(r,Z,t).$$
(26)
The vibrational eigenstatates have been calculated by imaginary time propagation. (See Appendix A for further details).

## IV Results and Discussion

The 2PACC of a hydrogen source is compared to that of a lithium atom laser source impinging on a surface with chemisorbed hydrogen atoms. The evolution of the wave packet on the reactant and the product channel are presented. The 2PACC signal and the vibrational analysis of the desorbing molecule are displayed. The control parameters are the time delay and relative phase between the two atom laser pulses.

### IV.1 H+H/Cu(111)

The dynamics of the 2PACC spectroscopy are demonstrated for a hydrogen atom laser source impinging on a Cu(111)-surface coated with hydrogen atoms. Compared to earlier calculationsJørgensen and Kosloff (2003, 2002) the grid spacing in both degrees of freedom ($`r`$,$`Z`$) was reduced by a factor of 2. The initial starting position of the wave function was $`z_s`$$`=`$6.8Å compared to 13.6Å in the earlier calculations. At the shorter distance the interactions between the impinging atom and the adsorbate and the surface is still negligible.

In Figures 2 and 3 snapshots of the evolution of the wave packet on the reactant and the product surfaces are shown for $`\theta `$$`=`$$`\frac{1}{2}\pi `$ and $`\mathrm{\Delta }t`$$`=`$4.84fs. First, the initial wave packet (Eq.(11)) is generated and this atom laser pulse evolves in time. The energy of the initial wave packet is -2.3 eV and the impinging atom has a kinetic energy of 0.2 eV. After the specified time delay a wave packet - the second atom laser pulse - is placed in the original position of the first wave-packet (see second snapshot of Figure 2). The relative phase between the two wave packets at the initial position may be different e.g. $`\theta 0`$. The wave function which resembles the two atom laser pulses propagates toward the non-adiabatic region where the reactant and the product surfaces intersect. As the wave packet enters the non-adiabatic region a part of the wave function is transferred to the molecular state where it can exit. This means that the approaching hydrogen atom has reacted with the adsorbed hydrogen and a H2 molecule is formed. The non-reactive part of the wave function collides with the adsorbed hydrogen atoms. Either it scatters back to the gas phase or it gets trapped on the surface due to the weak polarization forces between the impinging atom and the surface (physisorption).

The population which is transferred through the non-adiabatic coupling to the product channel builds up slowly as a function of time. In the beginning the newly formed hydrogen molecule is physisorbed on the surface. That is, it is trapped in the potential well. Later a fraction of the wave function exits the channel and the hydrogen molecule desorbs from the surface to be detected in the gas phase. The desorbing molecule is vibrationally excited. The node structure of the exiting wave function shows that the hydrogen molecule desorbs in the fifth vibrational state ($`\nu `$$`=`$4). This observation will be verified by a vibrational analysis.

The 2PACC signal, which is the difference between a one pulse and a two pulse desorbed molecular outcome is calculated from the total integrated flux at $`t=484`$ fs. Figure 4 shows the 2PACC signal as a function of time delay and relative phase between the two pulses. The amount of control of the 2PACC signal demonstrated in this model is an enhancement of 350 $`\%`$ for $`\theta `$$`=`$-$`\frac{1}{2}\pi `$ and $`\mathrm{\Delta }t`$$`=`$4.84 fs relative to one atomic pulse compared with a suppression of 95% at $`\theta `$$`=`$$`\pi `$ and $`\mathrm{\Delta }t`$$`=`$9.7 fs.

The 2PACC signal shows a variation with respect to both control parameters, meaning that the outcome of the Eley-Rideal reaction is coherently controlled by the time delay and the relative phase between the two atomic pulses. The application of the second pulse creates a quantum interference with the first pulse. Such interferences are either constructive or destructive resulting in increasing or decreasing the flux of the desorbing molecules in the product channel. The effect of these interferences can be visualized by considering the wave function just after the second atom pulse has been applied. In Figure 5 the total wave packet is shown for $`t`$$`=`$$`\mathrm{\Delta }t`$$`=`$14.5fs for different relative phases between the two atom laser pulses. An elongated structure of the wave packet immediately after the second pulse gives rise to destructive interference and decrease of the desorption yield whereas a ”node-like” structure gives rise to constructive interference and an enhancement of the yield.

In Figure 6 the accumulated flux in each vibrational state of desorbing hydrogen molecule is shown for a one pulse experiment. The hydrogen molecule leaves the surface predominantly in the fifth lowest vibrational excited state ($`\nu `$$`=`$4). This observation agrees with the node structure of the leaving wave function on the product channel (See Figure 3). Jackson et alJackson and Persson (1992) also observed a vibrational distribution of desorbing hydrogen molecules centered around $`\nu `$$`=`$4 for an Eley-Rideal reaction of two hydrogen atoms on a Cu(111)-surface in a collinear quantum mechanical calculation.

The extent of control in the accumulated vibrational flux between the two and one pulse scenario is shown in Figure 7. For all the calculations the vibrational distribution is centered around $`\nu `$$`=`$4. An enhancement of flux in the lowest vibrational states of the hydrogen molecule ($`\nu `$$``$3) is correlated with an increases of the total 2PACC yield. On the other hand an enhancement of the higher lying vibrational states ($`\nu `$$``$4) is anticorrelated with the total 2PACC yield.

### IV.2 Li+H/Cu(111)

Next, the lithium with an adsorb hydrogen Eley-Rideal reaction on a Cu(111)-surface is studied. A smaller probability of desorption for lithium hydride molecule is expected. This is due to the reduced energy difference between the product and the reactant and a stronger physisorption interaction between the surface and the lithium hydride. For a single matter-wave pulse, the desorbing flux of lithium hydride is suppressed by $`10^9`$ compared to desorption of hydrogen. The total energy of the initial wave packet is -2.4 eV where the initial kinetic energy of the impinging atom is 0.027 eV.

The evolution of the wave packet on the reactant and the product PES is shown in Figures 8 and 9. The dynamics of the 2PACC spectroscopy with a lithium atom laser is slower than the one for a hydrogen atom laser since the mass of the impinging atom increases by almost a factor of 7. As the wave packet on the reactant channel approaches the metal surface, part of the population is transferred to the product channel. The magnitude of population transfer is much smaller for lithium than for hydrogen as expected. The part of wave packet on the reactant channel which does not react is primarily trapped on the surface due to polarization forces and only a very small part of the wave function scatters back to the gas phase. The opposite was observed for the hydrogen case.

The predicted 2PACC signal is shown in Figure 10 as a function of time delay and phase between the two pulses. For certain values of time delay and phase between the two pulses the second pulse induces a large constructive interferences. These interferences enhance the probability of desorption for LiH by 2100$`\%`$ relative to a single-pulse experiment.

The desorbing molecule, LiH, is vibrationally excited. This is because the bond length LiH is considerably longer than chemisorption bond between the hydrogen and the Cu(111)-surface. Along the dividing line where the desorbing flux is collected, the fourteen lowest vibrational eigenstates of the lithium hydride have been evaluated. For a single pulse experiment (See Figure 6) a broad distribution of the vibrational states with a maximum at $`\nu `$$`=`$8 is observed. In Figure 11 the enhancement/suppression in the integrated vibrational flux relative to the single-pulse scenario is shown. The deviation in the integrated flux as a function of the phase reflects the 2PACC signal. If there is a large enhancement of the 2PACC signal the accumulated flux in each vibrational state increases.

## V Summary and Conclusions

A two-pulse atomic coherent control (2PACC) spectroscopy has been presented in this study. The coherent properties of an atom laser have been used to control a surface mediated chemical reaction, $`A+BC`$, where the $`A`$ wave function is generated from an atom laser and the target atom $`B`$ is immobilized by the surface. Two atom laser pulses are applied creating an interference pattern with each other. These interferences are the essence of the coherent control of the chemical reaction. The two pulses are necessary since the initial relative phase between the atom $`A`$ and atom $`B`$ on the surface is arbitraryBrumer and Shapiro (1992, 1986). The control knobs used were the time delay and a relative phase between two atom laser pulses. A significant enhancement of the 2PACC signal relative to single atom laser pulse was obtained.

The Eley-Rideal reaction forming H2 is highly exothermic whereas the recombination reaction leading to LiH is almost thermoneutral. Using a coherent matter-wave source enables us to coherently control the recombination reaction. The 2PACC spectroscopy opens up reaction channels which are almost closed to incoherent sources. The reaction yield by Eley-Rideal reaction of lithium atom laser with adsorbed hydrogen atom has been enhanced by more than 2100$`\%`$ compared to a one-pulse reference. Here, we manipulated the wave function of one atom transferred from a trapped state in the BEC to an untrapped and propagating state. The coherent properties of interest are projected onto this wave function. In this study a double Gaussians wave function was used where the source of coherent control is the time delay and relative phase between the two Gaussian wave functions. The design of the output coupler is the experimental ”bottleneck” in coherent control with matter-waves. In analogy with the optical pulse shaperWeiner et al. (1988); Nelson et al. (1991), a more elaborated matter-wave pulse shaper controlling the amplitude and phase of the matter-wave would eventually lead to a reaction probability of one.

The design of the wave function could further be used to direct the leaving molecule into a specific rovibrational state. The 2PACC spectroscopy could also be employed for endothermic reaction such as Eley-Rideal reaction between a adsorbed hydrogen atom and sodium (rubidium, cesium).

Additional coherent manipulations could be possible if the atomic matter-wave pulse is replaced by a molecular pulse where the source is a molecular Bose-Einstein condensate. For a heterogeneous molecular matter-wave the branching ratio between the two reaction channels could be controlled. From the prospective of coherent control methodology the current study demonstrates control of a recombination reaction. This is in contrast to optical coherent control which has been almost exclusively limited to the control of unimolecular reactions such as photo-dissociation.

Control of a recombination reaction is another direction where both atoms come from the same BEC source. In this case their initial relative phase is well defined while the surface serves to break the symmetry. Since both sources are the coherent the reaction product is also coherent. The ultimate goal is to design the wave functions of the atom lasers such that the reaction probability is unity for one specific rovibrational states of the product. This would lead to the formation of a stable molecular BEC. Control on these lines is under investigation.

###### Acknowledgements.

We would like to thank Christiane Koch for proofreading the manuscript. SJ thanks Marie Curie Fellowship Organization. This work was supported by the Israel Science Foundation and the European Research and Training Network Cold Molecules: Formation, Trapping and Dynamics. The Fritz Haber Center is supported by the Minerva Gesellschaft für die Forschung, GmbH München, Germany.

## Appendix A Vibrational Eigenstates

Vibrational eigenstates, $`\chi _n`$, are solutions of the one-dimensional, one channel time-independent Schrödinger equation for a fixed distance, $`Z_{flux}`$, from the surface

$$𝑯_{PP}(r;Z_{flux})\chi _n(r;Z_{flux})=E_n(Z_{flux})\chi _n(r;Z_{flux}).$$
(27)
Asymptotically when $`Z_{flux}\mathrm{}`$, the eigenstates represent the vibrational states of the diatomic molecule in the gas phase. The method for evaluating the eigenfunction is based on propagating a trial wave function according to the time dependent Schrödinger equation in imaginary time $`\tau =it`$. A Gaussian filterHammerich et al. (1989) has been used to project the eigenstates out in an energy region around an initial guess, $`ϵ`$,

$$\chi _{trial}(r,\tau )=e^{4(𝑯ϵ)^2\tau /\mathrm{}\mathrm{\Delta }E}\chi _{trial}(r,0).$$
(28)
The parameter $`\tau `$ has the dimension of time while $`\mathrm{\Delta }E`$ is the energy range covered by the numerical procedure which appears as a scaling factor for the normalization of the Hamiltonian in the Newtonian time propagation. This procedure can be interpreted as a relaxation of the ground stated of a modified Hamiltonian $`𝑯^{}=4(𝑯ϵ)^2/\mathrm{\Delta }E`$. Convergence onto a specific target eigenstate can be estimated from the energy dispersion relation

$$D(\tau )=\sqrt{\chi (\tau )𝑯^2\chi (\tau )\chi (\tau )𝑯\chi (\tau )^2}$$
(29)
which decreases uniformly by increasing the ”purity” of an eigenfunction and vanishes in the limit of an exact eigenstate. If the energy dispersion, $`D(\tau )`$ is less than 1.0E-6 the propagation is stopped and the wave function is a vibrational eigenstate of the diatomic molecule, $`\chi _n`$ for a fixed distance to the surface.


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# On singular connections and geometrically atomic maps

## 1. Singular connections

Let us recall some basic facts about the Harvey-Lawson theory of singular connections, see \[HL1\]111See also \[HL2\]-\[HL4\], \[N\] and \[Z\]. We consider a smooth bundle map $`\alpha :EF`$ between complex vector bundles with connections $`D^E`$ and $`D^F`$ correspondingly over the same manifold $`X`$. We denote by $`\nu =dim(X)`$, for a point $`x`$ of $`X`$ the fibers over $`x`$ are $`E_x`$ and $`F_x`$, $`\alpha _x:E_xF_x`$ is the restriction of $`\alpha `$ to these fibers, while $`m`$ and $`n`$ denote complex dimensions of these fibers.

For the Chern-Weil characteristic forms $`\mathrm{\Phi }(\mathrm{\Omega })`$ of $`(E,D^E)`$ and $`(F,D^F)`$ and the class of ”geometrically atomic” maps $`\alpha `$ the authors in \[HL1\] establish a canonical co-homology

$$\mathrm{\Phi }(\mathrm{\Omega })\underset{k0}{}Res_{\mathrm{\Phi },k}[\mathrm{\Sigma }_k(\alpha )]=dT,$$
$`1.1`$
where $`\mathrm{\Sigma }_k(\alpha )=\{xX:dimker(\alpha )=k\}`$, $`Res_{\mathrm{\Phi },k}`$ is a smooth residue form along $`\mathrm{\Sigma }_k(\alpha )`$, and $`T`$ is a canonical $`L_{loc}^1`$-form on $`X`$. When $`m=n`$ the last formula can be written

$$\mathrm{\Phi }(\mathrm{\Omega }^F)\mathrm{\Phi }(\mathrm{\Omega }^E)=\underset{k>0}{}Res_{\mathrm{\Phi },k}[\mathrm{\Sigma }_k(\alpha )]=dT.$$
$`1.2`$
A bundle morphism $`\alpha :EF`$ can be considered as a cross-section of the vector bundle $`\pi :Hom(E,F)X`$. Denote by $`\beta :\pi ^{}E\pi ^{}F`$ a tautological morphism between bundles $`\pi ^{}E`$ and $`\pi ^{}F`$ over the total space of the bundle $`Hom(E,F)`$ (which at $`AHom(E,F)`$ is given by itself). There is a natural compactification $`Hom(E,F)G`$ where $`\pi :GG_m(EF)X`$ is the Grassmann bundle of complex m-planes in $`EF`$ while we assign to $`A:E_xF_x`$ its graph $`V_A`$ in $`E_xF_x`$.

The key object in the construction of the co-cycle $`T`$ is the following multiplicative flow $`\varphi _t:EFEF`$ defined by $`\varphi _t(e,f)=(te,f)`$ for $`0<t<\mathrm{}`$. If $`P^1(R)=R\{\mathrm{}\}`$ is the projective line, $`G^2`$ the fibre product of $`G`$ with itself over $`X`$ then

$$𝒯=\{(t,\varphi _t(V),V)P^1(R)\times G^2|0<t<\mathrm{}\text{ and }VG\}$$
$`1.3`$
is called the total graph of the flow. Denote by \[$`𝒯`$\] the current given by integration over $`𝒯`$ and define $`T=pr_{}[𝒯]`$ where $`pr:P^1(R)\times G^2G^2`$ is the projection.

As the authors wrote in \[HL4\] the main observation they had made was the following statement.

###### Theorem~1. (see Proposition 3.1 in \[HL4\])

$`𝒯`$ is a sub-manifold of finite volume in $`P^1(R)\times G^2`$ over each compact subset of $`X`$.222It was concluded from the real analyticity of the multiplicative flow with the help of general results from a geometric measure theory, see \[F\].

The theory of singular connections was developed for a class of so called geometrically atomic bundle maps. The bundle map $`\alpha :EF`$ is called geometrically atomic if the subset

$$T_\alpha =\{(\frac{1}{t}\alpha _x,\alpha _x)G^2|xX,0<t<\mathrm{}\}$$
$`1.4`$
has locally finite $`(\nu +1)`$-dimensional measure in $`G^2`$ (recall that $`\nu =dim(X)`$).

The set $`T_\alpha `$ can be divided into two sets: the set $`T_\alpha ^s`$ consisting of points where $`\alpha `$ has zeros and therefore having locally finite $`\nu `$-dimensional measure; and the set $`T_\alpha ^r`$ which is a line bundle over the set $`X\backslash \text{Zero}(\alpha )`$. This last set is an open subset of $`X`$ while $`T_\alpha ^r`$ is a smooth sub-manifold which fibers over $`X\backslash \text{Zero}(\alpha )`$ with a fiber equals the trajectory $`(\frac{1}{t}\alpha _x,\alpha _x)`$ of $`\alpha _x`$ under the multiplicative flow. Therefore, by Fubini theorem the sub-manifold $`T_\alpha ^r`$ has locally finite $`(\nu +1)`$-dimensional measure if all these fibers $`\{\varphi _t(\alpha _x),0<t<\mathrm{}\}`$ have uniformly bounded length considered as curves in Grassmann manifolds $`G_x^2`$. In this note we prove this uniform boundedness of lengths of such curves in Grassmannians, see Theorem 3 below. This will imply our main result as follows.

###### Theorem~2

All bundle maps $`\alpha :EF`$ are geometrically atomic.

## 2. Linear curves of subspaces in Grassmannians

Denote $`p=2m`$, $`q=2n`$. Then every $`G_x^2`$ is $`G_{p+q}^p`$ \- the Grassmann manifold of all $`p`$-dimensional subspaces of the $`(p+q)`$-dimensional Euclidean space. We consider $`G_{p+q}^p`$ with a natural Riemannian metric $`g`$ such that the factorization $`\mathrm{\Pi }:O(p+q)O(p+q)/O(p)\times O(q)=G_{p+q}^p`$, where the orthogonal group $`O(p+q)`$ is provided with the Lipcshitz-Killing metric, is a Riemannian submersion.

We say that a curve $`V(t),0tT`$ in $`G_{p+q}^p`$ of $`p`$-subspaces is linear if the subspaces $`V(t)`$ are generated by some vectors $`e_i(t),i=1,\mathrm{},k`$ linearly depending on $`t`$, i.e., such that

$$e_i(t)=e_i+td_i.$$
$`2.1`$
In our case of the trajectories of the multiplicative flow are the following linear curves:

$$V(t)=\varphi _t(V_A)=(\frac{1}{t}\alpha _x,\alpha _x)$$

where the $`p`$-subspace $`V_A`$ is the graph of the map $`A=\alpha _x`$. If $`\{e_i,1ip\}`$ is some base of the first factor $`R^p`$ of $`R^{p+q}=R^p\times R^q`$ (where $`p=2m`$, $`q=2n`$) then $`V(1)=V_A`$ and is generated by $`e_i+Ae_i`$, while $`V(t)`$ is generated by the vectors

$$e_i(t)=e_i+tAe_i.$$
$`2.2`$
Denote $`d_i=Ae_i`$ and call these vectors derivatives.

As we said above our main technical result is:

###### Theorem~3

The lengths of all linear curves $`V(t)`$ in a Grassmann manifold $`G_{p+q}^p`$ are uniformly bounded.

###### Demonstration Proof

First we verify that geodesic curvatures of linear curves are uniformly bounded. Consider the point $`V(t_0)`$ on the linear curve $`V(t)`$ and estimate its geodesic curvature at this point. We split the space $`R^{p+q}`$ as $`R^{p+q}=R^p\times R^q`$ where the first factor $`R^p`$ of $`R^{p+q}=R^p\times R^q`$ coincide with $`V(t_0)`$ and will be called the vertical subspace and its vectors - vertical, the second factor $`R^q`$ of $`R^{p+q}=R^p\times R^q`$ which is orthogonal to the first one we call the horizontal subspace and its vectors - horizontal vectors. Vertical and horizontal components of the vector $`v`$ will be denoted below as $`𝒱v`$ and $`v`$ correspondingly.

Changing $`t`$ to $`(tt_0)`$ if necessary in (2.2) we assume from now on that $`t_0=0`$ and denote $`V(0)=V`$. In return the derivatives $`d_i`$ in a representation

$$V(t)=\{e_i(t)=e_i+td_i|1ip\}$$
$`2.2`$
may be no longer horizontal vectors as before. Continue the correspondence $`e_i𝒱d_i`$ to the linear map $`𝒱D:VV`$ and take its polar representation $`𝒱D=BU`$ where $`U:VV`$ is some orthogonal map $`U=(u_i^s)`$ from $`O(p)`$, and $`B`$ a diagonal in some orthonormal base.333$`B`$ can be assumed to be positive, see the construction in the Lemma 3 below of the partition $`\{\mathrm{}<t_1<\mathrm{}<t_m<\mathrm{}\}`$. The pre-image of this base under transformation $`U`$ we denote by $`\{e_1,\mathrm{},e_p\}`$ of $`V`$. Complete this base to some orthonormal base $`\{e_1,\mathrm{},e_p,e_{p+1},\mathrm{},e_{p+q}\}`$ of $`R^{p+q}`$ and continue the linear map $`D:VR^{p+q}`$ sending $`e_i`$ to $`d_i`$ to the map $`D:R^{p+q}R^{p+q}`$ given by a matrix

$$D=\left(\begin{array}{cc}B& (D)\\ (D)^{}& I\end{array}\right)\left(\begin{array}{cc}U& 0\\ 0& I\end{array}\right).$$
$`2.3`$
Now we see that the linear curve $`V(t)`$ is the image of the subspace generated by the first $`p`$ coordinate vectors of the orthonormal base $`\{e_1,\mathrm{},e_p,e_{p+1},\mathrm{},e_{p+q}\}`$ in $`R^{p+q}`$ under the map with the following matrix:

$$\left(\begin{array}{cc}I+t(𝒱D)& t(D)\\ t(D)^{}& I\end{array}\right)\left(\begin{array}{cc}U& 0\\ 0& I\end{array}\right).$$
$`2.4`$
where $`𝒱D=BU`$ and $`D`$ are the matrices of vertical and horizontal components of the derivatives $`d_i`$ correspondingly: $`𝒱D=(d_i)^j,i=1,\mathrm{},p;j=1,\mathrm{},p`$ and $`D=(d_i)^j,i=1,\mathrm{},p;j=p+1,\mathrm{},p+q`$.

Next we define another and ”nearly” orthogonal transformation of $`R^{p+q}`$ mapping $`V`$ into $`V(t)`$. First we divide every vector $`e_i,1ip`$ by its norm after $`I+tBU`$, i.e., by $`(1+t\lambda _i)`$. We denote this map $`C(t)=diag((1+t\lambda _1)^1,\mathrm{}(1+t\lambda _p)^1)`$. Its composition with the map given by (2.4)

$$\left(\begin{array}{cc}I+t(𝒱D)& t(D)\\ t(D)^{}& I\end{array}\right)\left(\begin{array}{cc}U& 0\\ 0& I\end{array}\right)\left(\begin{array}{cc}C(t)& 0\\ 0& I\end{array}\right)$$
$`2.5`$
also send $`V`$ onto $`V(t)`$. By a direct calculation it is easy to see that this last map is given in the orthonormal base $`\{e_i,1ip+q\}`$ by the matrix

$$A(t)=\left(\begin{array}{cc}\stackrel{~}{U}& t\stackrel{~}{D}\\ t\stackrel{~}{D}^{}& I\end{array}\right)$$
$`2.6`$
where $`\stackrel{~}{U}`$ is some orthogonal matrix and for the components of $`\stackrel{~}{D}=(\stackrel{~}{d}_i^j),1ip,p+1jp+q`$ it holds that

$$\stackrel{~}{d}_i^j=(1+t\lambda _i)^1u_i^sd_s^j.$$
$`2.7`$
Another calculation shows that the vectors $`\stackrel{~}{e}_i(t)=A(t)e_i,1ip+q`$ are ”nearly” orthonormal:

$$|(\stackrel{~}{e}_i(t),\stackrel{~}{e}_j(t))\delta _{ij}|t^2\stackrel{~}{D}^2,$$
$`2.8`$
where

$$\stackrel{~}{D}^2=\underset{i=1,\mathrm{},k;j=k+1,\mathrm{},n}{}((\stackrel{~}{d}_i)^j)^2.$$
$`2.9`$
For small $`t`$ it holds $`(1+t\lambda _i)^11+t\mathrm{\Lambda }_1`$ for $`\mathrm{\Lambda }_1=2max\{\lambda _i|1ip\}`$. Therefore, from (2.7) we see

$$\stackrel{~}{D}^2(1+t\mathrm{\Lambda }_1)D^2,$$
$`2.10`$
or

$$|(\stackrel{~}{e}_i(t),\stackrel{~}{e}_j(t))\delta _{ij}|t^2(1+t\mathrm{\Lambda }_1)D^2,$$
$`2.11`$
where

$$D^2=\underset{i=1,\mathrm{},k;j=k+1,\mathrm{},n}{}((d_i)^j)^2.$$
$`2.12`$
Now we apply inductively to $`\{\stackrel{~}{e}_i(t),i=1,\mathrm{}p+q\}`$ an orthogonalization process as follows. Denote $`W_1(t)`$ the subspace generated by all $`\{\stackrel{~}{e}_i(t),i<p+q\}`$ and find $`\overline{e}_{p+q}(t)`$ unit and normal to it. From (2.11) it follows that

$$\stackrel{~}{e}_{p+q}(t)\overline{e}_{p+q}(t)t^2(1+t\mathrm{\Lambda }_1^1)D^2$$
$`2.13`$
for some $`\mathrm{\Lambda }_1^1`$ depending on $`\mathrm{\Lambda }_1`$. Next find $`\overline{e}_{p+q1}(t)`$ in $`W_1(t)`$ which is unit and normal to the subspace $`W_2(t)`$ generated by all $`\{\stackrel{~}{e}_i(t),i<p+q1\}`$. Again from (2.11) and (2.13) we get

$$\stackrel{~}{e}_{p+q1}(t)\overline{e}_{p+q1}(t)t^2(1+t\mathrm{\Lambda }_1^2)D^2$$
$`2.14`$
for some $`\mathrm{\Lambda }_1^2`$ depending on $`\mathrm{\Lambda }_1`$ and $`\mathrm{\Lambda }_1^1`$. And so on. Finely we construct the orthonormal base $`\{\overline{e}_i(t),i=1,\mathrm{}p+q\}`$ of $`R^{p+q}`$ such that

$$\stackrel{~}{e}_i(t)\overline{e}_i(t)(1+t\mathrm{\Lambda }_2)t^2D^2$$
$`2.15`$
where the constant $`\mathrm{\Lambda }_2`$ again depends only on $`\mathrm{\Lambda }_1`$ and the dimension $`(p+q)`$. By construction the first $`p`$ vectors of $`\{\overline{e}_i(t),i=1,\mathrm{}n\}`$ generate $`V(t)`$, or $`V(t)`$ is the image of $`V(0)`$ under the orthogonal transformation with a matrix:

$$O(t)=\left(\begin{array}{cc}\stackrel{~}{U}& t(D)\\ t(D)& I\end{array}\right)+t^2G,$$
$`2.16`$
where for the norm of the matrix $`G`$ from (2.15) it follows

$$G(1+t\mathrm{\Lambda }_3)D^2,$$
$`2.17`$
for some constant $`\mathrm{\Lambda }_3`$ depending on $`\mathrm{\Lambda }_2`$. Finally note that the curve $`V(t)`$ in $`G_{p+q}^p`$ is the image under submersion $`\mathrm{\Pi }:O(p+q)G_{p+q}^p`$ of the curve $`O(t)`$ of orthogonal transformations in $`O(p+q)`$ so that the vector $`\dot{V}(0)`$ is the image of $`\dot{O}(0)`$ under the differential $`\mathrm{\Pi }_{}`$. From (2.14) we see that the tangent vector of the curve of the orthogonal transformations $`O(t)`$ at the moment $`t=0`$ is

$$\dot{O}(0)=\left(\begin{array}{cc}0& D\\ D& 0\end{array}\right).$$
$`2.18`$
By definition of the Lipschitz-Killing metric the length of this vector equals $`D`$. Note also that this vector is the horizontal one for the Riemannian submersion $`\mathrm{\Pi }:O(p+q)O(p+q)/O(p)\times O(q)=G_{p+q}^p`$, so that it has the same length as its image $`\dot{V}(0)`$ under the differential $`\mathrm{\Pi }_{}`$. Therefore, the length of the vector $`\dot{V}(0)`$ in $`G_{p+q}^p`$ equals the length of $`\dot{O}(0)`$ in the Lipschitz-Killing metric on $`O(p+q)`$, i.e., is exactly $`D`$; and we arrive at the following statement.

###### Lemma~1

$$\dot{V}(0)^2=D^2=\underset{i=1,\mathrm{},k;j=k+1,\mathrm{},n}{}((d_i)^j)^2.$$

###### Lemma~2

The geodesic curvature $`K(V(t))`$ of the linear curve $`V(t)G_{p+q}^p`$ is uniformly bounded.

###### Demonstration Proof

To prove this we use a well-known equality between a geodesic curvature of some curve in a Riemannian manifold and a distance from this curve to the geodesic, issuing from the same initial point with the same velocity vector. It is known that the geodesic curvature $`K(V(0))`$ of the curve $`V(t)`$ and the norm of its vector of velocity are related by the following equality:

$$K(V(0))=\underset{t0}{lim}2\frac{dist_{G_{p+q}^p}(V(t),\overline{V}(t))}{\dot{V}(0)^2t^2},$$
$`2.19`$
where $`\overline{V}(t)`$ is the geodesic in $`G_{p+q}^p`$ issuing from $`V(0)`$ with the same velocity vector: $`\dot{\overline{V}(0)}=\dot{V}(0)`$. Every geodesic $`\overline{V}(t)`$ in the base $`G_{p+q}^p`$ of the Riemannian submersion $`\mathrm{\Pi }:O(p+q)O(p+q)/O(p)\times O(q)=G_{p+q}^p`$ is the image under the map $`\mathrm{\Pi }`$ of some horizontal geodesic in $`O(p+q)`$, i.e., some 1-parameter subgroup of orthogonal transformations of $`R^{p+q}`$. Consider the 1-parameter subgroup $`\overline{O}(t)`$ of $`O(p+q)`$ generated by the vector $`\dot{O}(0)`$ above:

$$\dot{O}(0)=\left(\begin{array}{cc}0& D\\ D& 0\end{array}\right).$$

Because the vector $`\dot{O}(0)`$ is horizontal the geodesic $`\overline{O}(t)`$ in $`O(p+q)`$ is a horizontal geodesic and goes under submersion $`\mathrm{\Pi }`$ onto some geodesic in $`G_{p+q}^p`$. Because, as we verified above, the vector $`\dot{O}(0)`$ has the image under the differential $`\mathrm{\Pi }_{}`$ which is equal to $`\dot{V}(0)`$, this geodesic has the same velocity vector at initial point $`t=0`$, i.e., we conclude $`\overline{V}(t)=\mathrm{\Pi }(\overline{O}(t))`$. A direct calculation shows that

$$\overline{O}(t)=\mathrm{exp}(t\dot{O}(0))=I+t\dot{O}(0)+t^2\overline{G}+\mathrm{}$$
$`2.20`$
where for some constant $`\mathrm{\Lambda }_4`$ we have

$$\overline{G}\mathrm{\Lambda }_4D^2.$$
$`2.21`$
Because of (2.14) and (2.15) above this gives the inequality

$$\overline{O}(t)O(t)t^2\mathrm{\Lambda }_5D^2/2$$
$`2.22`$
for some constant $`\mathrm{\Lambda }_5`$ depending on $`\mathrm{\Lambda }_3`$ and $`\mathrm{\Lambda }_4`$. Because (as every Riemannian submersion) $`\mathrm{\Pi }`$ does not increase distances the last formula yields an inequality

$$\overline{V}(t)V(t)t^2\mathrm{\Lambda }_5D^2/2$$
$`2.23`$
implying the claim of the lemma. Lemma 2 is proved.

The next Lemma is the main technical point of our arguments.

###### Lemma~3

Let $`V(t),0tT`$ be some linear curve in $`G_{p+q}^p`$ such that its geodesic curvature $`K(V(t))`$ is bounded by some constant $`\mathrm{\Lambda }_5`$ for all $`0tT`$. Then the length of $`V(t)`$ is bounded by some constant $`\mathrm{\Lambda }_6`$ which depends on $`\mathrm{\Lambda }_5`$, but does not depend on $`T`$.

###### Demonstration Proof

Proof of the Lemma follows from simple compactness and monotonicity arguments as follows.

In addition to the Riemannian metric $`g`$ on $`G_{p+q}^p`$ we used above (coming from the Lipschitz - Killing metric on $`O(p+q)`$ under the submersion $`\mathrm{\Pi }`$), the Grassmanian $`G_{p+q}^p`$ also admits the following non-Riemannian metric $`\mathrm{}`$ (”angle”): for two subspaces $`V`$ and $`W`$ in $`R^{p+q}`$ the angle between them is

$$\mathrm{}(V,W)=\underset{vV}{sup}\underset{wW}{inf}\mathrm{}(v,w).$$
$`2.24`$
Clearly, we always have $`0\mathrm{}(V,W)\pi /2`$ and $`\mathrm{}(V,W)=\pi /2`$ if and only if some vector $`w`$ of $`W`$ is orthogonal to $`V`$.

Let $`V(t)`$ be our linear curve determined by $`\{e_i,d_i;i=1,\mathrm{},p\}`$ as above; i.e., $`V(t)=(I+tA)V`$ for some linear map $`A:VR^{p+q}`$. For a vector $`e(0)`$ of $`V(0)`$ we have $`(e(0),e(t))=0`$ for $`e(t)=(I+tA)e(0)`$ from $`V(t)`$ if and only if

$$(e(0),(I+tA)e(0))=0,$$
$`2.25`$
Note that there exists only a finite number of moments $`t_i`$ such that (2.25) holds for some non-zero $`e(0)`$ of $`V(0)`$. Indeed, if we denote by $`B:R^{p+q}V(0)`$ the orthogonal projection onto $`V(0)`$ then such vectors belong to the kernel of the operator $`B(I+tA):V(0)V(0)`$ which is non-zero if and only if the determinant function $`P(t)=det(B(I+tA))`$ vanishes. Because this determinant function is a polynomial of degree $`p`$ and is not identically zero (note that $`P(0)=1`$) it has at most $`p`$ zeros $`t_i,1imp`$.

For a partition $`\mathrm{}<t_1<\mathrm{}<t_m<\mathrm{}`$ it is not difficult to see that for arbitrary $`t_i<t^{}<t\mathrm{"}<t_{i+1}`$ we have

$$(e(t^{}),e(t\mathrm{"}))>0.$$
$`2.26`$
because otherwise (as is easy to check) for some $`t^{}`$ from the interval $`(t^{},t\mathrm{"})`$ it would follow $`(e(0),e(t^{}))=0`$.

Condition (2.26) implies that the angle between some fixed vector $`e(t^{})`$ and $`e(t\mathrm{"})`$ is a monotonely increasing function on $`t\mathrm{"}`$ when $`t^{}<t\mathrm{"}`$ are from $`(t_i,t_{i+1})`$. The same condition implies, that the angle between $`e(t\mathrm{"})`$ and $`V(t^{})`$ is also a monotonely increasing function on $`t\mathrm{"}`$ under the same restriction. Indeed, by definition for all $`t`$ we have $`e(t)=e(0)+td`$ for some $`e(0)`$ from $`V(0)`$. Let $`d=v+w`$, where $`v`$ belongs to the subspace $`V(t^{})`$, and $`w`$ is normal to it. Let also $`e(t^{})=a+b`$, where the vector $`a=\lambda v`$ is parallel to $`v`$, and $`b`$ is normal to $`v`$. Then $`e(t\mathrm{"})=b+(\lambda +(t\mathrm{"}t^{}))v+(t\mathrm{"}t^{})w`$, and (2.26) means that

$$(e(t^{}),e(t^{}))+(t\mathrm{"}t^{})(e(t^{}),v)>0.$$
$`2.27`$
The component of $`e(t\mathrm{"})`$ normal to $`V(t^{})`$ equals $`(t\mathrm{"}t^{})w`$ while the tangent component of $`e(t\mathrm{"})`$ to $`V(t^{})`$ is $`e(t^{})+(t\mathrm{"}t^{})v`$. So for the angle $`\varphi (t\mathrm{"})`$ between $`e(t\mathrm{"})`$ and the subspace $`V(t^{})`$ we have

$$tg(\varphi (t\mathrm{"}))=\frac{\sqrt{(w,w)}(t\mathrm{"}t^{})}{\sqrt{(e(t^{})+(t\mathrm{"}t^{})v,e(t^{})+(t\mathrm{"}t^{})v)}},$$

and by a direct calculation we see, that due to (2.27) the derivative of $`\varphi (t\mathrm{"})`$ is positive. Because this is true for an arbitrary $`e(t\mathrm{"})`$ we conclude that the angle between $`V(t\mathrm{"})`$ and $`V(t^{})`$ is also a monotonely increasing function on $`t\mathrm{"}`$ when $`t^{}<t\mathrm{"}`$ are from $`(t_i,t_{i+1})`$. To prove this it is sufficient to note that the derivative of the angle between $`V(t^{})`$ and $`V(t\mathrm{"})`$ on $`t\mathrm{"}`$ equals the maximum of derivatives of angles between $`V(t^{})`$ and those vectors $`e(t\mathrm{"})`$ of $`V(t\mathrm{"})`$ which have a maximum angle with $`V(t^{})`$.

Thus, every linear curve $`V(t)`$ we can divide into not more than $`p+1`$ intervals $`\{V(t)|t_i<t<t_{i+1}\}`$ such that the ”angle”-function $`\varphi _s(t)=\mathrm{}(V(s),V(s+t))`$ is monotonely increasing for $`0<t<t_{i+1}s`$ and monotonely decreasing for $`t_is<t<0`$. The claim of the Lemma will follow if we prove it for every such interval. In order to do this we note that this monotonicity of the angle means that the curve $`\{V(t)|t_i<t<t_{i+1}\}`$, leaving at some moment the $`ϵ`$-neighborhood of $`V(s)`$ in the metric $`\mathrm{}`$ never comes back, or that every ball in $`\mathrm{}`$-metric with the center $`V(s)`$ contains only one connected arc of the considered interval of the curve $`V(t)`$. Denote by $`U(V,ϵ)`$ an $`ϵ`$-neighborhood in the metric $`\mathrm{}`$ of the point $`V`$ of $`G_{p+q}^p`$.

For a given number $`\mathrm{\Lambda }_5`$ there exists some $`\omega `$ depending on $`\mathrm{\Lambda }_5`$ such that in every $`\omega `$-ball in the Riemannian metric $`g`$ the length of every connected arc of an arbitrary curve with geodesic curvature bounded by $`\mathrm{\Lambda }_5`$ is bounded by some constant $`L`$, which depends on $`\omega `$ and $`\mathrm{\Lambda }_5`$ and has order $`2\omega `$ as $`\omega 0`$.

Because topologies generated by two metrics $`\mathrm{}`$ and $`g`$ coincide, there exists a function $`\omega (ϵ)`$ (where $`\omega (ϵ)0`$ as $`ϵ0`$) such that every $`ϵ`$-ball in the metric $`\mathrm{}`$ is contained in $`\omega (ϵ)`$-ball in the metric $`g`$. Find some $`ϵ`$ such that $`\omega (ϵ)\omega `$. Using compactness of $`G_{p+q}^p`$ find some finite covering $`G_{p+q}^p=_iU(V_i,ϵ/2)`$. If some point $`V(t^{})`$ belongs to some $`U(V_i,ϵ/2)`$, then because of the triangle inequality the intersection of the considered interval $`V(t),t_i<t<t_{i+1}`$ with this $`U(V_i,ϵ/2)`$ lies in $`U(V(t^{}),ϵ)`$, and by the arguments above has length less than $`L`$, which obviously means that the length of the whole interval is bounded by $`LN`$, where $`N`$ is the number of all $`U(V_i,ϵ/2)`$ in the finite covering of $`G_{p+q}^p`$. As was said above, the number of intervals $`V(t),t_i<t<t_{i+1}`$ with described monotone behavior of the ”angle”-function $`\varphi _s(t)`$ is not bigger than $`(p+1)`$, so that the length of $`V(t),\mathrm{}<t<\mathrm{}`$ is bounded by $`nLN`$, i.e.,

$$_{\mathrm{}}^{\mathrm{}}\dot{V}(t)𝑑t<\mathrm{\Lambda }_6$$
$`2.28`$
for some constant $`\mathrm{\Lambda }_6`$ depending only on $`\mathrm{\Lambda }_5`$. Lemma 3 and hence, Theorem 3 and Theorem 2 consequently are proved.

References


text:
# Five-loop renormalization-group expansions for two-dimensional Euclidean 𝜆ϕ⁴ theory

(May 19, 2000)

## Abstract

The renormalization-group functions of the two-dimensional $`n`$-vector $`\lambda \varphi ^4`$ model are calculated in the five-loop approximation. Perturbative series for the $`\beta `$-function and critical exponents are resummed by the Pade-Borel-Leroy techniques. An account for the five-loop term shifts the Wilson fixed point location only briefly, leaving it outside the segment formed by the results of the lattice calculations. This is argued to reflect the influence of the non-analytical contribution to the $`\beta `$-function. The evaluation of the critical exponents for $`n=1`$, $`n=0`$ and $`n=1`$ in the five-loop approximation and comparison of the results with known exact values confirm the conclusion that non-analytical contributions are visible in two dimensions. For the $`2D`$ Ising model, the estimate $`\omega =1.31(3)`$ for the correction-to-scaling exponent is found that is close to the values resulting from the high-temperature expansions.

The field-theoretical renormalization-group (RG) approach proved to be a powerful tool for calculating the critical exponents and other universal quantities of the basic three-dimensional (3D) models of phase transitions. Today, many-loop RG expansions for $`\beta `$-functions (six-loop), critical exponents (seven-loop), higher-order couplings (four-loop), etc. of the 3D $`O(n)`$-symmetric and cubic models are known resulting in the high-precision numerical estimates for experimentally accessible quantities \[1-7\]. The main aim of this report is to elaborate further the field-theoretical RG technique, namely, to clear up how effective is this machinery in two dimensions where i) the RG series are stronger divergent and ii) singular (non-analytic) contributions to RG functions are expected to be larger than for 3D systems.

The Hamiltonian of the model describing the critical behaviour of various two-dimensional systems reads:

$$H=d^2x\left[\frac{1}{2}(m_0^2\phi _\alpha ^2+(\phi _\alpha )^2)+\frac{\lambda }{24}(\phi _\alpha ^2)^2\right],$$
(1)
where $`\phi _\alpha `$ is a real $`n`$-vector field, $`m_0^2`$ is proportional to $`TT_c^{(0)}`$, $`T_c^{(0)}`$ being the mean-field transition temperature.

We calculate the $`\beta `$-function and the critical exponents for the model (1) within the massive theory. The Green function, the four-point vertex and the $`\varphi ^2`$ insertion are normalized in a conventional way:

$`G_R^1(0,m,g_4)=m^2,{\displaystyle \frac{G_R^1(p,m,g_4)}{p^2}}|_{p^2=0}=1,`$ (2)
$`\mathrm{\Gamma }_R(0,0,0,m,g)=m^2g_4,\mathrm{\Gamma }_R^{1,2}(0,0,m,g_4)=1.`$
Since the four-loop RG expansions at $`n=1`$ are known  we are in a position to find corresponding series for arbitrary $`n`$ and to calculate the five-loop terms. The results of our calculations are as follows:

$`{\displaystyle \frac{\beta (g)}{2}}=g+g^2{\displaystyle \frac{g^3}{(n+8)^2}}\left(10.33501055n+47.67505273\right)`$
$`+{\displaystyle \frac{g^4}{(n+8)^3}}\left(5.000275928n^2+149.1518586n+524.3766023\right)`$
$`{\displaystyle \frac{g^5}{(n+8)^4}}\left(0.0888429n^3+179.69759n^2+2611.1548n+7591.1087\right)`$
$`+{\displaystyle \frac{g^6}{(n+8)^5}}\left(0.00408n^4+80.3096n^3+5253.56n^2+53218.6n+133972\right).`$ (3)
$`\gamma ^1=1{\displaystyle \frac{n+2}{n+8}}g+{\displaystyle \frac{g^2}{(n+8)^2}}(n+2)3.375628955`$
$`{\displaystyle \frac{g^3}{(n+8)^3}}\left(4.661884772n^2+34.41848329n+50.18942749\right)`$
$`+{\displaystyle \frac{g^4}{(n+8)^4}}\left(0.3189930n^3+71.703302n^2+429.42449n+574.58772\right)`$
$`{\displaystyle \frac{g^5}{(n+8)^5}}\left(0.09381n^4+85.4975n^3+1812.19n^2+8453.70n+10341.1\right).`$ (4)
$`\eta ={\displaystyle \frac{g^2}{(n+8)^2}}(n+2)0.9170859698{\displaystyle \frac{g^3}{(n+8)^2}}(n+2)0.05460897758`$
$`+{\displaystyle \frac{g^4}{(n+8)^4}}\left(0.09268446n^3+4.0564105n^2+29.251167n+41.535216\right)`$
$`{\displaystyle \frac{g^5}{(n+8)^5}}\left(0.07092n^4+1.05240n^3+57.7615n^2+325.329n+426.896\right).`$ (5)
In more details, the calculations are described in Ref.. Instead of the renormalized coupling constant $`g_4`$, a rescaled coupling

$$g=\frac{n+8}{24\pi }g_4,$$
(6)
is used as an argument in above RG series. This variable is more convenient since it does not go to zero under $`n\mathrm{}`$ but approaches the finite value equal to unity.

To evaluate the Wilson fixed point location $`g^{}`$ and numerical values of the critical exponents, the resummation procedure based on the Borel-Leroy transformation

$$f(x)=\underset{i=0}{\overset{\mathrm{}}{}}c_ix^i=\underset{0}{\overset{\mathrm{}}{}}e^tt^bF(xt)𝑑t,F(y)=\underset{i=0}{\overset{\mathrm{}}{}}\frac{c_i}{(i+b)!}y^i,$$

is used. The analytical extension of the Borel transforms is performed by exploiting relevant Padé approximants \[L/M\]. In particular, four subsequent diagonal and near-diagonal approximants $`[1/1]`$, $`[2/1]`$, $`[2/2]`$, and $`[3/2]`$ turn out to lead to numerical estimates for $`g^{}`$ which rapidly converge, via damped oscillations, to the asymptotic values; this is cleary seen from Table 1. These asymptotic values, i. e. the final five-loop RG estimates for $`g^{}`$ are presented in Table 2 for $`0n8`$ (to avoid confusions, let us note that models with $`n2`$ possessing no ordered phase are studied here only as polygons for testing the numerical power of the perturbative RG technique). As Table 2 demonstrates, the numbers obtained differ appreciably from numerical estimates for $`g^{}`$ given by the lattice and Monte Carlo calculations \[9-15\]; such estimates are usually extracted from the data obtained for the linear ($`\chi `$) and non-linear ($`\chi _4`$) susceptibilities related to each another via $`g_4`$:

$$\chi _4=\frac{^3M}{H^3}|_{H=0}=\chi ^2m^2g_4,$$
(7)
Since the convergence of the numerical estimates for $`g^{}`$ given by the resummed RG series is oscillatory, an account for higher-order (six-loop, seven-loop, etc.) terms in the expansion (3) will not avoid this discrepancy . That is why we believe that it reflects the influence of the singular (non-analytical) contribution to the $`\beta `$-function.

The critical exponents for the Ising model ($`n=1`$) and for those with $`n=0`$ and $`n=1`$ are estimated by the Padé-Borel summation of the five-loop expansions (4), (5) for $`\gamma ^1`$ $`\eta `$. Both the five-loop RG (Table 1) and the lattice (Table 2) estimates for $`g^{}`$ are used in the course of the critical exponent evaluation. To get an idea about an accuracy of the numerical results obtained the exponents are estimated using different Padé approximants, under various values of the shift parameter $`b`$, etc. In particular, the exponent $`\eta `$ is estimates in two principally different ways: by direct summation of the series (5) and via the resummation of RG expansions for exponents

$$\eta ^{(2)}=\frac{1}{\nu }+\eta 2,\eta ^{(4)}=\frac{1}{\nu }2,$$
(8)
which possess a regular structure favouring the rapid convergence of the iteration procedure. The typical error bar thus found is about 0.05.

The results obtained are collected in Table 3. As is seen, for small exponent $`\eta `$ and in some other cases the differences between the five-loop RG estimates and known exact values of the critical exponents exceed the error bar mentioned. Moreover, in the five-loop approximation the correction-to-scaling exponent $`\omega `$ of the 2D Ising model is found to be close to the value 4/3 predicted by the conformal theory  and to the estimate $`1.35\pm 0.25`$ extracted from the high-temperature expansions  but differs markedly from the exact value $`\omega =1`$  and contradicts to recent conjecture $`\omega =2`$ . This may be considered as an argument in favour of the conclusion that non-analytical contributions are visible in two dimensions.

We thank B. N. Shalaev for numerous useful discussions of the critical thermodynamics of 2D systems. The work was supported by the Ministry of Education of Russian Federation (Grant 97-14.2-16), by the International Science Foundation (A. I. S., Grant 99-943), and by Saint Petersburg Administration (E. V. O., grant ASP 298496).


text:
# Magnetic control of the interaction in ultracold K-Rb mixtures

## Abstract

We predict the presence of several magnetic Feshbach resonances in selected Zeeman sublevels of the isotopic pairs 40K-87Rb and 41K-87Rb at magnetic fields up to $`10^3`$ G (1G = $`10^4`$ T). Positions and widths are determined combining a new measurement of the 40K-87Rb inelastic cross section with recent experimental results on both isotopes. The possibility of driving a K-Rb mixtures from the weak to the strong interacting regime tuning the applied field should allow to achieve the optimal conditions for boson-induced Cooper pairing in a multi component 40K-87Rb atomic gas and for the production of ultracold polar molecules.

The possibility of controlling the interactions in an ultracold atomic gas using magnetically tunable Feshbach resonances inouye98nature  has been successfully exploited in recent remarkable experiments. It has indeed allowed to reach Bose-Einstein condensation (BEC) for species difficult to condense in zero field and to study their stability properties roberts01prl ; weber02science , to form bright solitons khajkovich02science , to produce ultracold homonuclear molecules donley02nature  and a strongly interacting Fermi gas ohara02science . The presence of Feshbach resonances between atoms of different species could open new possibilities, thereby in this paper we carry out a detailed investigation in this direction.
We focus on two potassium-rubidium mixtures that have allowed the production of a two-species BEC (41K-87Rb) science1 ; modugno02prl  and of a strongly interacting Fermi-Bose mixture (40K-87Rb) roati02prl . We predict the positions and the widths of several Feshbach resonances in selected magnetic sublevels of the ground electronic state by combining collisional measurements on the two isotopes. These resonances might for instance allow the observation of boson-induced Cooper pairing bijlsma00pra  or the formation of ultracold bosonic or fermionic polar molecules paul .
We use for our calculations the collision model presented in Ref. ferrari , where the Hamiltonian now includes the Zeeman interaction with the external magnetic field pot . Denoting “a” and “b” potassium and rubidium, collisions are labeled as $`(f_am_{fa})`$+$`(f_bm_{fb})`$, where $`f_a`$, $`f_b`$ are the hyperfine angular momenta with projection $`m_{fa}`$, $`m_{fb}`$ along the quantization axis. Please recall that the model is parameterized by the singlet and triplet $`s`$-wave scattering lengths $`a_{s,t}`$ and by the long-range dispersion coefficients $`C_n`$ with $`n`$=6,8,10. We adopt a $`\pm 2\%`$ uncertainty in the highly accurate van der Waals coefficient $`C_6=4274`$ a.u. (1 a.u. = 0.0957345$`\times `$10-24J$``$nm6) in order to account for the combined uncertainty in all the $`C_n`$’s. In the absence of weak relativistic spin-interactions the projection $`m_f=m_{fa}+m_{fb}`$ and the rotational angular momentum of the atoms about the center of mass $`\mathrm{}`$ are good quantum numbers for the collision event. In this work we limit ourselves to $`\mathrm{}=0`$ collisions which, at least in the absence of $`\mathrm{}>0`$ low-energy resonances, give the dominant contribution to the interaction in the ultracold regime.
Two key measurements on 40K-87Rb mixtures provide the best range of input parameters to our model available to date. First, the elastic cross-section for $`(9/2,9/2)`$+$`(2,2)`$ has been directly measured by inter-species thermalization roati02prl  and by damping of coupled K-Rb dipole oscillations modugno02science . Combining the systematic uncertainties in these two determinations we estimate $`a_t=a_{\frac{9}{2}\frac{9}{2},22}=410_{80}^{+80}a_0`$ (1 $`a_0`$ = 0.0529177 nm). Mass scaling of this value to 41K-87Rb allows us to strongly tighten the upper bound on the triplet scattering length of Ref. ferrari , leading to $`a_t(4187)`$ = 156$`{}_{5}{}^{}{}_{}{}^{+10}`$ and to reduce the original uncertainty in the number of triplet bound states to $`N_b^t(4187)=31\pm 1`$.
Second, in order to determine $`a_s`$ we measure the $`(9/2,9/2)`$\+ $`(2,1)`$ atom-loss rate in a nondegenerate sample. We prepare a doubly spin-polarized sample in the magnetic trap containing about 104 K atoms and 105 Rb atoms at temperatures in the range $`(300900)`$ nK, and then transfer about 30% of the Rb sample in the $`(2,1)`$ state using a fast radio-frequency sweep. After a short rethermalization period we measure the time-evolution of the number of K atoms, which decays through inelastic collisions with Rb according to the rate equation $`\dot{n}^K(t)=G^{inel}n_{9/2,9/2}^K(t)n_{2,1}^{Rb}(t)`$. We find $`G^{inel}`$ = 5.0(2.5)$`\times 10^{12}`$ cm3 s-1, where the uncertainty is dominated by that on the atom numbers. In this work we make a conservative choice and adopt only the order of magnitude $`G=(10^{12}10^{11})`$ cm3 s-1.

Figure 1 shows $`G^{inel}`$ numerically calculated as a function of $`a_s`$ varying $`a_t`$ within the bounds determined above. The horizontal axis is labeled by a scaled “scattering phase” $`\xi _s=(2/\pi )\mathrm{arctan}(a_s/a_{sc})`$, where $`a_{sc}=\frac{1}{2}(2\mu C_6)^{1/4}72a_0`$ is a typical length for a purely van der Waals potential, with $`\mu `$ the K-Rb reduced mass. To be noted the strong suppression of the inelastic rate for $`a_sa_t`$. Comparison with the experimental value leads either to a very large (positive or negative) or to a negative singlet scattering length $`a_s(4087)=185_{225}^{+83}a_0`$. Mass-scaling with $`N_b^s(4187)=98\pm 2`$ gives a singlet scattering length for the bosons pair $`a_s(4187)=5.0_{34}^{+23}a_0`$ and, by compatibility with the $`a_s(4187)`$ of Ref. ferrari , rules out the range of very large $`|a_s|(4087)`$. With these $`a_s,a_t`$ we can predict the zero-field scattering length and Feshbach resonances of different magnetic polarization states. Let us first consider the boson-fermion pair 40K-87Rb.
The inverted hyperfine structure of the fermionic potassium, with the $`f=9/2`$ lying below the $`f=7/2`$ level, leads to a peculiar and very favorable feature of this pair, namely the stability under spin-exchange collisions of any combination where either atom is in its lowest Zeeman sublevel. We therefore find it important to summarize in Tab. 1 the scattering properites of the $`(9/2,9/2)`$+$`(1,m_{fb})`$ states and of at least the most easily experimentally realizable $`(9/2,m_{fa})`$+$`(1,1)`$ magnetic states. Note all of these hyperfine states have a relatively large ( i.e. $`|a|>a_{sc}`$ ) and negative zero-field scattering length. This ensures that the two clouds will remain miscible even in the ultracold regime, see Ref. molmer98prl .

A magnetic Feshbach resonance arises when a molecular bound-state crosses an atomic threshold laue02pra . Across a Feshbach resonance the scattering length $`a`$ presents a typical dispersive dependence on the strength of the applied field $`B`$, $`a(B)=\stackrel{~}{a}(1\frac{\mathrm{\Delta }}{BB_0})`$, where $`B_0`$ is the field strength on resonance, $`\mathrm{\Delta }`$ is the resonance width and $`\stackrel{~}{a}`$ is the off-resonance background scattering length. The resonance parameters $`B_0`$ and $`\mathrm{\Delta }`$ have been extracted from an accurate close-coupled calculation on a fine $`B`$-grid and are shown in Tab. 1.
Homonuclear collisions between alkali atoms in a magnetic field have been studied in great detail. Only a relatively small amount of Feshbach spectroscopy is often necessary as input to theoretical models in order to gain an impressive power in determining the interaction potential and in predicting the position of additional resonances Cs ; vankempen02prl . The parameters $`a_s,a_t`$ and $`C_n`$’s of our collision model can in principle be determined following a similar procedure. At least three resonances between the ones shown in Tab. 1 would be needed as input to the model. Inclusion of the high-field $`(9/2,7/2)`$+$`(1,1)`$ resonance would improve the procedure since this latter resonance is nearly purely triplet in character with average electron spin $`S^2`$1.95 and very sensitive to $`C_6`$, $`\delta B_0/B_0`$ = -1.2 $`\delta C_6/C_6`$.
The relatively strong and tunable interaction between different magnetic polarization states opens up the possibility of realizing Bose-Fermi mixtures where the fermions undergo a Cooper-pairing phase transition to a superfluid state via exchange of density fluctuations of the background BEC bijlsma00pra ; viverit02pra . Due to identical particle symmetrization, direct as well as boson-mediated $`s`$-wave collisions between a pair of fermionic K atoms are allowed only in a Fermi gas with at least two internal components, which we denote as “1” and “2” in the following. We also let $`a_{Rb}`$ be the intra-species scattering length for collisions of Rb atoms, $`a_K`$ the intra-species scattering length for collisions of K in state “1” and K in state “2” and $`a_{KRb,i}`$, with $`i=1,2`$, the inter-species scattering lengths for collisions of Rb and K in state “$`i`$”.
The critical temperature $`T_c`$ for boson induced $`s`$-wave Cooper pairing can be given an analytic expression valid in the limit of low boson-densities and of a BEC larger than the fermionic cloud, see Eq. (13) of Ref. viverit02pra . As long as $`a_{KRb,1}a_{KRb,2}>>a_{Rb}a_K`$, the critical temperature is independent of $`a_K`$, and increases exponentially with $`a_{Rb}/(k_Fa_{KRb,2}a_{KRb,1})`$, where $`k_F`$ is the Fermi vector. It must be noted however that as soon as $`k_Fa_{KRb,i}^2a_{Rb}`$, the $`i`$-th component of K and Rb will become dynamically unstable and collapse modugno02science ; roth02pra . As a consequence the optimal condition for Cooper pairing are $`a_{KRb,1}a_{KRb,2}a_{KRb}`$ and $`a_{KRb}^2k_Fa_{Rb}`$.
From Tab. 1 a mixture composed of K$`(9/2,9/2)`$, K$`(9/2,7/2)`$ and Rb$`(1,1)`$ seems to be the most appropriate in order to fulfill this condition. However, for the nominal values of the zero-field scattering lengths between these components, we estimate that at least a factor of four increase in the average trapping frequency would be necessary with respect to our current experimental setup. If the actual $`a_{KRb,i}`$ turned out to be smaller than the nominal value, this factor would increase even further. Fortunately, at least for some potential parameters, a pair of resonances exist that allow simultaneous tuning of $`a_{KRb,1}`$ and $`a_{KRb,2}`$ to a large value at the same time, making such a large trapping frequency unnecessary.

A very favorable situation is shown in Fig. 2, where for $`B725.89`$ G we get $`a_{KRb}687a_0`$ . In order to have this value stabilized to within 10 $`a_0`$ the magnetic field must be stabilized to within $`0.1`$ G, which is a stringent yet possible to be met requirement vankempen02prl . The field at which $`a_{KRb,1}=a_{KRb,2}`$ and the common value $`a_{KRb}`$ are extremely sensitive to the details of the potential, and a conclusive word on what is the largest achievable common $`a_{KRb}`$ is at this stage left to forthcoming precision experiments on K-Rb Feshbach resonances. As a trend, $`|a_{s,t}|`$ smaller than the nominal values tend to have a good working field for inducing the Cooper pairing instability, for $`|a_{s,t}|`$ larger than the nominal values (which however implies larger zero-field $`a`$’s) such a field may not exist.

We now consider the boson-boson pair 41K-87Rb. We summarize in Tab. 2 the collision properties of the states $`(2,2)`$+$`(2,2)`$ and $`(1,1)`$+$`(1,1)`$, which are collisionally stable for any field, and of the state $`(1,1)`$+$`(1,1)`$ which is only stable up to a threshold value $`B^t143.45`$ G, where the $`(2,2)`$+$`(1,0)`$ channel opens up and becomes the stable one. The $`a_{11,11}`$ and $`a_{11,11}`$, which are equal at zero field, are relatively large.
The $`(1,1)`$+$`(1,1)`$ collision always presents at least two broad and one narrow resonance below $`10^3`$ G, see Tab. 2 and Fig. 3. The analytical expression for the scattering length of a pair of overlapping resonances with positions $`B_{0,\pm }`$ and widths $`\mathrm{\Delta }_\pm `$

$`{\displaystyle \frac{a(B)}{\stackrel{~}{a}}}=1{\displaystyle \frac{(BB_{0,+})\mathrm{\Delta }_{}+(BB_{0,})\mathrm{\Delta }_+}{(BB_{0,+})(BB_{0,})}},`$
has been used to fit both low-field resonances in the table. The lowest-field resonance exists only if $`a_{11,11}>0`$, for $`a_{11,11}<0`$ it turns into a real bound-state below the $`(1,1)`$+$`(1,1)`$ atomic threshold and cannot be observed in a standard scattering experiment.

The $`(1,1)`$+$`(1,1)`$ collision presents a feature near the threshold value $`B^t`$. In this situation virtual excitations to the $`(2,2)`$+$`(1,0)`$ channel can strongly modify the real part of the scattering length (see Fig. 3), defined as $`a_{11,11}=lim_{k0}S_{11,11}/(2ik)`$, with $`S`$ the scattering matrix and $`k`$ the wave vector of the incoming atoms. Such fluctuations-induced feature is always present in our range of parameters if $`a_{11,11}>0`$ but turns out to be important for $`a_{11,11}<0`$ only for very large $`|a_{11,11}|`$. To be noted the cusp at $`B=B_t`$ that follows from the analytical properties of the scattering matrix near the opening of a new threshold newton .
Finally, a field induced resonance in the $`(2,2)`$+$`(2,1)`$ inelastic loss-rate has been included in Tab. 2 since it may be important in order to constrain the collision model from Feshbach-resonance spectroscopy carried out on the boson-boson isotope. The width $`\mathrm{\Delta }`$ shown in the table is in this case the inelastic one, defined through the expression of the total scattering eigenphase across resonance, $`\delta (B)=\delta _0\mathrm{arctan}\frac{\mathrm{\Delta }^{inel}}{(BB_0)}`$, with $`\delta _0`$ the background scattering phase. Moreover, near this resonance we find a dramatic reduction of the $`(2,2)`$+$`(2,1)`$ inelastic decay rate down to $`G10^{15}`$ cm3 s-1, a value that ensures the collisional stability of a two-species $`(2,2)`$+$`(2,1)`$ BEC.
An interesting application of our results is to the production of polar molecules via photoassociation, as proposed in Ref. paul . First step in this scheme is a Mott-insulator transition of a double K-Rb BEC into a state where only pairs of molecules are loaded into the cells of an optical potential. Whether K-K and Rb-Rb or K-Rb pairs are loaded together depends upon the ratio of the interaction strength between all pairs. Using the low-field resonance shown in Fig. 3 one can clearly vary the interaction from strongly attractive, thus favoring formation of K-Rb pairs, to strongly repulsive, thus favoring K-K and Rb-Rb pairs. For instance, the condition $`a_{KRb(11,11)}=0.5\sqrt{a_{K(11,11)}a_{Rb(11,11)}}`$ required in Ref. paul  in order to load a single K and a single Rb per cell can easily be reached. A Raman photoassociation pulse or a direct microwave pulse can then be used to associate atoms into molecules at each lattice cell. In alternative, a time-dependent magnetic field has also been proposed for near-unity conversion of atoms into molecules, see Ref. mies00pra . This technique can of course be used for both the isotopic pairs investigated in this work.
We are grateful to P. S. Julienne, E. Tiesinga, and C. J. Williams for stimulating discussions and for making available the ground-state collisions code. We aknowledge useful discussions with F. Riboli and L. Viverit. This work was supported by MIUR under a PRIN project, by ECC under the Contract HPRICT1999-00111, and by INFM, PRA ”Photonmatter”.