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# Molecular Alignment and Orientation: From Laser-Induced Mechanisms to Optimal Control

## 1. Introduction

Laser-induced molecular alignment and orientation are challenging control issues with a wide range of applications, extending from chemical reactivity to nanoscale design . They address molecular manipulation, involving external angular degrees of freedom, aiming at a parallel positioning of the molecular axis with respect to the laser polarization vector (*alignment*) or, even more demanding, with a given direction (*orientation*). One of the basic motivations remains the drastic increase of reactive cross sections, highly sensitive to stereodynamical effects (frontal collisions). Laser-induced isomerization , isotope separation , molecular trapping , or surface processing and catalysis  are some of the illustrations of the widely growing interest in molecular manipulation.

The most common idea is to excite a broad rotational band $`\mathrm{\Delta }J`$ in order to recover a narrow angular distribution $`\mathrm{\Delta }\theta `$, through the celebrated relation $`\mathrm{\Delta }J\mathrm{\Delta }\theta \mathrm{}`$ ($`J`$ being the total angular momentum and $`\theta `$ the molecule-laser angle). Our approach to this problem is, however, different. The emphasis is put on the depiction and study of some laser-induced dynamical mechanisms that are relevant to the alignment/orientation process: pendular states in high-frequency fields; two-photon (fundamental and second-harmonic) excitations; the kick mechanism. The question of how to take advantage of such mechanisms in a control scheme is brought up only in a second step. Adiabatic transport from an isotropic distribution to a pendular state; two IR laser pulses with frequencies in a ratio 2, the second harmonic being in resonance with a vibrational transition; very asymmetric and short-duration (sudden) half-cycle pulses imparting sudden kicks to the molecule, are some of the scenarios which are depicted and discussed in the following. Finally, in a third step, this knowledge is fully exploited in optimal control schemes, not merely for initial guesses in parameter sampling, but mainly to get a better understanding and interpretation of otherwise black-box type calculations.

The paper is organized as follows. Section 2 is devoted to intense laser alignment of the HCN molecule, through pendular states as the elementary mechanism and adiabatic/sudden transport as the control strategy. Section 3 presents the two-color orientation of HCN by a parity mixing scenario in the rotational distribution. The kick mechanism with a half-cycle pulse sudden excitation scenario is examined in section 4, as illustrated on the LiCl molecule. Sudden-excitation-based optimal control scenarios, with a thorough analysis of the role of different orientation criteria, are analyzed, using HCN and LiF, in section 5.

## 2. Laser-controlled alignment

### 2.1. The model

The linear HCN molecule, taken as an illustrative example, is described by its internal stretching motions (collectively labelled $`𝐑`$) and external rotational motions described by its polar $`\theta `$ and azimuthal $`\phi `$ angles with respect to the laser polarization vector (see figure 1).

The Hamiltonian involves a single Born-Oppenheimer potential curve $`V(𝐑)`$ (the molecular electronic ground state) and the radiative coupling $`\widehat{H}_{\mathrm{rad}}(𝐑,\theta ,\phi ,t)`$ given by the scalar product of the field-induced dipole moment $`𝝁(𝐑)`$ with the electric field amplitude $`𝓔(t)`$, i.e.,

$$\widehat{H}(𝐑,\theta ,\phi ,t)=\widehat{T}_𝐑+\frac{\mathrm{}^2}{2I(𝐑)}\widehat{J}^2+V(𝐑)+\widehat{H}_{\mathrm{rad}}(𝐑,\theta ,\phi ,t),$$
(2.1)
where $`\widehat{T}_𝐑`$ is the kinetic energy operator in $`𝐑`$, $`\widehat{J}^2`$ the angular momentum operator, and $`I(𝐑)`$ the moment of inertia of the molecule. The dipole moment itself is taken as the sum of a permanent dipole $`𝝁_0`$ and a polarizability $`\stackrel{=}{\alpha }`$

$$𝝁(𝐑,t)=𝝁_0+\frac{1}{2}\stackrel{=}{\alpha }𝓔(t),$$
(2.2)
such that

$$\widehat{H}_{\mathrm{rad}}(𝐑,\theta ,\phi ,t)=\mu _0(t)\mathrm{cos}\theta \frac{1}{2}^2(t)\left(\alpha _{}\mathrm{cos}^2\theta +\alpha _{}\mathrm{sin}^2\theta \right).$$
(2.3)
In the last equation, we have made use of the fact that, for a linear molecule, $`\stackrel{=}{\alpha }=\text{Diag}\{\alpha _{xx},\alpha _{yy},\alpha _{zz}\}`$, with $`\alpha _{xx}=\alpha _{yy}\alpha _{}`$ and $`\alpha _{zz}\alpha _{}`$, when the $`z`$ axis is chosen to be collinear with the molecular axis. Due to cylindrical symmetry and since the laser-molecule coupling term does not depend explicitly on $`\phi `$, the motion on $`\phi `$ can be considered separately and is no longer taken into account.

The laser pulses are of the form $`(t)=_0(t)\mathrm{cos}\left(\omega t+\varphi \right)`$, with $`_0(t)`$ the time varying envelope of the electric field of frequency $`\omega `$ and phase $`\varphi `$. We will consider laser pulses of a maximum intensity of the order of $`10^{13}\mathrm{W}/\mathrm{cm}^2`$, to avoid ionization damage to the molecule. The frequency $`\omega `$ is taken in the infra-red region, so it is considerably higher than the rotational frequency of the molecule.

The dynamics of the molecular system are then obtained by solving numerically the time-dependent Schrödinger equation

$$i\mathrm{}\frac{}{t}\psi (𝐑,\theta ,t)=\widehat{H}(𝐑,\theta ,t)\psi (𝐑,\theta ,t)$$
(2.4)
(on a discretized grid using the split-operator method ), starting from an initial wave function $`\psi (𝐑,\theta ,t=0)`$ taken, in most cases, as the ground (rotationally isotropic) state of the molecule.

### 2.2. Pendular states

In this high-frequency regime, two different motions are considered: a fast motion associated with the electric field $`\omega t`$ and a slow motion associated with the molecular rotation described by $`\theta `$. To simplify the presentation, we freeze the molecular internal motions, assuming a rigid rotor behavior. The eigenvectors of the slow motion $`\xi _{nJ}(\theta )`$ obey, after averaging over the fast motion within an optical period (and some high-frequency approximations) a Schrödinger equation given by

$`\left[{\displaystyle \frac{\mathrm{}^2}{2I}}\widehat{J}^2+{\displaystyle \frac{\mathrm{}^2}{2I}}{\displaystyle \frac{M^2}{\mathrm{sin}^2\theta }}+\left(\mathrm{\Delta }\alpha +{\displaystyle \frac{\mu _0^2}{I\omega ^2}}\right){\displaystyle \frac{_0}{4}}\mathrm{sin}^2\theta +{\displaystyle \frac{\mathrm{\Delta }\alpha ^2_0^4}{256I\omega ^2}}\mathrm{sin}^22\theta \right]\xi _{nJ}(\theta )`$
$`=\left(\lambda _nJ\mathrm{}\omega +{\displaystyle \frac{\alpha _{}_0^2}{4}}\right)\xi _{nJ}(\theta ),`$ (2.5)
where $`\mathrm{\Delta }\alpha =\alpha _{}\alpha _{}`$. The $`\theta `$-dependent laser-induced effective potential has a $`\mathrm{sin}^2\theta `$ shape and supports the eigenvectors $`\xi _{nJ}(\theta )`$ which are localized around $`\theta =0`$ and $`\pi `$ (aligned geometry), in a way which is more marked for increasing intensity. Because of the resulting libration motion for a molecule that is in one of these eigenstates, they are dubbed *pendular states* .

It is interesting to note a close analogy with the classical Lagrange equation of the laser-driven rigid rotor under the combined effect of the permanent dipole and the polarizability ,

$$I\ddot{\theta }\frac{M^2}{I}\frac{\mathrm{cos}\theta }{\mathrm{sin}^3\theta }\left(\mathrm{\Delta }\alpha +\frac{\mu _0^2}{I\omega ^2}\right)\frac{_0^2}{4}\mathrm{sin}2\theta \frac{\mathrm{\Delta }\alpha ^2_0^4}{128I\omega ^2}\mathrm{sin}4\theta .$$
(2.6)
The classical force of the right-hand-side of equation (2.6) is nothing but the gradient of the effective potential of the Hamiltonian version, equation (2.5). This classical analogy leads, upon a change of variable $`\mathrm{\Theta }=2\theta `$, to the well-known equation of the pendulum,

$$\ddot{\mathrm{\Theta }}+\mathrm{\Omega }^2\mathrm{sin}\mathrm{\Theta }=0,$$
(2.7)
that librates with small oscillations $`\theta `$ around the laser polarization axis with a frequency

$$\mathrm{\Omega }=\frac{1}{\sqrt{I}}\left(\frac{1}{2}\frac{\mu _0^2_0^2}{I\omega ^2}+\frac{1}{2}\mathrm{\Delta }\alpha _0^2\right)^{1/2},$$
(2.8)
where the polarizability remains the leading term as soon as the laser frequency exceeds 315 cm<sup>-1</sup> (for the HCN molecule), whatever the intensity.

### 2.3. Control scheme

The question of how to take advantage of the pendular mechanism to control molecular alignment can be answered by referring to adiabatic vs sudden transport dynamics, starting from an initial isotropic distribution ($`J=M=0`$, as prepared, for instance, by laser cooling methods ).

The adiabatic switching of a laser with rise and fall times of 10 ps (same order as the molecular rotational period) and an intensity of $`10^{12}\mathrm{W}/\mathrm{cm}^2`$ allows an adiabatic transport on a single (lowest) pendular state with a good alignment during the excitation. Figure 2(a) illustrates the alignment dynamics through the expectation value of $`\mathrm{cos}^2\theta `$, i.e.,

$$\mathrm{cos}^2\theta (t)=_0^\pi \mathrm{cos}^2\theta \left|\psi (\theta ,t)\right|^2\mathrm{sin}\theta d\theta .$$
(2.9)
The higher the value, the better the alignment, with $`\mathrm{cos}^2\theta =1/3`$ corresponding to an isotropic distribution. An alignment of $`\mathrm{cos}^2\theta 0.64`$ is achieved during the pulse but, as expected, the laser extinction adiabatically transports the pendular state back to the isotropic ($`J=M=0`$) state.

To achieve post-pulse alignment, one may proceed with sudden excitations. Figure 2(b) shows the effect of a sudden pulse of 1.7 ps duration, which excites several pendular states with a specific distribution (for a field frequency resonant with HCN internal vibrations). The particular $`J`$ distribution reached is such that alignment remains even after the pulse is off, $`\mathrm{cos}^2\theta (t)`$ showing small amplitude oscillations around a value of $`0.5`$.

## 3. Two-color laser control of orientation (Parity breaking scenarios)

As compared to alignment, orientation, which imposes a given direction, is a more challenging goal that requires symmetry breaking in the forward and backward directions. Two such scenarios are considered in this work. The first concerns the use of two-color pulses, that is a combination of a fundamental frequency $`\omega `$ and its second harmonic $`2\omega `$ with a resulting field

$$(t)=_0(t)\left[\mathrm{cos}\omega t+\gamma \mathrm{cos}\left(2\omega t+\varphi \right)\right],$$
(3.1)
where maximum asymmetry is reached for $`\gamma =0.5`$ and $`\varphi =0`$. But the asymmetry we are referring to is not in the time dependence of $`(t)`$, which in any case is not enough to produce orientation as, in average over an optical period of the field, the positive and negative contributions are canceling each other. We are rather referring to parity breaking in the rotational quantum numbers $`J`$. As opposite to a monochromatic field that excites $`J`$’s of the same parity, two-color excitation has the potentiality to mix $`J`$’s of different parity. Actually, by taking $`2\omega `$ in resonance with the $`v=01`$ vibrational transition of HCN, the absorption of a single photon $`2\omega `$ excites odd $`J`$’s through the permanent dipole interaction $`\mu _0`$, whereas the absorption of two photons $`\omega `$ excites even $`J`$’s through the polarizability interaction $`\alpha ^2`$ (starting from an initial state $`J=M=0`$. It is precisely the mixture of odd and even $`J`$’s that produces, by the superposition of associated spherical harmonics, the asymmetrical angular distributions that are looked for. The result is shown in figure 3(a) as the expectation value of $`\mathrm{cos}\theta `$, which is a measure of orientation (the higher the absolute value, the better the orientation).

We see that orientation is actually achieved at the extinction of the laser pulse and more efficiently a short time after the pulse is off, with $`\mathrm{cos}\theta `$ reaching $`0.3`$.

Orientation can also be achieved by an adiabatic transport from an initial isotropic state to an asymmetric combination of pendular states by a two-color excitation scheme . Contrary to the result shown in figure 3, such an orientation can only be maintained while the laser is on, similarly to what is observed for alignment in figure 2(a).

## 4. Half-cycle pulses and the kick mechanism

The second symmetry breaking scenario addresses the temporal shape of the electric field. The most asymmetrical situation that is experimentally reachable is the use of half-cycle pulses (HCP’s) . Such picosecond, far-IR electromagnetic pulses are generated when illuminating a GaAs wafer, in the presence of a pulsed electric field applied across the surface, by a Ti-Sapphire laser . Such pulses have three interesting characteristics (as illustrated on figure 4):

1. their intensities remain less than $`10^8\mathrm{W}/\mathrm{cm}^2`$, therefore present no risk of ionization damage on typical diatomic molecules;
2. their relatively broad Fourier transform ($`30\mathrm{cm}^1`$) shows the presence of non-negligible field components that can induce rotational excitations;
3. they are very sudden with respect to rotation (their positive component lasts typically 1 ps) and very asymmetric (the ratio of the positive to the negative maximum is more than 10).

A direct consequence is that such unipolar pulses can impart a “kick” to the molecule that effectively orients it in the direction of the positive field component, the transfer of angular momentum taking place on the timescale of the short pulse . The long-duration negative tail of the HCP is adiabatic enough not to induce further noticeable changes in the dynamics. Actually, the kick seems the most efficient orientation mechanism up to date. The results are illustrated on the LiCl molecule in terms of the dynamics of the average value of $`\mathrm{cos}\theta `$, in figure 5.

As in the two-color excitation scenario, the orientation remains modest during the positive part of the pulse, but it develops later and reaches the value $`\mathrm{cos}\theta 0.5`$ over a large time period of $`4\mathrm{ps}`$. The kick mechanism by itself can be evidenced by working out a sudden impact model . Such a model is based on the short duration ($`t_\mathrm{p}=1\mathrm{ps}`$) of the pulse as compared to the molecular rotational period ($`T_{\mathrm{rot}}=24\mathrm{ps}`$). The calculation consists in freezing the rotational dynamics during the time the positive part of the HCP is acting. At the lowest order, the approximation is valid as far as

$$\frac{B\widehat{J}^2t_\mathrm{p}}{\mathrm{}}0.13J\left(J+1\right)1,$$
(4.1)
where $`\widehat{J}`$ is the rotational kinetic operator and $`B`$ the rotational constant. The excellent agreement between this sudden impact approximation and the exact time-dependent calculation, with a root-mean-squared difference less than 0.03, eloquently advocates for the kick mechanism.

## 5. Optimal control scenarios

### 5.1. General frame

A completely different approach in its philosophy, without a priori reference to any dynamical mechanism, is optimal control. Such a scheme presents a general structure resting on three steps:

1. an evaluation function, $`\mathrm{cos}\theta (t)`$, involving the numerical solution of the time-dependent Schrödinger equation (using split operator  or basis expansion  techniques). For a laser-driven rigid rotor this amounts to solving

$$i\mathrm{}\frac{}{t}\psi (\theta ,\phi ,t)=\widehat{H}(t)\psi (\theta ,\phi ,t)$$
(5.1)
with

$$\widehat{H}(t)=B\widehat{J}^2\mu _0(t)\mathrm{cos}\theta \left[\left(\alpha _{}\alpha _{}\right)\mathrm{cos}^2\theta +\alpha _{}\right]\frac{^2(t)}{2}$$
(5.2)
in order to calculate

$$\mathrm{cos}\theta (t)=_0^{2\pi }_0^\pi \left|\psi (\theta ,\phi ;t)\right|^2\mathrm{cos}\theta \mathrm{sin}\theta d\theta d\phi $$
(5.3)
2. a set of parameters defining the temporal shape of the laser pulse, given here as a superposition of individual sine-square functions with intermediate plateau values,

$$(t)=\underset{n=1}{\overset{N}{}}_n(t)\mathrm{sin}\left(\omega _nt+\varphi _n\right)$$
(5.4)
with

$$_n(t)=\{\begin{array}{ccccc}0\hfill & \text{if }\hfill & & t& t_{n0}\hfill \\ _{n0}\mathrm{sin}^2\left[\frac{\pi }{2}\left(\frac{tt_{n0}}{t_{n1}t_{n0}}\right)\right]\hfill & \text{if }\hfill & \hfill t_{n0}& t& t_{n1}\hfill \\ _{n0}\hfill & \text{if }\hfill & \hfill t_{n1}& t& t_{n2}\hfill \\ _{n0}\mathrm{sin}^2\left[\frac{\pi }{2}\left(\frac{t_{n3}t}{t_{n3}t_{n2}}\right)\right]\hfill & \text{if }\hfill & \hfill t_{n2}& t& t_{n3}\hfill \\ 0\hfill & \text{if }\hfill & & t& t_{n3}\hfill \end{array}$$
(5.5)
3. a target $`j`$, i.e., an optimization criterion.

The optimization aims at the obtainment of the laser parameters (intensity, frequency, temporal shape defined by rise and fall times, together with possible plateau durations) that optimally satisfy the target $`j`$. The optimization procedure we use is based on genetic algorithms  operating in a $`7N`$ dimensional parameter space (i.e., 7 parameters for each of the $`N`$ individual pulses). It is worthwhile noting that a given criterion puts the emphasis on a specific feature of the orientation, such that different criteria may lead to quite different results. This is basically related to the fact that orientation can by no way be achieved by monitoring a single quantum state or a unique and pre-determined superposition of states. We will analyze in some detail the consequences of the choice of specific criteria. But before doing this, let us proceed to a first optimization retaining an intuitive, simple criterion that consists in the maximization of $`\mathrm{cos}\theta `$ for a single time $`t_\mathrm{f}`$ when the laser field is off,

$$j=\left|\mathrm{cos}\theta (t_\mathrm{f})\right|.$$
(5.6)
### 5.2. The kicked molecule

The optimal electric field which is obtained and illustrated in figure 6(a) turns out to be one of the most enlightening results of this study.

A combination of three individual pulses (i.e., 21 parameters to be optimized) leads to a very sudden and asymmetric pulse, followed by a null plateau and some rather symmetrical oscillations. The molecule (HCN taken as a rigid rotor, in this example) orients through the already discussed kick mechanism due to the fast angular momentum transfer by the unipolar pulse at about $`t=0.3\mathrm{ps}`$ and during the null plateau lasting 1 ps. The symmetrical oscillations of this field between 1 and 1.7 ps do not seem to play a major part in this dynamics. Here again, the kick mechanism can be evidenced by a sudden impact approximation which closely follows the $`\mathrm{cos}\theta `$ dynamics at least until 1.5 ps \[see figure 6(b)\]. It is important to note that an accuracy of 4 digits in the genetic algorithm is achieved for the intensities, frequencies, and absolute phase differences in order to produce the particular shape of the electric field of figure 6(a), responsible of the subsequent kick mechanism. Figure 7 accounts for the long-time dynamics (i.e., for full rotational period).

Maximum orientation is reached at about $`t10\mathrm{ps}`$ and lasts for about 3 ps. It is interesting to note that the result of the sudden impact model based on the first kick (at $`0.5\mathrm{ps}`$) can further be improved by introducing the effect of the oscillatory field acting after the null plateau as a second kick (that is again freezing the rotational motion during the time over which the molecule experiences this second interaction).

An analysis of the optimized laser pulse obtained can be carried out using the short-time Fourier transform of the electric field, given by

$$(\omega ,t)=_{\mathrm{}}^+\mathrm{}(\tau )f_\mathrm{w}(\tau t)e^{i\omega \tau }𝑑\tau ,$$
(5.7)
with $`f_\mathrm{w}`$ a windowing function (we have taken a Tukey-Hanning window  of total width 0.29 ps). The result is shown in figure 8

as a 2D representation of the electric field amplitude as a function of $`\omega `$ and $`t`$. The asymmetric feature present in the field at around $`0.15\mathrm{ps}`$ turns out to be the superposition of two components at frequencies $`\omega `$ and $`2\omega `$. This corresponds to the most asymmetrical electric field which, when truncated at a time that is not an integer of the optical period, leads to a non-zero field integral imparting the kick to the molecule. This is followed later on by a component centered around a single frequency which also leads to a second, smaller kick. Such a result has a broader applicability: the same pulse applied to a different molecule (e.g., LiF) produces similar orientation dynamics .

### 5.3. The optimization criteria

We now return to a thorough analysis of the consequences of choosing different criteria in the optimization scheme. Ideally, the best orientation is the one which is the most efficient (i.e., with a value of $`\mathrm{cos}\theta `$ close to one) and which lasts forever. The relative merits of the different criteria can thus be quantitatively measured in terms of the efficiency and the duration of the orientation. All calculations that are presented hereafter apply to the LiF molecule and are conducted within a parameter sampling space limited to frequencies comprised in between 500 and $`4000\mathrm{cm}^1`$, to individual pulses extinction times less than $`t_\mathrm{f}`$ taken as one tenth of a rotational period (as we are seeking post-pulse orientation resulting from a sudden excitation, which also helps in keeping calculations within acceptable CPU times) and to laser intensities not exceeding $`3\times 10^{13}\mathrm{W}/\mathrm{cm}^2`$ (to avoid risk of ionization damage, having in mind that $`1.1\times 10^{14}\mathrm{W}/\mathrm{cm}^2`$ is the predicted first ionization threshold for LiF).

The criteria can roughly be classified into two groups: simple, when they emphasize either efficiency or duration; hybrid, when they realize a compromise between efficiency and duration. Aiming at the best orientation efficiency, a more flexible criterion then the one that has been used so far \[equation (5.6)\] is

$$j_1\underset{t[t_f,t_f+T_{\mathrm{rot}}]}{\mathrm{max}}\left|\mathrm{cos}\theta (t)\right|,$$
(5.8)
the maximum being now taken at any time within the interval $`[t_f,t_f+T_{\mathrm{rot}}]`$ (taking into account the periodical behavior of the orientation dynamics with respect to the rotational period $`T_{\mathrm{rot}}`$). The result is displayed in figure 9.

The electric field thus obtained is built up from two individual pulses of comparable intensities, with frequencies in a ratio of 2 responsible for the double wiggles in the amplitude, as illustrated in figure 10.

Excellent orientation ($`\mathrm{cos}\theta 0.8`$) is achieved with a time delay of about 6 ps after the pulse is off. This molecular response time to the laser interaction is the time needed for the specific phase interferences to occur in the rotational wave packet. Such occurrences of the field-free dynamics are periodical (molecular rotational periodicity $`T_{\mathrm{rot}}`$), give rise to the revival structures discussed in the literature , and are common to all results presented hereafter.

The criterion $`j_1`$ fails in producing long-lasting orientation (the time interval over which $`\left|\mathrm{cos}\theta \right|`$ remains larger than 70% of its maximum value does not exceed 0.37 ps). Another criterion is built to precisely maximize the orientation duration $`\tau `$,

$$j_2\underset{t[t_f,t_f+T_{\mathrm{rot}}]}{\mathrm{max}}\frac{\tau }{T_{\mathrm{rot}}},$$
(5.9)
where $`\tau `$ is defined as the time over which an orientation exceeding $`j_1/\sqrt{2}`$ is kept,

$$\frac{j_1}{\sqrt{2}}\left|\mathrm{cos}\theta (t)\right|j_1.$$
(5.10)
The optimized electric field shows two intense, sudden, high frequency and well separated components (see figure 11), inducing a smooth behavior for $`\mathrm{cos}\theta (t)`$ as expected for large values of $`\tau `$, but unfortunately the orientation is very inefficient.

The weakness of these simple criteria may be overcome by building physically more sound hybrid criteria that combine the advantages of the previous requirements for a better compromise between efficiency and duration. Our best result is obtained with a criterion that maximizes a functional of $`\mathrm{cos}\theta ^2(t)`$ over an entire rotational period,

$$j_3\mathrm{max}\frac{1}{T_{\mathrm{rot}}}_{t_f}^{t_f+T_{\mathrm{rot}}}𝒞^2(t)𝑑t,$$
(5.11)
where $`𝒞(t)`$ is tailored as to put the emphasis on time intervals where $`\mathrm{cos}\theta `$ is larger than some fixed value (0.4 in our case) through an appropriate weighting factor (0.1 in our case):

$$𝒞(t)=\{\begin{array}{cc}0.1\mathrm{cos}\theta (t)& \text{if }\mathrm{cos}\theta (t)<0.4\hfill \\ \mathrm{cos}\theta (t)& \text{elsewhere}\hfill \end{array}$$
(5.12)
Figure 12 displays the optimized field built up from two sudden, intense pulses, with very close frequencies (742 cm<sup>-1</sup> and 808 cm<sup>-1</sup>) giving a beat-like structure. It is worthwhile noting that the resulting field appears as two beats of similar frequency $`780\mathrm{cm}^1`$ (see figure 13), but we failed in analyzing them in terms of a double kick mechanism (the sudden impact model not providing the expected orientation dynamics). Finally, in terms of quantitative measurements, this field achieves orientation which lasts for 0.7 ps with a $`\left|\mathrm{cos}\theta \right|`$ larger than 0.5, and is one of the best results of the literature.

### 5.4. Robustness with respect to temperature

All calculations so far presented concern an initially rotationless molecule, $`J=M=0`$, $`M`$ being the quantum number labelling the projection of the rotational angular momentum on the laser polarization vector taken as the laboratory reference axis. With respect to experimental conditions, such a situation concerns a molecule at a temperature of $`T=0\mathrm{K}`$. Starting from such a state (prepared by laser cooling methods, for instance ), linearly polarized photon absorption only populate higher $`J`$ levels; $`M`$, being a good quantum number (labelling an azimuthal angular motion, well separated due to cylindrical symmetry), remains unchanged (i.e., zero). Increasing temperature, on the other hand, populates higher $`J`$ levels with all their $`M`$ components, $`\left|M\right|=0,1,\mathrm{},J`$, within a Boltzmann distribution. For a given component, a vectorial representation of the field-driven classical rigid rotor leads to

$$\mathrm{sin}\theta =\frac{\left|M\right|}{J},$$
(5.13)
the total angular momentum vector $`𝐉`$ being orthogonal to the rigid rotor axis $`𝐑`$ and $`\theta `$ being the polar angle positioning $`𝐑`$ with respect to the laser polarization vector. Large values of $`M`$ would thus prevent alignment and orientation, $`\theta `$ reaching a value as high as $`\pi /2`$ for $`\left|M\right|=J`$, as illustrated in figure 14.

Using linearly polarized laser sources, no reduction of $`M`$ could be achieved, showing that orientation is no more a mathematically controllable process at non-zero temperature. Because they are breaking the overall cylindrical symmetry, elliptically polarized lasers are possible tools for modifying the values of $`M`$, in an optimally controlled way to lead again to alignment and orientation. Work in this direction is now undertaken in our group.

It remains however that the robustness of our optimal control scheme can be checked at least for some low temperatures. Instead of our previous evaluation function (5.3), we have to refer to a temperature dependent Boltzmann averaging of $`\mathrm{cos}\theta `$,

$$\mathrm{cos}\theta (t)=Q^1\underset{J}{\overset{J_{\mathrm{max}}}{}}\mathrm{exp}\left[\frac{BJ(J+1)}{k_BT}\right]\underset{M=J}{\overset{J}{}}\mathrm{cos}\theta _{J,M}(t),$$
(5.14)
where $`\mathrm{cos}\theta _{J,M}(t)`$ results from the dynamics of an individual initial state $`J,M`$ included in a summation over $`J`$ and $`M`$ with its appropriate exponential weighting factor, and a partition function

$$Q=\underset{J}{\overset{J_{\mathrm{max}}}{}}\left(2J+1\right)\mathrm{exp}\left[\frac{BJ(J+1)}{k_BT}\right],$$
(5.15)
for normalization.

Figure 15 presents the results for the LiF molecule at $`T=5\mathrm{K}`$.

Here again, simple ($`j_1`$) and hybrid ($`j_3`$-like) criteria are referred to. The dotted line (panel a) represents the orientation dynamics at 5 K \[equation (5.14)\] but with the electric field of figure 9(a) optimized for $`T=0\mathrm{K}`$. This is, precisely, to show how orientation effects are rapidly washed out when incorporating higher initial $`M`$’s. A field optimized for $`T=5\mathrm{K}`$ restitutes again the oscillatory structures of $`\mathrm{cos}\theta (t)`$, with however reduced amplitudes (solid line of panel a). A more satisfactory result requires the introduction of an additional individual pulse bringing 21 free parameters in the optimization scheme. The result in given in figure 9(b) with an orientation higher than $`\mathrm{cos}\theta =0.27`$ kept over a time of about $`0.25`$ ps. The result of the hybrid criterion $`j_3`$ with a 21-free-parameters optimization is illustrated in figure 9(c). A much longer time duration ($`0.4\mathrm{ps}`$) is achieved for about the same efficiency.

## 6. Conclusion

The complementarity between basic mechanisms and optimal control schemes can be summarized either by referring to the way of implementing mechanisms in control, or reversely of identifying mechanisms revealed from control.

The first strategy rests on three observations:

1. there is no single solution arising from optimal control scenarios (not only different criteria, but also different sampling spaces for parameters would lead to different results);
2. a careful study of the laser-induced dynamics can help to the identification (or guess) of some basic mechanisms leading to the desired observable;
3. by appropriately building the targets and delineating the parameter sampling space, we can help the optimal control scheme to take advantage of the mechanisms.

The second strategy consists in learning a dynamical mechanism presenting some robustness from the optimal control results. This mechanism may be used directly for reaching the desired observable (strategy 2) or further improved by implementing it again in a control scenario with some additional flexibility (strategy 1).

The kick mechanism and the optimal control carried out using sudden pulses is an example that illustrates these two routes. The mechanism has actually been depicted using half-cycle pulses and a sudden impact model. The parameter sampling space for the optimal control, although not constrained, has been limited to sudden pulses that are precisely compatible with the kick mechanism. This control scenario has finally revealed a double-kick mechanism which can serve as a starting point of a train of kicks, that we can merely guess to provide even better orientation. Finally, this mechanism, together with some additional free parameters such as the time delay between the successive kicks, can be re-injected (re-introduced) in an optimal control scheme (strategy 1) aiming at improving its efficiency. We are presently pursuing some investigations in this direction.


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# Expressing Decoherence with Spectral and Stochastic Methods

## 1 Introduction

Decoherence in an open quantum system is the loss of quantum coherence due to the entanglement with its environment as a consequence of their mutual interaction . It precludes thus the formation of some superpositions of states, creating in the system environment-induced superselection rules . The rigorous mathematical expression of this phenomenon runs parallel to this scheme, namely, one should first consider the joint evolution of both the system and the environment and then take the partial trace over the environmental degrees of freedom . In general, the resulting evolution equation for the density operator of the system $`\rho _\mathrm{S}`$ is non-markovian and extremely difficult to handle. This is the reason why suitable approximations have been traditionally pursued. In particular, adequate methods to derive an approximate *markovian* equation have been found . On the other hand, more axiomatic results have also been developed which pose some general physical conditions for the evolution of the system density operator  and arrive at the general form for the evolution equation of $`\rho _\mathrm{S}`$. Both approaches show pros and cons: the axiomatic program starts by assuming the markovianity of the evolution as one of the physical hypotheses, thus making rather difficult the generalization to non-markovian situations, which, due to experimental progress, are becoming interesting enough to develop theoretical tools. On the other hand, the constructive approach depends very sensitively on the particular model of interaction between the system and its environment, thus rendering it rather inappropiate for generic discussion beyond precise details.
Here we suggest another proposal which embraces both markovian and non-markovian situations, like the constructive approach, but it does not depend, in general terms, on the specific features of the system-environment interaction. The physical picture which motivates this scheme models the effect of the environment upon the system by a random perturbation of the evolution operator. Since the origin of the stochasticity is rooted upon the environment and since we do not have control over its degrees of freedom, we then take the stochastic expectation value. This is of course not new, and indeed it has been used in classical physics too . The novel proposal stems from the combination of this old idea with the spectral decomposition theorem for the evolution operator . This combination will turn out to be quite useful to express decoherence in certain models.
The paper is organized as follows. In section 2 the general scheme of this proposal is presented, then in section 3 the case of global random perturbations of the Hamiltonian spectrum is studied to arrive at a Lindblad-type evolution equation both when the Lindblad operators are selfadjoint (subsection 3.1) and nonselfadjoint (subsection 3.2). In the following section (4) a detailed example of the conjuction of the spectral decomposition and stochastic methods is worked out. A brief discussion and some conclusions are then presented in section 5. Finally we close the paper with a computational appendix (A) and a mathematical proof (B).

## 2 General scheme

To show how stochastic methods and the spectral decomposition theorem are combined, consider a quantum system with hamiltonian $`H`$, which for simplicity’s sake will be discrete and nondegenerate. The evolution equation for this system will then be given by the evolution operator $`U(t)=\mathrm{exp}(\mathrm{}tH)`$, which by means of the spectral decomposition of $`H=_kϵ_kP_k`$ can be expressed as ($`\mathrm{}=1`$ as usual)

$$U(t)=\underset{k}{}e^{\mathrm{}ϵ_kt}P_k$$
(2.1)
The operator $`U(t)`$ will then be randomly perturbed as the following relation shows

$$U(t)=\underset{k}{}e^{\mathrm{}ϵ_kt}P_kU_{st}(t)=\underset{k}{}e^{\mathrm{}\chi _k(t)}P_k$$
(2.2)
where $`\chi _k(t)`$ denotes a real-valued stochastic process for each $`k`$. The system density operator $`\rho _\mathrm{S}(t)`$ at time $`t`$ will then be given by the expectation value $`\rho _\mathrm{S}(t)=𝔼[U_{st}(t)\rho (0)U_{st}^{}(t)]`$. The density operator, in the Hamiltonian eigenvector basis, is then given by

$$\rho _{n,m}(t)=𝔼[e^{\mathrm{}(\chi _n(t)\chi _m(t))}]\rho _{n,m}(0)$$
(2.3)
where it has been supposed that the system and the environment are not initially correlated, thus $`\rho (0)`$ is not random. Both the original unitary evolution and the decoherence function are contained in the expectation value $`𝔼[e^{\mathrm{}(\chi _n(t)\chi _m(t))}]`$ and should then be properly disentangled. To do this note that the “stochastic promotion” expressed by (2.2) can be very intuitively understood if we express the argument of the exponential in the original evolution operator as an integral and the stochastic process $`\chi _k(t)`$ is written as an Ito process

$$e_kt=_0^te_k𝑑s\chi _k(t)=_0^ta_k(s)𝑑s+_0^tb_k(s)𝑑_k(s)$$
(2.4)
where $`a_k(t)`$ and $`b_k(t)`$ are real-valued stochastic processes for each $`k`$ and $`_k(t)`$ are standard real Brownian motions for each $`k`$.
Under full generality the previous expectation value cannot be computed, but with some general physical assumptions some useful results may rapidly arise. As a very elementary example consider for instance the white-noise perturbation, i.e.

$$e_kte_kt+_0^te_k\xi (s)𝑑s=e_kt+e_k_k(t)$$
(2.5)
where $`\xi (t)`$ denotes white noise with correlation properties $`𝔼[\xi (t)]=0`$, $`𝔼[\xi (t)\xi (s)]=\gamma \delta (ts)`$. Note that all eigenvalues are perturbed by the same stochastic noise $`\xi (t)`$. Under this assumption and after computing the expectation value

$$𝔼[e^{\mathrm{}(e_ke_k^{})_0^t\xi (s)𝑑s}]=e^{\frac{\gamma t}{2}(e_ke_k^{})^2}$$

the elements of $`\rho _\mathrm{S}(t)`$ in the Hamiltonian eigenvector basis are given by

$$\rho _{n,m}(t)=\rho _{n,m}^{(0)}(t)e^{\frac{\gamma t}{2}(e_ne_m)^2}$$
(2.6)
where $`\rho ^{(0)}(t)`$ denotes the unitarily evolved density operator. The corresponding evolution equation for $`\rho _\mathrm{S}`$ is straightforwardly shown to be the markovian phase-destroying master equation (see  for an alternative deduction)

$$\frac{d\rho _\mathrm{S}(t)}{dt}=\mathrm{}[H,\rho _\mathrm{S}(t)]\frac{\gamma }{2}[H,[H,\rho _\mathrm{S}(t)]]$$
(2.7)
Thus the effect of the environment can be understood as a *global* random energy “kick” upon the system. This method also provides a very fast way to solve equation (2.7) provided one knows the solution to the unitary evolution (cf.  for an explicit example).

## 3 Global perturbations

### 3.1 Selfadjoint Lindblads

The *global* random perturbations like in the example in the preceding section can also be expressed without resorting to the spectral decomposition theorem. A partial treatment was provided in , where the most general Lindbladian evolution with selfadjoint Lindblad operators was obtained. Here we offer a complementary proof of this result which uses different techniques and thus paves the way for later generalizations (nonselfadjoint Lindblad operators). Let $`H`$ be the Hamiltonian of the system. Introduce now a global random perturbation by adding the operator $`\eta (t)V`$ to $`H`$, where $`\eta (t)`$ denotes an arbitrary real-valued stochastic process and $`V`$ an arbitrary selfadjoint operator. The evolution operator will then read

$$U_{st}(t)=\mathrm{exp}[\mathrm{}tH\mathrm{}\eta (t)V]$$
(3.1)
The main trouble to compute $`\rho (t)𝔼[U_{st}(t)\rho (0)U_{st}^{}(t)]`$ stems from the commutativity properties of $`H`$ and $`V`$. If $`[H,V]=0`$ it can be readily shown  that the evolution equation for $`\rho _\mathrm{S}`$ is

$$\frac{d\rho _\mathrm{S}(t)}{dt}=\mathrm{}[H,\rho _\mathrm{S}(t)]\frac{1}{2}\frac{d}{dt}\eta _t[V,[V,\rho _\mathrm{S}(t)]]$$
(3.2)
where $`\eta _t`$ denotes the quadratic variation of $`\eta (t)`$ . When $`[H,V]0`$, the computation cannot be performed in the same way. An option to overcome this difficulty was presented in , where the stochastic perturbation was performed in the Heisenberg picture; here we resort to Feynman’s operational calculus . In particular, the following three Feynman’s heuristic rules to deal with functions of noncommuting operators will be thoroughly used:

1. Attach time indices to the operators to specify the order of operators in products.
2. With time indices attached, form functions of these operators by treating them as though they were commuting.
3. Finally, “disentangle” the resulting expressions; that is, restore the conventional ordering of the operators.

A mathematical formalization of each of these rules can be found in . Here we will only show how they can be used to prove our result. Consider then the evolution operator (3.1); attach time indices both to $`H`$ and $`V`$ so that one can write

$$U_{st}(t)=\mathrm{exp}\left(\mathrm{}_0^tH(s)𝑑s\mathrm{}_0^tV(s)𝑑\mu (s)\right)$$
(3.3a)
where $`d\mu (t)`$ denotes the Lebesgue-Stieltjes measure $`\eta (t)dt`$. Now treat both factors as though they were commuting:

$$U_{st}(t)=\mathrm{exp}\left(\mathrm{}_0^tH(s)𝑑s\right)\mathrm{exp}\left(\mathrm{}_0^tV(s)𝑑\mu (s)\right)$$
(3.3b)
The density operator then reads

$$\rho (t)=e^{\mathrm{}_0^tH(s)𝑑s}𝔼\left[\mathrm{exp}\left(\mathrm{}_0^tV(s)𝑑\mu (s)\right)\rho (0)\mathrm{exp}\left(\mathrm{}_0^tV(s)𝑑\mu (s)\right)\right]e^{\mathrm{}_0^tH(s)𝑑s}$$
(3.3c)
Now the expectation value can be computed using (see also appendix A) $`\mathrm{}^\mathrm{}AB\mathrm{}^\mathrm{}A=\mathrm{}^{\mathrm{}[A,]}B`$ with $`A=A^{}`$, where $`\mathrm{}^{\mathrm{}[A,]}B_{n=0}^{\mathrm{}}\frac{(\mathrm{})^n}{n!}[A,[A,[A,\stackrel{n}{\mathrm{}},[A,B]]]]`$:

$$𝔼\left[\mathrm{exp}\left(\mathrm{}_0^tV(s)𝑑\mu (s)\right)\rho (0)\mathrm{exp}\left(\mathrm{}_0^tV(s)𝑑\mu (s)\right)\right]=\mathrm{exp}\left(\frac{1}{2}[_0^tV^2(s)d\eta _s,]\right)\rho (0)$$
(3.3d)
And finally, restore the conventional ordering of the operators:

$$\rho _\mathrm{S}(t)=\mathrm{exp}\left(\mathrm{}[H,]\frac{1}{2}\eta _t[V^2,]\right)\rho (0)$$
(3.3e)
which drives us to the master equation

$$\frac{d\rho _\mathrm{S}(t)}{dt}=\mathrm{}[H,\rho _\mathrm{S}(t)]\frac{1}{2}\frac{d}{dt}\eta _t[V,[V,\rho _\mathrm{S}(t)]]$$
(3.3f)
We have proved the main result found in  with other means: *Any Lindbladian master equation, either markovian or non-markovian, with selfadjoint Lindblad operators, can be understood as a random unitary evolution*. The generalization to many Lindblad operators can be readily accomplished by using several uncorrelated stochastic processes $`\eta _i(t)`$ $`i=1,\mathrm{},n`$. Note that the markovian case is obtained only when $`\eta _t`$ is linear in time, i.e. when $`\eta (t)=\mathrm{const}.+\gamma ^{1/2}_\mathrm{t}`$ which amounts to perturbing the original Hamiltonian by a white noise like in (2.5).

Complementarily one can also use these techniques to study the evolution of a system given by a Hamiltonian with one or several stochastic parameters in it. Take for instance the system with Hamiltonian $`H=H_1+\lambda (t)H_2`$ and let the parameter $`\lambda (t)`$ be uncontrollably random. Following the previous prescriptions the corresponding evolution operator will read

$$U_{st}(t)=𝒯\mathrm{exp}\left[\mathrm{}tH_1\mathrm{}H_2\left(\mu (t)+_0^t\stackrel{~}{\lambda }(s)𝑑(s)\right)\right]$$
(3.3d)
where $`𝒯`$ denotes the time-ordering operator and by definition $`_0^t\lambda (s)𝑑s\mu (t)+_0^t\stackrel{~}{\lambda }(s)𝑑(s)`$. The master equation for $`\rho _\mathrm{S}`$ will then be

$$\frac{d}{dt}\rho _\mathrm{S}(t)=\mathrm{}[H_1,\rho _\mathrm{S}(t)]\mathrm{}\dot{\mu }(t)[H_2,\rho _\mathrm{S}(t)]\frac{1}{2}\frac{d}{dt}\mu (t)+_0^t\stackrel{~}{\lambda }(s)𝑑(s)_t[H_2,[H_2,\rho _\mathrm{S}(t)]]$$
(3.3e)
This scheme has already been used  to study the effects of laser intensity and phase fluctuations in ion traps. In more general terms, these techniques appear very suitable to deal with approximate models in which the approximation renders the physical realistic situation mathematically manageable to perform computations, but on the other hand it ineludibly carries some decohering effect in it. An explicit example was worked out in , where the Jaynes-Cummings model (JCM hereafter) was revisited within this approach. The JCM is a crude, though very appropiate, approximation to deal with the interaction between an atom and the electromagnetic field in certain circumstances (cf. ) which reduces both systems to a two-level system and a harmonic oscillator, respectively, interacting via a Hamiltonian $`H_I=\lambda (\sigma _{}a^{}+\sigma _+a)`$, where $`\lambda `$ is the coupling constant, $`\sigma _\pm `$ are the raising/lowering atomic operators and $`a(a^{})`$ are the annihilation (creation) field mode operators. It is then clear that the rest of field modes as well as other atomic degrees of freedom are completely neglected, thus providing an ideal situation to quantitatively describe some physical phenomena like Rabi oscillations, periodic collapses and revivals or squeezing . Decoherence is absent in this model, however experimental results  show the opposite, though extremely difficult to be attributed to the environment. This tiny decoherence effect may be incorporated into the model from the beginning by letting the coupling constant $`\lambda `$ have a random character, this randomness coming from the effect of the neglected degrees of freedom. The theoretical predictions are in good agreement with experimental results . Note that within this approach decoherence should be understood as an *intrinsic* phenomenon stemming out from the adopted approximation and thus being an inherent property in those models which neglects degrees of freedom of the system. Notice how despite providing the same analytical behaviour, this approach conceptually differs from others in which a quantum bosonic reservoir is explicitly taken into account .

### 3.2 Nonselfadjoint Lindblads

A natural question arises concerning whether it is possible or not ot arrive at a Lindbladian master equation with Lindblad operators not necessarily selfadjoint like in the previous examples. And the answer is positive but with important remarks. To be concrete let us consider a spin-$`1/2`$ interacting with a random magnetic field $`𝐁(t)=B_\mathrm{x}(t)\widehat{𝐱}+B_\mathrm{y}(t)\widehat{𝐲}+B_\mathrm{z}(t)\widehat{𝐱}`$. The Hamiltonian describing the evolution of the spin will then be

$$H(t)=\omega _0\sigma _\mathrm{z}+𝐁(t)𝝈$$
(3.3f)
Complementarily this can be viewed as a quantum bit (left term of the rhs of (3.3f)) undertaking a logical operation in a noisy environment (right term of the rhs). Without loss of generality we can focus on those cases in which $`𝐁(t)𝐳=0`$, since otherwise we can use the tools developed in the preceding section. The evolution operator will then be

$$U_{st}(t)=𝒯\mathrm{exp}\left[\mathrm{}\omega _0t\mathrm{}_0^t\left(B_\mathrm{x}(s)\sigma _\mathrm{x}+B_\mathrm{y}(s)\sigma _\mathrm{y}\right)𝑑s\right]$$
(3.3ga)
Since we will make use of Feynman’s operational calculus as in previous paragraphs, we can concentrate on the operator

$$\stackrel{~}{U}_{st}(t)=𝒯\mathrm{exp}\left[\mathrm{}_0^t\left(B_\mathrm{x}(s)\sigma _\mathrm{x}(s)+B_\mathrm{y}(s)\sigma _\mathrm{y}(s)\right)𝑑s\right]$$
(3.3gb)
The magnetic field components will be expressed through Ito integrals as

$`{\displaystyle _0^t}B_\mathrm{x}(s)𝑑s`$ $``$ $`{\displaystyle _0^t}b_\mathrm{x}(s)𝑑_\mathrm{x}(s)`$ (3.3gha)
$`{\displaystyle _0^t}B_\mathrm{y}(s)𝑑s`$ $``$ $`{\displaystyle _0^t}b_\mathrm{y}(s)𝑑_\mathrm{y}(s)`$ (3.3ghb)
where the $`b_k(t)`$’s are arbitrary deterministic real-valued functions and $`_k(t)`$ denotes nonstandard real Brownian motions (cf. below). The careful reader may argue at first sight that this is not the more general form for a real stochastic process, and it is not, though it contains all physically relevant cases which interest us in this analysis. To prove that, we begin by demanding that the magnetic field components be martingales , which is general enough from a physical standpoint. Then making use of the martingale representation theorem, they can be uniquely written as

$$_0^tB_k(s)𝑑s=𝔼\left[_0^tB_k(s)𝑑s\right]+_0^tg_k(s)𝑑_k(s)k=\mathrm{x},\mathrm{y}$$
(3.3ghi)
where $`g_k(t)`$ is a real stochastic process depending on the particular choice of $`B_k(t)`$. Without loss of generality we take $`𝔼[B_k]=0`$ since otherwise this factor can be included in the dropped-out exponential after application of Feynman’s rules and finally recovered back in the final step. We are interested in those effects coming out from the stochasticity of the Hamiltonian and which are at the end detected after calculating the stochastic average. This is the reason why we can also consider the processes $`g_k(t)`$’s as being deterministic.
The correlations properties of the magnetic field components will be generically expressed through the correlation properties of the Brownian motions

$`𝔼[_\mathrm{x}^2(t)]`$ $`=`$ $`\gamma _\mathrm{x}t`$ (3.3ghja)
$`𝔼[_\mathrm{y}^2(t)]`$ $`=`$ $`\gamma _\mathrm{y}t`$ (3.3ghjb)
$`𝔼[_\mathrm{x}(t)_\mathrm{y}(t)]`$ $`=`$ $`\gamma _{\mathrm{xy}}t`$ (3.3ghjc)
In order to expouse clearly the role played by the correlation properties between both componentes, let us concentrate upon white-noise process, i.e. $`b_\mathrm{x}(t)=b_\mathrm{y}(t)=1`$ (equivalently $`B_\mathrm{x}(t)=B_\mathrm{y}(t)=\xi (t)`$). Now we decompose $`\sigma _\mathrm{x}`$ and $`\sigma _\mathrm{y}`$ in terms of the raising and lowering operators to rewrite (3.3gb) as

$$\stackrel{~}{U}_{st}(t)=𝒯\mathrm{exp}\left[\mathrm{}_0^t\left(B(s)\sigma _+(s)+B^{}(s)\sigma _{}(s)\right)𝑑s\right]$$
(3.3ghjka)
where $`B(t)`$ is a *complex* stochastic process with $`B(t)=B_\mathrm{x}(t)`$ and $`B(t)=B_\mathrm{y}(t)`$. Alternatively equation (3.3ghjka) can be rewritten as

$$\stackrel{~}{U}_{st}(t)=𝒯\mathrm{exp}\left[\mathrm{}_0^t\sigma _+(s)𝑑(s)\mathrm{}_0^t\sigma _{}(s)𝑑^{}(s)\right]$$
(3.3ghjkb)
where $`(t)`$ is a complex stochastic process with correlation properties given by

$`𝔼[B^2(t)]`$ $`=`$ $`\left(\gamma _\mathrm{x}\gamma _\mathrm{y}\mathrm{}2\gamma _{\mathrm{xy}}\right)t`$ (3.3ghjkla)
$`𝔼[B(t)B^{}(t)]`$ $`=`$ $`(\gamma _\mathrm{x}+\gamma _\mathrm{y})t`$ (3.3ghjklb)
Now using again $`\mathrm{}^\mathrm{}AB\mathrm{}^\mathrm{}A=\mathrm{}^{\mathrm{}[A,]}B`$ with $`A=A^{}`$ we compute the stochastic expectation value $`\stackrel{~}{\rho }(t)𝔼\left[\stackrel{~}{U}_{st}(t)\rho (0)\stackrel{~}{U}_{st}^{}\right]`$:

$$\stackrel{~}{\rho }(t)=𝒯𝔼\left[\mathrm{exp}\left(\mathrm{}_0^t[\sigma _+(s),]𝑑(s)\mathrm{}_0^t[\sigma _{}(s),]𝑑^{}(s)\right)\right][\rho (0)]$$
(3.3ghjklm)
After computing this expectation value (see appendix A) and restoring the conventional time ordering of operators, the final result is (up to Hamiltonian factors)

$$\stackrel{~}{\rho }(t)=\mathrm{exp}\left[t\left(_{\mathrm{xy}}+_++_{}+𝒟_{\mathrm{xy}}\right)\right][\rho (0)]$$
(3.3ghjkln)
where

$`_{\mathrm{xy}}`$ $``$ $`{\displaystyle \frac{\gamma _\mathrm{x}\gamma _\mathrm{y}}{2}}\left([\sigma _\mathrm{x},[\sigma _\mathrm{x},]][\sigma _\mathrm{y},[\sigma _\mathrm{y},]]\right)`$ (3.3ghjkloa)
$`_\mathrm{j}`$ $``$ $`(\gamma _\mathrm{x}+\gamma _\mathrm{y})([\sigma _\mathrm{j},\sigma _\mathrm{j}^{}]+[\sigma _\mathrm{j},\sigma _\mathrm{j}^{}])j=+,`$ (3.3ghjklob)
$`𝒟_{\mathrm{xy}}`$ $``$ $`2\gamma _{\mathrm{xy}}\left(\sigma _\mathrm{x}\sigma _\mathrm{y}+\sigma _\mathrm{y}\sigma _\mathrm{x}\right)`$ (3.3ghjkloc)
The first two generators are Lindblad generators, thus denoting a completely positive markovian evolution  whereas the last one is not. Since the evolution is clearly markovian, this means that complete positivity is not ensured during the evolution. It is remarkable how once more the presence of correlations spoils the complete positivity . In fact this is a clear example of how correlations *within the environment*, even in the case of no correlations between the system and this environment, prevents the evolution from being completely positive (see B for a mathematical proof of this fact). Notice however that when the random magnetic field is isotropic ($`\gamma _\mathrm{x}=\gamma _\mathrm{y}`$) and the components are uncorrelated ($`\gamma _{\mathrm{xy}}=0`$), a fully Lindblad evolution is recovered with dissipative generator given by (3.3ghjklob), i.e. a Lindblad evolution with nonselfadjoint Lindblad operators. Nevertheless this generator shows two opposite parts which within this approach cannot be separated. Physically this is rooted upon the isotropy of the magnetic field which, as expected, drives the system with equal probability both to the ground and to the excited state.
The generalization to nonmarkovian evolution can be performed with little extra effort. For simplicity we keep the isotropy condition, thus $`b_\mathrm{x}(t)=b_\mathrm{y}(t)b(t)`$. The random evolution operator will then be

$$\stackrel{~}{U}_{st}(t)=𝒯\mathrm{exp}\left(\mathrm{}_0^tb(s)\sigma _+(s)𝑑(s)\mathrm{}_0^tb(s)\sigma _{}(s)𝑑^{}(s)\right)$$
(3.3ghjklop)
where the complex stochastic process $`(t)`$ have the same correlation properties as above. The calculation proceeds along similar lines with result

$$\stackrel{~}{\rho }(t)=\mathrm{exp}\left[\mathrm{\Lambda }(t)\left(_{\mathrm{xy}}+_++_{}+𝒟_{\mathrm{xy}}\right)\right][\rho (0)]$$
(3.3ghjkloq)
where the generators are the same as before and $`\mathrm{\Lambda }(t)_0^tb^2(s)𝑑s`$. This is clearly nonmarkovian and reduces to the markovian case only when $`b(t)=\mathrm{const}`$. Regretfully the previous calculations show that the dissipative generator appears always in opposite pairs. The conditions under which a single dissipative Lindblad generator is obtained are being currently under study (see also  for an alternative approach).

## 4 Local perturbations

But the versatility of the spectral decomposition theorem appears when the perturbation does not affect the whole system globally, as in the previous examples. By this we mean that in the random perturbation (2.4) the Brownian motions $`_k(t)`$ do not show singular correlation properties<sup>1</sup><sup>1</sup>1Note that in the previous cases –global perturbations– the processes $`_k(t)`$’s satisfied $`𝔼[_k(t)_k^{}(t)]=t`$ for all pairs $`k,k^{}`$, i.e. all $`_k(t)`$’s were esentially copies of the same standard one $`(t)`$ in (2.5)., but rather general ones. Take for instance the case in which

$$e_kte_kt+\gamma e_k_k(t)$$
(3.3ghjkloa)
with correlation properties $`𝔼[_k(t)_k^{}(t)]=\delta _{kk^{}}t`$. Under this assumption (which physically can be understood as the independent or incoherent effect of the environment upon each system energy level), the density operator components are given by

$`\rho _{nm}(t)`$ $`=`$ $`\rho _{nn}^{(0)}(t)n=m`$ (3.3ghjkloba)
$`=`$ $`\rho _{nm}^{(0)}(t)e^{\frac{\gamma t}{2}(e_n^2+e_m^2)}nm`$ (3.3ghjklobb)
which show a faster decoherence than (2.6). By choosing another correlation properties among the $`_k(t)`$’s one can arrive at more general decoherence functions for the decay of off-diagonal terms of the density operator. As a prominent example let us consider two quantum particles interacting through a central potential $`V(r_{12})`$. The Hamiltonian will then be given by

$$H=H_1^0+H_2^0+H_{12}=\frac{1}{2m_1}\mathrm{\Delta }_1\frac{1}{2m_2}\mathrm{\Delta }_2+\lambda V(r_{12})$$
(3.3ghjklobc)
where $`\lambda `$ is a coupling constant and $`r_{12}|𝐫_1𝐫_2|`$. In terms of the center-of-mass $`𝐑_{CM}𝐑`$ and the relative position $`𝐫_{12}𝐫`$ coordinates, the Hamiltonian is given by

$$H=\frac{1}{2M}\mathrm{\Delta }_{\mathrm{CM}}\frac{1}{2\mu }\mathrm{\Delta }_{\mathrm{rel}}+\lambda V(r)$$
(3.3ghjklobd)
with $`M`$ and $`\mu `$ the total and reduced masses respectively. The total energy is written as

$$E_T=E_{CM}+E_{rel}$$
(3.3ghjklobe)
so that the corresponding evolution operator will then be given by

$$U(t)=_{\sigma (H_{\mathrm{CM}})\times \sigma (H_{\mathrm{rel}})}e^{\mathrm{}tE_T}𝑑P(E_T)$$
(3.3ghjklobf)
Now a weak environment-system coupling can be expressed through a random perturbation of the total energy $`E_T`$ by a stochastic amount generically expressed like $`e(s;E_T)𝑑(s;E_T)`$ where $`e(s;E_T)\overline{e}(s;E_{\mathrm{CM}})`$ only depends on the center of mass and where the standard real Brownian motions show correlation properties only dependent on the center of mass variables as well. This is the main physical hypothesis and it is expressed as follows

$`U_{st}(t)`$ $`=`$ $`{\displaystyle _{\sigma (H_{\mathrm{CM}})\times \sigma (H_{\mathrm{rel}})}}e^{\mathrm{}tE_T\mathrm{}_0^te(s;E_T)𝑑(s;E_T)}𝑑P(E_T)`$ (3.3ghjklobga)
$`=`$ $`{\displaystyle _{\sigma (H_{\mathrm{CM}})\times \sigma (H_{\mathrm{rel}})}}e^{\mathrm{}tE_T\mathrm{}_0^t\overline{e}(s;E_{\mathrm{CM}})𝑑(s;E_T)}𝑑P(E_T)`$ (3.3ghjklobgb)
with $`𝔼[(t;E_T)(t;E_T^{})]=g(t;E_T,E_T^{})`$. Note that the correlation function satisfies

$`g(t;E_T,E_T)`$ $`=`$ $`1`$ (3.3ghjklobgha)
$`g(t;E_T,E_T^{})`$ $``$ $`1`$ (3.3ghjklobghb)
$`g(t,E_T,E_T^{})`$ $`=`$ $`\overline{g}(t;E_{\mathrm{CM}},E_{\mathrm{CM}}^{})`$ (3.3ghjklobghc)
where the last equation reflects the assumed physical hypothesis. Then if we denote the stochastic process

$$\eta (t;E_T,E_T^{})_0^te(s;E_T)𝑑(s;E_T)_0^te(s;E_T^{})𝑑(s;E_T^{})$$

the components of the density operator in the basis $`|E_{\mathrm{CM}};E_{\mathrm{rel}}`$ will then be given by

$$E_{\mathrm{CM}};E_{\mathrm{rel}}|\rho (t)|E_{\mathrm{CM}}^{};E_{\mathrm{rel}}^{}=\rho ^{(0)}(E_{\mathrm{CM}},E_{\mathrm{rel}};E_{\mathrm{CM}}^{},E_{\mathrm{rel}}^{})e^{\frac{1}{2}\eta (;E_T,E_T^{})_t}$$
(3.3ghjklobghi)
Now the quadratic variation of $`\eta `$ can be calculated in terms of the correlation function $`g`$ above:

$`\eta (;E_T,E_T^{})_t`$ $`=`$ $`{\displaystyle _0^t}\left[e^2(s;E_T)+e^2(s;E_T^{})2g(s;E_T,E_T^{})e(s;E_T)e(s;E_T^{})\right]𝑑s=`$ (3.3ghjklobghj)
$`=`$ $`{\displaystyle _0^t}\left[\overline{e}^2(s;E_{\mathrm{CM}})+\overline{e}^2(s;E_{\mathrm{CM}}^{})2\overline{g}(s;E_{\mathrm{CM}},E_{\mathrm{CM}}^{})\overline{e}(s;E_{\mathrm{CM}})\overline{e}(s;E_{\mathrm{CM}}^{})\right]𝑑s`$
$``$ $`\overline{\eta }(;E_{\mathrm{CM}},E_{\mathrm{CM}}^{})_t`$
Note that $`\eta (;E_T,E_T)_t=0`$, thus the trace is conserved. Also notice that components showing quantum coherence for different center-of-mass modes asymptotically vanish, since

$$\frac{d}{dt}\eta (;E_T,E_T^{})_t(\overline{e}(s;E_{\mathrm{CM}})\overline{e}(s;E_{\mathrm{CM}}^{}))^20$$
(3.3ghjklobghk)
On the other hand, full quantum coherence is kept for the relative coordinate, thus internal dynamics is not affected. A particular example of this scheme has been applied to arrive at the experimental expressions obtained in the study of Rabi oscillations in an ion trap .
This same technique can also be applied in those cases in which the randomness appears only in one part of the total Hamiltonian. Let for instance $`H=H_0+H_\mathrm{I}`$ be the total Hamiltonian of a quantum system and suppose that the randomness affects only the interaction part of $`H`$, i.e. $`H_\mathrm{I}`$. One has two complementary alternatives. On one hand, one may change to the $`H_0`$-picture and then apply the preceding techniques to the evolution operator $`U_{\mathrm{int}}(t)=𝒯\mathrm{exp}\left(\mathrm{}_0^tH_\mathrm{I}(s)𝑑s\right)`$ where $`H_\mathrm{I}(t)`$ denotes the $`H_\mathrm{I}`$ Hamiltonian in $`H_0`$ representation, i.e. $`H_\mathrm{I}(t)=\mathrm{}^{\mathrm{}tH_0}H_\mathrm{I}\mathrm{}^{\mathrm{}tH_0}`$. On the other hand, one may also resort to Feynman’s operational calculus and “break” the exponential into two parts: a first deterministic exponential involving only $`H_0`$ and a second one involving the random interaction Hamiltonian $`H_I`$, which can now be expressed through the spectral decompostion theorem and then stochasticly promoted like above. Both approaches are equivalent.

## 5 Discussion and conclusions

The use of stochastic methods in Hilbert space is of course not new (cf.  and references therein). Here they have been used in conjuction with the spectral decomposition to accomodate a great variety of decoherence functions which may appear in realistic situations and which otherwise require more or less complex calculations. It is important to remark that the whole scheme presented above preserves the unitarity of the evolution operator, i.e. $`U_{st}(t)`$ is unitary with probability $`1`$. This is in contrast to the radically different usage of these methods in stochastic dynamical reduction theories (cf.  and references therein for diverse examples within this philosophy), where the norm of the initial state vector is not preserved (reduction) and thus one is obliged to introduce non-linear terms to keep the probability interpretation. A clear-cut example of the difference between the decoherence and the reduction behaviours appears in . Possible connections between these two distinct pictures (decoherence and reduction) are currently under study. We argue that these possible connections, if any, appear in those cases where an analytical continuation in the complex plane of the spectrum of the Hamiltonian is used , which requires extending the quantum mathematical formalism of Hilbert spaces to that of rigged Hilbert spaces. We further conjecture that obtaining a Lindbladian evolution equation with just one nonselfadjoint Lindblad operator is also related to the existence of complex Hamiltonian eigenvalues and thus to micro-irreversibility .
In author’s opinion, a remarkable advantage of the approach presented above (apart from some mathematical benefits in solving some master equations ) stems from the possibility of dealing with approximate (though necessary) descriptions such as the JCM, where the approximation itself carries an inherent decohering effect as a result of neglecting some degrees of freedom of the system. This effect has been expressed through the randomization of some internal parameters of the system Hamiltonian and contrasted with some experimental data . The good agreement achieved invites us to look for new realistic situations in which we can further check the utility of this approach. A second advantage obtained from the involved mathematical formalism is the easy and fast generalization to nonmarkovian situations. However the approach is of phenomenological nature, consequently if one is interested in specific details depending e.g. on the concrete interaction between the system and the environment, it is compulsory to resort to the well-known “tracing-out” methods .
To sum up, in this work we have shown how the conjuction of stochastic methods and the spectral decomposition theorem can provide the analytical expression for the experimental behaviour of certain decohering quantum systems in a rather simple form. The main idea consists of identifying the pervasive effect of the surrounding environment upon a quantum system as a random perturbation of its evolution operator. Diverse decoherence functions can be obtained by adequately choosing the correlation properties of the random parameters. As a matter of fact it can be proved that when there exists correlation between these different parameters, then the system evolution is not completely positive, providing a further physical condition by which complete positivity is broken. It has been shown, as a noticeable example, how in a compound system the center of mass may suffer from decohering effects whereas the internal dynamics, i.e. the internal modes of the system are completely unaffected. The utility of this approach to deal with some approximate descriptions of quantum systems has been briefly discussed.

## Appendix A Computation of $`𝔼\left[\mathrm{exp}\left(\mathrm{}𝔄(t)\right)\right]`$

Here we include the computation of the stochastic average of the exponential of a *random superoperator* $`𝔄(t)=_0^t\beta (s)𝔖(s)𝑑(s)`$, where $`\beta (s)`$ is a deterministic function, $`𝔖(s)`$ is an arbitrary superoperator and $`(s)`$ is a complex or real Brownian motion. By linearity of the expectation value, the computation reduces to find the $`n`$th order moment of $`𝔄(t)`$. To do this, notice that it can be expressed through the Ito equation $`d𝔄(t)=\beta (t)𝔖(t)d(t)`$ and then applying Ito’s formula to the function $`\psi (𝔄(t))=𝔄^n(t)`$. The $`n`$th order moment $`𝔐_n(t)𝔼[𝔄^n(t)]`$ then satisfies the recursive differential equation

$$d𝔐_n(t)=\frac{n(n1)}{2}𝔐_{n2}(t)\beta ^2(t)𝔖^2(t)d_tn2$$
(3.3ghjklobgha)
Recalling that $`𝔐_0=1`$ and $`𝔐_1=0`$ one finally arrives at

$`𝔐_{2n}(t)`$ $`=`$ $`{\displaystyle \frac{(2n)!}{2^nn!}}𝔎^n(t)`$ (3.3ghjklobghb)
$`𝔐_{2n+1}(t)`$ $`=`$ $`0`$ (3.3ghjklobghc)
where $`𝔎(t)_0^t\beta ^2(s)𝔖^2(s)dB_s`$. Substituting these relations in the series development of the exponential one immediately arrives at

$$𝔼[\mathrm{exp}\left(\mathrm{}𝔄(t)\right)]=\mathrm{exp}\left(\frac{𝔎(t)}{2}\right)$$
(3.3ghjklobghd)
## Appendix B Initially correlated environments might preclude completely positive system evolutions

Here we prove how the presence of quantum correlations inside the environment might prevent the system evolution from being completely positive, even when the system is not initially correlated with the environment. Let the whole system+environment be represented by a Hilbert space $`_\mathrm{S}_1_2`$, where $`_\mathrm{S}`$ corresponds to the system and $`_1_2`$ to the environment. Let the respective dimensions be $`N_\mathrm{S}`$, $`N_1`$ and $`N_2`$ and the generators of the group $`\mathrm{SU}(\mathrm{N}_\mathrm{k})`$ be denoted by $`\sigma _j^{(k)}`$, with $`j=1,\mathrm{},N_k`$. The most general joint density operator can then be written as

$`\rho _{\mathrm{S12}}`$ $`=`$ $`{\displaystyle \frac{1}{N_\mathrm{S}N_1N_2}}[𝕀_{\mathrm{S12}}+\alpha _i\sigma _i^{(\mathrm{S})}𝕀_1𝕀_2+\beta _j𝕀_\mathrm{S}\sigma _j^{(1)}𝕀_2+\gamma _k𝕀_\mathrm{S}𝕀_1\sigma _k^{(2)}+`$ (3.3ghjklobgha)
$`+`$ $`\delta _{ij}\sigma _i^{(\mathrm{S})}\sigma ^{(1)}𝕀_2+ϵ_{ik}\sigma _i^{(\mathrm{S})}𝕀_1\sigma _k^{(2)}+\eta _{jk}𝕀_\mathrm{S}\sigma _j^{(1)}\sigma _k^{(2)}+`$
$`+`$ $`\nu _{ijk}\sigma _i^{(\mathrm{S})}\sigma _j^{(1)}\sigma _k^{(2)}]`$
Then denoting $`\rho _k(t)=\mathrm{Tr}_{\mathrm{lm}}\left(\mathrm{U}_{\mathrm{S12}}(\mathrm{t})\rho _{\mathrm{S12}}(0)\mathrm{U}_{\mathrm{S12}}^{}(\mathrm{t})\right)`$ with $`lkm`$, it is elementary to prove that $`\rho _{\mathrm{S12}}`$ can be rewritten as

$`\rho _{\mathrm{S12}}`$ $`=`$ $`\rho _\mathrm{S}\rho _1\rho _2+\delta _{ij}^{}\sigma _i^{(\mathrm{S})}\sigma ^{(1)}𝕀_2+ϵ_{ik}^{}\sigma _i^{(\mathrm{S})}𝕀_1\sigma _k^{(2)}+`$ (3.3ghjklobghb)
$`+`$ $`\eta _{jk}^{}𝕀_\mathrm{S}\sigma _j^{(1)}\sigma _k^{(2)}+\nu _{ijk}^{}\sigma _i^{(\mathrm{S})}\sigma _j^{(1)}\sigma _k^{(2)}`$
where

$`\delta _{ij}^{}{\displaystyle \frac{1}{N_\mathrm{S}N_1N_2}}\left(\delta _{ij}\alpha _i\beta _j\right)`$ $`ϵ_{ij}^{}{\displaystyle \frac{1}{N_\mathrm{S}N_1N_2}}\left(ϵ_{ij}\alpha _i\gamma _j\right)`$ (3.3ghjklobghca)
$`\eta _{ij}^{}{\displaystyle \frac{1}{N_\mathrm{S}N_1N_2}}\left(\eta _{ij}\beta _i\gamma _j\right)`$ $`\nu _{ijk}^{}{\displaystyle \frac{1}{N_\mathrm{S}N_1N_2}}\left(\nu _{ijk}\alpha _i\beta _j\gamma _k\right)`$ (3.3ghjklobghcb)
From this and after well-known arrangements , it is easy to arrive at

$`\rho _\mathrm{S}(t)`$ $`=`$ $`{\displaystyle \underset{ab}{}}{\displaystyle \underset{a^{}b^{}}{}}M_{ab,a^{}b^{}}(t)\rho _\mathrm{S}(0)M_{ab,a^{}b^{}}^{}+`$
$`+`$ $`\delta _{ij}^{}\mathrm{Tr}_{12}\left(\mathrm{U}(\mathrm{t})\sigma _\mathrm{i}^{(\mathrm{S})}\sigma _\mathrm{j}^{(1)}𝕀_2\mathrm{U}^{}(\mathrm{t})\right)+ϵ_{\mathrm{ik}}^{}\mathrm{Tr}_{12}\left(\mathrm{U}(\mathrm{t})\sigma _\mathrm{i}^{(\mathrm{S})}𝕀_1\sigma _\mathrm{k}^{(2)}\mathrm{U}^{}(\mathrm{t})\right)+`$
$`+`$ $`\eta _{ij}^{}\mathrm{Tr}_{12}\left(\mathrm{U}(\mathrm{t})𝕀_\mathrm{S}\sigma _\mathrm{i}^{(1)}\sigma _\mathrm{k}^{(2)}\mathrm{U}^{}(\mathrm{t})\right)+\nu _{\mathrm{ijk}}^{}\mathrm{Tr}_{12}\left(\mathrm{U}(\mathrm{t})\sigma _\mathrm{i}^{(\mathrm{S})}\sigma _\mathrm{j}^{(1)}\sigma _\mathrm{k}^{(2)}\mathrm{U}^{}(\mathrm{t})\right)`$
From (LABEL:RedDensMat) it is clear that even when the system and the environment are not initially correlated ($`\delta _{ij}^{}=ϵ_{ik}^{}=\nu _{ijk}^{}=0`$), the initial correlations inside the environment $`\eta _{jk}^{}0`$ might introduce a non-Kraus term in the evolved reduced density matrix of the system, thus precluding complete positivity. An example has been provided in the text using different methods.
However note that when the coefficients satisfy

$`\alpha _i=\overline{\alpha }_i`$ $`\beta _j=\overline{\beta }_j`$ $`\gamma _k=\overline{\gamma }_k`$ (3.3ghjklobghcea)
$`\delta _{ij}=\overline{\alpha }_i\overline{\beta }_j`$ $`ϵ_{ik}=\overline{\alpha }_i\overline{\gamma }_k`$ $`\eta _{jk}=\overline{\eta }_{jk}`$ (3.3ghjklobghceb)
$`\nu _{ijk}=\overline{\alpha }_i\overline{\eta }_{jk}`$ (3.3ghjklobghcec)
for arbitrary “barred” quantities, the joint density operator can then be factorized as $`\rho _{\mathrm{S12}}=\rho _\mathrm{S}\rho _{12}`$ and the reduced dynamics is then completely positive as expected. Another sufficient condition to get a completely positive evolution even in the case of initial correlation arises when the dynamics is not entangling , i.e. when the evolution operator can be written as $`U_{\mathrm{S12}}(t)=U_\mathrm{S}(t)U_1(t)U_2(t)`$ (see  for details).

One of us (D.S.) acknowledges the support of Madrid Education Council under grant BOCAM 20-08-1999.

## References


text:
# Quantum secret sharing without entanglement

## I Introduction

Suppose the president of a bank, Alice, wants to give access to a vault to two vice presidents, Bob and Charlie, who are not entirely trusted. Instead of giving the combination to any one individual, it may be desirable to distribute information in such a way that no vice president alone has any knowledge of the combination, but both of them can jointly determine the combination. Classical cryptography provides an answer which is known as secret sharing. Alice creates two coded messages and one of them is sent to Bob and the other to Charlie. Each of the encrypted message contains no information about her original message, but together they contain the complete message.

However, either a fourth party or the dishonest member of the Bob-Charlie pair gains access to both of Alice’s transmissions can learn the contents of her message in this classical procedure. Quantum secret sharing protocols have been proposed to accomplish this work securely\[2, 3, 4, s4.\] where multi-photon entanglement is employed. Recently, many kinds quantum secret sharing with entanglement have been proposed. As the quantum key distribution and classical sharing protocol can be used straightforward to accomplish secret sharing safely, the aim of the quantum secret sharing protocols is to allow one to determine whether an eavesdropper has been active during the secret sharing and reduce the resources necessary to implement such multi-party secret sharing tasks. But the efficiency of those quantum secret sharing protocols using entanglement can only approach 50% in principle, the lack of the multi-parties entanglement also holds their experimental implementation. The efficiency of preparing even tripartite or four-partite entangled states is very low.

There is another thing that should be noted in this quantum secret sharing scheme with GHZ states. It uses the correlation of the measurement value of the three qubits of the GHZ state: $`\sigma _x^a\sigma _x^b\sigma _x^c=\sigma _x^a\sigma _y^b\sigma _y^c=\sigma _y^a\sigma _x^b\sigma _y^c=\sigma _y^a\sigma _y^b\sigma _x^c=1,`$where $`\sigma _j^i`$ means the measurements value $`\pm 1`$ of qubit $`i`$ along basis $`j`$ with $`i=a,b,c`$ and $`j=x,y,z.`$ So only the cases that even of the three qubits are measured along the $`y`$ direction are kept to share secret in this scheme and its theory efficiency is only $`50\%.`$

In the security analysis of the case that Bob eavesdrops both qubits $`b`$ and $`c`$, the authors assume that he measures them jointly in the $`\left(|00\pm |11\right)/\sqrt{2}`$or $`\left(|00\pm i|11\right)/\sqrt{2}`$basis. But we find if Bob measures qubits $`b`$ and $`c`$ separately (measures qubits $`b`$ and $`c`$ in product states ), he can cheat and get Alice’s secret without being detected. For example, suppose Bob measures the qubits $`b`$ and $`c`$ in the product basis $`\sigma _y^b\sigma _y^c`$, he can thus infer Alice’s value if she measures in the basis $`\sigma _x^a`$. Then Bob can send a qubit in arbitrary state to Charlie. In the procedure of announcing basis, Bob tries to announce his direction after Charlie and cheats his announcement to let Alice keep the choose that she has measured his particle in the basis $`\sigma _x^a`$. Different from the eavesdropping analysis in the paper, this eavesdropping will not introduce a higher than usual failure rate. For example, if Charlie announces that he has chosen his measurement in the basis $`\sigma _x^c`$, Bob can announce that his measurement is also in the basis $`\sigma _x^b`$. Then if Alice also makes her measurement in the basis $`\sigma _x^a`$, she will believe that there is correlation between those three man’s measurement value and keep this measurement value as secret. But Bob has successfully eavesdrop this secret value.

Although Bob has changed the state of qubit sending to Charlie, he can cheat again in the check procedure if Charlie announces his check bit before Bob and then escapes detection. For example, when he had measured the qubits $`b`$ and $`c`$ in the product basis such as $`\sigma _y^b\sigma _y^c`$, Bob can infer that if Alice measures her particle in the basis $`\sigma _x^a`$ will gets the value $`+1`$. When Charlie that his measurement is $`1`$, Bob can announces that his measurement is also $`1`$. Then no error will occur in this check procedure. Thus Bob successfully eavesdrops the secret without being detected by Alice and Charlie. It means that if one party (say Bob) can reveal his directions and values after the other party (say Charlie), he is able to discover Alice’s secret bit value, without any assistance from Charlie, and escape being detected. The feature of this eavesdropping is that Bob directly measures qubits $`b`$ and $`c`$ in product basis to learn Alice’s value. He cheats in the basis announcing procedure and check procedure again. Bob needn’t know Alice measurement direction, but he can let Alice only keep the measurements he desired by announcing his direction according to Charlie’s measurement direction. Then this eavesdropping is more powerful than those having been analyzed in the paper.

In order to detect this kind of eavesdropping, Alice should randomly require one party to reveal his directions before the other one, sometimes Bob before Charlie, sometimes Charlie before Bob. And in the check procedure, she also randomly requires one party to reveal his value before the other. This random can ensure the security of this quantum secret sharing protocol based on GHZ state correlation. It has also been pointed out in the paper, Alice and Bob can prevent this eavesdropping by releasing the outcomes for the check bits before the announcement of their measurement directions. We can see that the paper introduce the EPR state correlations to split the secret. The efficiency of those quantum secret sharing protocols with entanglement can only reach 50% in principle.

In this paper, we propose the idea to directly encode the qubits of quantum key distributions classically and present a quantum secret sharing scheme employing product states to achieve the aim mentioned above. Its security is based on the quantum no-cloning theory just as the BB84 quantum key distribution. Comparing with the efficiency 50% limiting for the existing quantum secret sharing protocols with quantum entanglement, the present scheme can be 100% efficient in principle. It has been pointed out in the paper that the quantum key distribution can accomplish the task of secret sharing, the resources necessary can be much smaller with our present protocol although it is very simple and alike the BB84 quantum key distribution scheme. Our emphasis is that the classically encoding the qubits of quantum key distributions simply may be more economical than the idea of the paper to use EPR states correlations to split secret. This may suggests that the introduce of entanglement into the quantum secret sharing may be unworthiness.

## II Efficiency quantum secret sharing without entanglement

Now we present a quantum secret sharing protocol where no entanglement is employed. Its essence is to encode the sources of two BB84 key distribution schemes. The particular process of this quantum secret sharing is as follows:

1. Alice creates two random $`n`$-bit string $`L`$ and $`A`$. For each bit of $`L`$ and $`A`$, she creates a two-qubit product state $`|bc`$ in the basis $``$ ( if the corresponding bit of $`L`$ is 0) or the basis $``$ (if the bit of $`L`$ is 1) where the XOR result of the two qubits $`b`$ and $`c`$ equals to the bit value of the string $`A`$. The two-qubit vectors of the basis $``$ and $``$ are $`S1(|\alpha \beta _{bc}^{})=\{|00_{bc},|10_{bc},|01_{bc},|11_{bc}\}`$ and $`S2(|\alpha ^{}\beta ^{}_{bc}^{})=\left\{\right|++_{bc},|+_{bc},|+_{bc},|_{bc}\}`$ respectively where $`|+=\frac{1}{\sqrt{2}}(|0+|1)`$ and $`|=\frac{1}{\sqrt{2}}(|0|1)`$ . Table 1 summarizes the coding two-qubit states in the corresponding basis. For example, if the bits of $`L`$ and $`A`$ are 1 and 0 respectively, then the two-qubit state Alice prepared can be $`|++_{bc}`$ or $`|_{bc}`$ each with 50% probability. But she knows exactly which pair he prepares.

2. Alice sends the resulting two strings $`B`$ and $`C`$ to Bob and Charlie separately. It should be emphasized that every bit of the two strings $`B`$ and $`C`$ are corresponding and their XOR result equals to the corresponding bit of the string $`A`$.

3. When both Bob and Charlie have announced the receiving of their strings $`B`$ and $`C`$, Alice announces the string $`L`$.

4. Bob and Charlie then measure each qubit of their string in the basis $``$ or $``$ according to the corresponding bit value of string $`L`$.

5. In the check procedure, Bob and Charlie are required to announce the values of their check bits. If Alice finds too few of these values agree, they abort this round of operation and restart from the first step.

6. The rest unchecked bits of strings $`A`$, $`B`$ and $`C`$ can be used as raw keys for secret sharing. Alice’s secret encrypted by her keys can only be decrypted by Bob and Charlie when they cooperate with each other.

Obviously, the qubits $`b`$ and $`c`$ need not be sent out simultaneously in this quantum secret sharing scheme. Alice can send them separately to Bob and Charlie. They can hold their strings until Alice wants them to extract out her information and announces her the string $`L`$. It is virtually a combination of two modified BB84 quantum key distribution protocols, Alice to Bob and Alice to Charlie, where the states Alice sent out have been classically encoded so that her keys are shared in the strings $`B`$ and $`C`$. Either of them can learn nothing about Alice’s keys without the cooperation of the other one. Furthermore, this secret sharing protocol is almost 100% efficient as all the keys can be used in the ideal case of no eavesdropping, while the quantum secret sharing protocols with entanglement states can be at most 50% efficient in principle. However, in this procedure of making measurements after the announcement of bases, quantum memory is required to store the qubits which has been shown available in the present experimental technique. Adjusting the measurements order in the similar way the BB84 quantum key distribution protocol can also double its efficiency of to nearly 100%. When no quantum memory is employed, Bob and Charlie measure their qubits before Alice’s announcement of basis in our protocol, the efficiency of the present protocol falls to 50%.

As the present scheme is more efficient than employing two BB 84 procedures, one between Alice and Bob and the other between Alice and Charlie, which has been briefly discussed in the references, it allows the possible eavesdropper, who obtains both of the particles that Alice sent, to gain more information than the two-BB-84 scheme, when the qubits $`b`$ and $`c`$ are sent simultaneously. Suppose an eavesdropper, Eve, obtains both of the particles that Alice sent, and measures them in the Bell basis. Then when the two qubits $`b`$ and $`c`$ are measured in the state $`|\mathrm{\Phi }^{}=\frac{1}{\sqrt{2}}(|00|11)`$, Eve can infers that the secret is $`1`$. And if they in the state $`|\mathrm{\Psi }^+=\frac{1}{\sqrt{2}}(|01|10)`$, he knows that the secret is $`0`$. But we can prevent this kind of information leakage causing by the jointed measurements, either by sending the two qubit un-synchronously or by encoding the two qubit as Table 2. Then in the same security degree, the present protocol is double efficient as the two-BB-84 scheme.

## III Eavesdropping and generalization to the multi-party secret sharing

In this quantum secret sharing scheme, only product states are employed and one cannot get any information about the value of one qubit from measurement on the other qubit. In fact it is exactly two independent BB84 quantum key distribution protocols, which has been proved security generally. The only difference is that the qubits Alice sent out have been classical encoded. Obviously, any eavesdropping on individual quantum channel for example Alice to Charlie will get nothing useful and will unavoidably introduce errors.

Now suppose an adversary ( who could also be either Bob or Charlie) eavesdrops the qubits $`b`$ and $`c`$ jointly. His object is to extract out Alice’s information without any assistance from Charlie in a way that cannot be detected. But what ever he does, if Bob eavesdrops qubit $`c`$, Alice will find some error in the check procedure although Bob could cheat again in this check procedure. Then the security for the present quantum secret sharing is guaranteed.

The generalization of this quantum secret sharing scheme to multi-parties is straightforward.. For each bit of $`L`$ and $`A`$, Alice can creates an $`N`$-qubit product state $`|b_1b_2\mathrm{}b_N`$ in the basis $``$ ( if the corresponding bit of $`L`$ is 0) or the basis $``$ (if the bit of $`L`$ is 1) where the XOR result of the $`N`$ qubits $`b_1,b_2\mathrm{}b_N`$ equals to the bit value of the string $`A`$. The two-qubit vectors of the basis $``$ and $``$ are $`S1(|\alpha _1\alpha _2\mathrm{}\alpha _N_{12\mathrm{}N}^{})=\{|00\mathrm{}0_{12\mathrm{}N},|00\mathrm{}1_{12..N},\mathrm{},|11\mathrm{}1_{12\mathrm{}N}\}`$ and $`S2(|\alpha _1^{}\alpha _2^{}\mathrm{}\alpha _N^{}_{12\mathrm{}N}^{})=\left\{\right|++\mathrm{}+_{12\mathrm{}N},|++\mathrm{}_{12\mathrm{}N},\mathrm{},|\mathrm{}_{12\mathrm{}N}\}`$. Obviously, if there are odd numbers $`|1`$ in $`|\alpha _1\alpha _2\mathrm{}\alpha _N_{12\mathrm{}N}^{}`$ ($`|`$ in $`|\alpha _1^{}\alpha _2^{}\mathrm{}\alpha _N^{}_{12\mathrm{}N}^{}`$), the bit value of $`A`$ is 1. The case of even numbers $`|1`$ stands for 0. The following steps are the same as the above two-party sharing case. As no entanglement, especially inaccessible multi-parties entangled states, are required, it may be more experimentally realizable than the original one.

Finally, let us discuss the resources necessary to implement this quantum secret sharing protocol. In the most obvious way of sharing secret, Alice first must establish mutual keys among different pairs of parties, and then use quantum cryptographic protocols to send each of the bit strings which result from the classical procedure. While in our secret sharing protocol of direct encoding the qubits of the two BB84 quantum key distribution, once the key has been established, Alice needs to send only one string of classical bits to either Bob or Charlie. Then in order to share a classical bit(cbit) information between two parties, Bob and Charlie, quantum cryptography as BB84 protocol ideally needs 2 qubits, 2 cbit and no ebit on average. The quantum secret sharing with EPR states needs 4 qubits, 1cbit and 2ebits. While our protocol with product states needs only 2 qubits, 1cbit and no ebit. In general, the more parts into which the secret is split, the greater the difference between the number of classical bits which be sent in those two ways. We see the direct encoding to the source qubits is able to act as a substitute for transmitted random bits. Furthermore, the efficiency of the existing entangled-state scheme can only reach 50% in principle while the present secret sharing protocol can be 100% efficient.

## IV Conclusion

In this paper, we analyze the main quantum secret sharing protocol based on the GHZ-state and propose a quantum secret sharing scheme where only product states are employed. As entanglement, especially the inaccessible multi-party entangled state, is not necessary in the present quantum secret sharing protocol, it may be more applicable when the number of the parties of secret sharing is large. Its theoretic efficiency is also doubled to approach 100%.

Although those quantum secret sharing with entanglement can be a demonstrator of concepts of various entanglement applications, the inherent efficiency limiting of these protocols and the difference for the preparation of multi-party entanglement may suggest that the employing of the quantum entanglement in quantum secret sharing be unworthiness in some cases. After all the practicality is an important pursuit of the quantum information theory.

This work was funded by National Fundamental Research Program(2001CB309300), National Natural Science Foundation of China, the Innovation funds from Chinese Academy of Sciences, and also by the outstanding Ph. D thesis award and the CAS’s talented scientist award entitled to Luming Duan.