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# Density-correlator signatures of the vulcanization transition

## I Introduction and basic ingredients

The vulcanization transition (VT) is an equilibrium phase transition from a liquid state of matter to an amorphous solid state. It occurs when a sufficient number of permanent random constraints (e.g. chemical crosslinks)—the quenched randomness—are introduced to connect the constituents (e.g. macromolecules) whose locations are the thermally fluctuating variables. A rather detailed description of the VT has emerged over the past few years, ranging from a mean-field theory of the emerging amorphous solid state  to the critical properties of the VT itself .

The purpose of the present Paper is to investigate the properties of correlators that solely involve the local monomer density, and to examine the extent to which such correlators provide access to informative signatures of the VT and the emergent amorphous solid state. Along the way, we shall explore the relationship of these density correlators to various experimental probes, and also discuss their relationship to the diagnostics of “non-ergodic media” studied by Pusey, Van Megen and collaborators in their work on amorphous states of colloidal and gel systems . We note that density correlators closely related to the ones we shall be considering also feature in certain recent approaches to structural glasses , and we shall touch upon the relationship between our results and those of these recent approaches.

Apart from their connections with related studies by other researchers, we are motivated to explore the properties of density correlators in the context of the VT for the following reason. From the theoretical perspective, the natural collective coordinate from which to view the VT is not the local density; rather it is the amorphous solid order parameter, which becomes nonzero as the amorphous solid state is entered and whose correlator-decay properties directly mark the onset of amorphous solidification. However, as we shall discuss further below, from the perspective of experiment, the amorphous solid order parameter is rather more elusive than one would like, the most direct way to measure it being via incoherent quasi-elastic neutron scattering, whereas probes that couple to the density are more plentiful. For this reason, we wish to examine density correlators in the vicinity of the VT, and the extent to which they can provide access to both the structure of the amorphous solid state and the long-ranged amorphous solid order-parameter correlations that develop near the VT.

The approach that we shall adopt to study these density correlators is based upon a minimal model that takes into account the integrity of the macromolecules, their thermal position-fluctuations, the short-range repulsion of the constituent monomers, and the permanent random constraints imposed by crosslinking. This minimal model has previously been shown to give an accurate picture of the universal properties of the VT, in the sense that its predictions for the mean-field properties of the amorphous solid state have been verified in the computer simulations of Barsky and Plischke , and those of its critical properties that have been elucidated so far (i.e. the percolative aspects) are in accordance with the predictions of percolation and related field-theoretic approaches . In order for our discussion to be concrete and physical, we shall adopt language specific to randomly crosslinked macromolecular systems(RCMSs), although our results apply to a broader class of systems.

Let us now turn to the issue of the order parameter for the VT. This order parameter is crafted to detect and diagnose amorphous solidification; it is the following function of $`n+1`$ wavevectors $`\{𝐤^0,𝐤^1,\mathrm{},𝐤^n\}`$:

$$\left[\frac{1}{N}\underset{j=1}{\overset{N}{}}_0^1𝑑s\mathrm{exp}i𝐤^0𝐜_j(s)_\chi \mathrm{exp}i𝐤^1𝐜_j(s)_\chi \mathrm{}\mathrm{exp}i𝐤^n𝐜_j(s)_\chi \right],$$
(1)
where $`N`$ is the total number of macromolecules, $`𝐜_j(s)`$ (with $`j=1,\mathrm{},N`$ and $`0s1`$) is the position in $`d`$-dimensional space of the monomer at fractional arclength $`s`$ along the $`j^{\mathrm{th}}`$ macromolecule, $`\mathrm{}_\chi `$ denotes a thermal average for a particular realization $`\chi `$ of the quenched disorder (i.e. the crosslinking), and $`\left[\mathrm{}\right]`$ represents a suitable averaging over realizations of the quenched disorder. As discussed in detail in Ref. , this order parameter does indeed detect and diagnose the amorphous solid state.

Why is the amorphous solid order parameter measurable in neutron scattering experiments? In quasi-elastic neutron scattering the incoherent contribution of the scattering cross-section is proportional to

$$\underset{j=1}{\overset{N}{}}_0^1𝑑s\mathrm{exp}\left(i𝐪𝐜_j(s,0)\right)\mathrm{exp}\left(i𝐪𝐜_j(s,t)\right)_\chi ,$$
(2)
where $`𝐜_j(s,t)`$ is the position of the monomer at time $`t`$, the $`t\mathrm{}`$ limit of the correlator being proportional (up to disorder averaging) to a special case of Eq. (1), viz.,

$$\frac{1}{N}\underset{j=1}{\overset{N}{}}_0^1𝑑s\mathrm{exp}i𝐪𝐜_j(s)_\chi \mathrm{exp}i𝐪𝐜_j(s)_\chi .$$
(3)
On the other hand, in several other experimental techniques, such as those discussed below, it is some form of correlator involving the local monomer density

$$\rho (𝐫,t)\underset{j=1}{\overset{N}{}}_0^1𝑑s\delta (𝐫𝐜_j(s,t))$$
(4)
that is probed. One frequently-measured correlator is the auto-correlation function of the local density $`\rho (𝐱,0)\rho (𝐲,t)_\chi `$, or equivalently $`\rho (𝐪,0)\rho (𝐪,t)_\chi `$, where $`\rho (𝐪)`$ is the Fourier transform of $`\rho (𝐱)`$, i.e., $`\rho (𝐪)=d^dx\rho (𝐱)\mathrm{exp}(i𝐪𝐱)`$ . For example, in neutron scattering experiments this quantity is proportional to the coherent part of the quasi-elastic neutron scattering cross-section (see, e.g., Ref. , Sec. IIIE), and in dynamical light scattering experiments, such as those performed on ‘non-ergodic’ media by Pusey and van Megen , this quantity is proportional to the intermediate scattering function (also known as the dynamical structure factor) $`F(k,t)`$. (The average over quenched disorder $`[\mathrm{}]`$ in the present work essentially plays the role of the ensemble average $`\mathrm{}_\mathrm{E}`$ of Refs. .) The present theoretical framework is a static equilibrium framework and, as such, is not suitable for computing dynamical correlators. However, by using the cluster property (i.e. the fact that the connected correlators vanish for $`t\mathrm{}`$) we see that the long-time limit of the density-density auto-correlation function is built from the equilibrium entity $`\rho (𝐱)_\chi \rho (𝐲)_\chi `$ or, equivalently, its Fourier transform $`\rho (𝐪)_\chi \rho (𝐪)_\chi `$, an entity that is calculable (up to disorder averaging) within our static equilibrium framework. In fact, our approach to the VT is capable of calculating precisely this kind of quantity and, therefore, of providing contact with experiments.

As our results for density correlators are relatively straightforward, we first report the results, deferring the construction and operation of the necessary theoretical machinery to subsequent sections. Specifically, we find that: (i) The usual (i.e. disorder-averaged) density-density correlator $`[\rho (𝐪)\rho (𝐪)_\chi ]`$ is insensitive to the VT, depending only analytically on the constraint density, both at the level of mean-field theory and beyond (i.e. to one-loop order). (ii) The density-density correlator involving two thermal averages, $`[\rho (𝐪)_\chi \rho (𝐪)_\chi ]`$, is zero in the liquid phase but becomes nonzero, continuously, as the system enters the amorphous solid phase. This behavior is a manifestation of the freezing-in of random density fluctuations, which is the hallmark of the amorphous solid state. This correlator turns out to be proportional the order parameter (at least for weak coupling between the density and the order parameter fluctuations). As the order parameter encodes the fraction of localized particles and the distribution of localization lengths, this result indicates that these physical diagnostics are accessible via this density-density correlator. (iii) The four-density correlator involving two thermal averages, $`[\rho (𝐤)\rho (𝐤)_\chi \rho (𝐪)\rho (𝐪)_\chi ]`$, which can be realized as $`lim_t\mathrm{}[\rho (𝐤,0)\rho (𝐤,0)\rho (𝐪,t)\rho (𝐪,t)_\chi ]`$, becomes long-ranged as the VT is approached from the liquid side. We exhibit this phenomenon at the level of mean-field theory. (iv) The two density-chanel signatures of the VT given in (ii) and (iii) also provide a means for identifying certain critical exponents at the VT, such as the gel-fraction exponent $`\beta `$, and the correlation-length exponent $`\nu `$. Therefore, these density signatures provide another avenue for accessing experimentally the critical exponents of the VT.

## II Field-theoretic formulation: Minimal model and coupling to density field

We approach the VT by adopting the spirit of the Landau-Wilson scheme for continuous phase transitions. To handle the presence of the random constraints we invoke the replica trick and adopt the Deam and Edwards model  for the statistics of the quenched randomness (viz. that the statistics of the random constraints are determined by the instantaneous correlations of the unconstrained system). Thus, we are led to the need to work with the $`n0`$ limit of systems of $`n+1`$ replicas. The additional replica, labeled by $`\alpha =0`$, incorporates the constraint distribution. With the effective spatial dimensionality thus being determined to be $`(n+1)d`$, symmetry considerations lead to the following minimal model , which takes the form of a cubic field theory involving an order parameter field $`\mathrm{\Omega }(\widehat{k})`$ that lives on $`(n+1)`$-fold replicated $`d`$-dimensional space :

$`f`$ $``$ $`\underset{n0}{lim}n^1\mathrm{ln}[Z^n],`$ (6)
$`\left[Z^n\right]`$ $``$ $`{\displaystyle \overline{𝒟}^{}\mathrm{\Omega }\mathrm{exp}(_n^{\mathrm{HRS}})},`$ (7)
$`_n^{\mathrm{HRS}}\left(\mathrm{\Omega }\right)`$ $`=`$ $`N{\displaystyle \underset{\widehat{k}\mathrm{HRS}}{}}\left(a\tau +{\displaystyle \frac{b}{2}}|\widehat{k}|^2\right)\left|\mathrm{\Omega }(\widehat{k})\right|^2Ng{\displaystyle \underset{\widehat{k}_1,\widehat{k}_2,\widehat{k}_3\mathrm{HRS}}{}}\mathrm{\Omega }(\widehat{k}_1)\mathrm{\Omega }(\widehat{k}_2)\mathrm{\Omega }(\widehat{k}_3)\delta _{\widehat{k}_1+\widehat{k}_2+\widehat{k}_3,\widehat{0}}.`$ (8)
Here, $`\tau `$ is the VT control parameter, which measures the reduced density of random constraints, and the coefficients $`a`$, $`b`$ and $`g`$ depend on the microscopic details of the system. We use the symbol $`\widehat{k}`$ to denote the replicated wavevector $`\{𝐤^0,𝐤^1,\mathrm{},𝐤^n\}`$, and define the extended scalar product $`\widehat{k}\widehat{c}`$ by $`𝐤^0𝐜^0+𝐤^1𝐜^1+\mathrm{}+𝐤^n𝐜^n`$. The symbol $`\widehat{k}\mathrm{HRS}`$ denotes that the summation over replicated wavevectors is restricted to those containing at least two nonzero component-vectors $`𝐤^\alpha `$. (We say that this kind of wavevector lies in the higher-replica-sector, i.e., the HRS.) This condition on $`\widehat{k}`$ reflects the fact that no crystalline order (or any other kind of macroscopic inhomogeneity) is present or fluctuates critically in the vicinity of the VT.

We now extend the effective free energy, Eq. (8), by including the field $`R`$ that is associated with spatial monomer density fluctuations. The field $`R`$ takes as its argument replicated wavevectors having exactly one nonzero component-vector $`𝐤\widehat{e}^\alpha `$. (We denote by $`\{\widehat{e}^\alpha \}_{\alpha =0}^n`$ the collection of unit vectors in replicated space, so that, e.g., a generic replicated vector $`\widehat{p}`$ can be expressed as $`_{\alpha =0}^n𝐩^\alpha \widehat{e}^\alpha `$.) We term the subset of replicated wavevectors having exactly one nonzero component-vector the one-replica-sector (1RS) of wavevectors; we term the corresponding fields $`R(𝐤\widehat{e}^\alpha )`$ 1RS fields. We extend the effective Landau free energy, Eq. (8), by incorporating the 1RS fields , which represent local density fluctuations, and add the significant symmetry-allowed cubic term that couples the order-parameter and density fields, thus arriving at

$`_n(\mathrm{\Omega },R)`$ $`=`$ $`_n^{\mathrm{HRS}}\left(\mathrm{\Omega }\right)+_n^{1\mathrm{R}\mathrm{S}}\left(R\right){\displaystyle \frac{h}{N}}{\displaystyle \underset{\genfrac{}{}{0pt}{}{\widehat{k}_3\mathrm{HRS}}{\widehat{k}_1,\widehat{k}_21\mathrm{R}\mathrm{S}}}{}}R(\widehat{k}_1)R(\widehat{k}_2)\mathrm{\Omega }(\widehat{k}_3)\delta _{\widehat{k}_1+\widehat{k}_2+\widehat{k}_3,\widehat{0}},`$ (10)
$`_n^{1\mathrm{R}\mathrm{S}}\left(R\right)`$ $`=`$ $`{\displaystyle \frac{1}{N}}{\displaystyle \underset{\widehat{k}1\mathrm{R}\mathrm{S}}{}}\left(r^2+{\displaystyle \frac{c}{2}}|\widehat{k}|^2\right)\left|R(\widehat{k})\right|^2+\mathrm{}.`$ (11)
The term $`_n^{1\mathrm{R}\mathrm{S}}\left(R\right)`$ is the effective free energy for the density fluctuations; in principle, it also includes non-linear couplings between the $`R`$ fields. This effective free energy term already incorporates the effects of the short-range repulsion between macromolecules. The parameter $`r`$ is the correlation length for density fluctuations. (In the context of a dense melt, it is simply determined by the monomer density and the effective excluded-volume interaction strength .) The correlation length $`r`$ remains large and varies analytically (with the constraint density) across the VT, and the $`R`$ field remains a non-ordered field. This is representative of the fact that the disorder-averaged physical monomer-density is homogeneous in both the liquid state and the amorphous solid state.

In addition to the coupling presented in Eq. (10), there is one further term at cubic order that couples the $`R`$ and $`\mathrm{\Omega }`$ fields, i.e., the vertex $`\mathrm{\Omega }\mathrm{\Omega }R`$ consisting of two $`\mathrm{HRS}`$ fields and one $`1\mathrm{R}\mathrm{S}`$ field. It can readily be shown by dimensional analysis that both this cubic vertex and that given in Eq.( 10) are irrelevant with respect to the fixed points of HRS $`\mathrm{\Omega }`$ theory near $`d=6`$ and, therefore, the critical properties of the VT (i.e. the fixed point structure, the flow equation and the critical exponents) are not affected by the coupling to density fluctuations(at least near $`d=6`$). Based on the effective free energy (10), our approach is to explore the correlators of the 1RS fields (and hence the density correlators), taking into account the effects of the VT in the HRS fields by treating what happens in the HRS as “input” to be added to the effective free energy of the 1RS theory, and working perturbatively (i.e. effectively we assume that $`h`$ is small).

The reason that we ignore the the cubic coupling $`\mathrm{\Omega }\mathrm{\Omega }R`$, besides its irrelevance in the renormalization-group sense, is that it does not contribute to the density correlators that we are interested in (at least to one-loop order). There are two points to make in this regard. First, at the mean-field level, the $`\mathrm{HRS}`$ field can be viewed as an external source for the $`1\mathrm{R}\mathrm{S}`$ field in the cubic coupling $`\mathrm{\Omega }\mathrm{\Omega }R`$. Due to translational invariance, $`\mathrm{\Omega }(\widehat{k}_1)\mathrm{\Omega }(\widehat{k}_2)^{_n^{\mathrm{HRS}}}=0`$. (We use $`\mathrm{}^{_n^{\mathrm{HRS}}}`$ to denote a statistical average weighted by $`_n^{\mathrm{HRS}}`$.) Therefore, on average, the term $`\mathrm{\Omega }\mathrm{\Omega }R`$ will not generate a non-zero $`R`$ \[$`\mathrm{}`$ denotes an average weighted by the replicated effective free energy presented in Eq. (10)\]. Second, at the one-loop level (and beyond), this term will renormalize the coefficient $`r^2`$ (in a singular way) but, as has already been shown in App. B of Ref. , at least to the one-loop level, there is (in the replica limit) no contribution to the density-density correlator coming from HRS critical fluctuations via this kind of vertex.

In order to help make the physical content of the results that we shall present clear, we pause to give the relationship between the physical density correlators and the $`R`$ correlators:

$`\underset{n0}{lim}R(𝐤\widehat{e}^\alpha )R(𝐤\widehat{e}^\beta )_\mathrm{c}=\{\begin{array}{cc}\left[\rho (𝐤)\rho (𝐤)_\chi \right];\hfill & \text{for }\alpha =\beta \text{,}\hfill \\ \multicolumn{2}{c}{}\\ \left[\rho (𝐤)_\chi \rho (𝐤)_\chi \right];\hfill & \text{for }\alpha \beta \text{,}\hfill \end{array}`$ (12)
where $`\mathrm{c}`$ denotes that a correlator is connected. (Such connections can be established by following the replica technique that is used in Appendix A of Ref. .) On the right hand side of Eq.( 12), the correlators differ in the locations of the thermal averages; on the left hand side they differ in their replica indices, the former being diagonal and the latter being off-diagonal in replica space.

## III Freezing-in of density fluctuations

Now that we have constructed an extended model containing not only the critical order parameter (i.e. HRS) fields but also the noncritical replicated density (i.e. 1RS) fields, we proceed to study the effect of critical HRS phenomena on the density fields, treating the latter at the tree level. The basic mechanism at work is that the order parameter field, which is capable of ordering spontaneously, couples to the density fluctuations via a cubic vertex that is replica-off-diagonal as far as the density fields are concerned. A non-zero value of $`\overline{\mathrm{\Omega }}\mathrm{\Omega }^{_n^{\mathrm{HRS}}}`$, as occurs in the amorphous solid state due to spontaneous symmetry breaking in the HRS, contributes replica-off-diagonal terms to the “mass matrix” of the $`R`$-field and, hence, leads to the existence of nonzero replica-off-diagonal density-field correlators.

In order to see this more clearly, we replace $`\mathrm{\Omega }`$ by its expectation value plus fluctuations, i.e., we write $`\mathrm{\Omega }=\overline{\mathrm{\Omega }}+\delta \mathrm{\Omega }`$ and, hence, arrive at the effective free energy

$`_n(R,\mathrm{\Omega })`$ $`=`$ $`_n^{\mathrm{HRS}}\left(\mathrm{\Omega }\right)+\stackrel{~}{}_n^{1\mathrm{R}\mathrm{S}}(R,\overline{\mathrm{\Omega }}){\displaystyle \frac{h}{N}}{\displaystyle \underset{\genfrac{}{}{0pt}{}{\widehat{k}_3\mathrm{HRS}}{\widehat{k}_1,\widehat{k}_21\mathrm{R}\mathrm{S}}}{}}R(\widehat{k}_1)R(\widehat{k}_2)\delta \mathrm{\Omega }(\widehat{k}_3)\delta _{\widehat{k}_1+\widehat{k}_2+\widehat{k}_3,\widehat{0}},`$ (14)
$`\stackrel{~}{}_n^{1\mathrm{R}\mathrm{S}}(R,\overline{\mathrm{\Omega }})`$ $`=`$ $`{\displaystyle \frac{1}{N}}{\displaystyle \underset{𝐤\mathrm{𝟎}}{}}{\displaystyle \underset{\genfrac{}{}{0pt}{}{\alpha ,\beta =0}{(\alpha \beta )}}{\overset{n}{}}}\left((r^2+{\displaystyle \frac{c}{2}}k^2)\delta ^{\alpha ,\beta }h\overline{\mathrm{\Omega }}(𝐤\widehat{e}^1+𝐤\widehat{e}^2)(1\delta ^{\alpha ,\beta })\right)R(𝐤\widehat{e}^\alpha )R(𝐤\widehat{e}^\beta )+\mathrm{}.`$ (15)
To arrive at this result, we have taken advantage of the facts that both $`_n`$ and $`\overline{\mathrm{\Omega }}`$ are replica (i.e. permutation) symmetric, and that $`\overline{\mathrm{\Omega }}(𝐤_1\widehat{e}^\alpha 𝐤_2\widehat{e}^\beta )`$ is macroscopically translational invariant (i.e. it contains a factor of $`\delta _{𝐤_1+𝐤_2,\mathrm{𝟎}}`$.

We now aim to compute the correlator $`R(𝐤\widehat{e}^\alpha )R(𝐤\widehat{e}^\beta )`$. By treating $`h`$ as a small quantity and expanding perturbatively, a direct calculation yields

$$R(𝐤\widehat{e}^\alpha )R(𝐤\widehat{e}^\beta )=R(𝐤\widehat{e}^\alpha )R(𝐤\widehat{e}^\beta )^{\stackrel{~}{}_n^{1\mathrm{R}\mathrm{S}}}+O(h^2).$$
(16)
To obtain the correlator at the tree (in $`R`$) level, we neglect the nonlinear self-couplings of $`R`$ and then invert the coefficient matrix of the quadratic term in Eq. (15). Thus, in the $`n0`$ limit, we arrive at

$$\underset{n0}{lim}R(𝐤\widehat{e}^\alpha )R(𝐤\widehat{e}^\beta )=\{\begin{array}{cc}\frac{N}{2r^2+ck^2},\hfill & \text{for }\alpha =\beta \text{;}\hfill \\ \frac{1}{2}\frac{Nh\overline{\mathrm{\Omega }}(𝐤\widehat{e}^1+𝐤\widehat{e}^2)}{(r^2+\frac{1}{2}ck^2)((r^2+\frac{1}{2}ck^2)+h\overline{\mathrm{\Omega }}(𝐤\widehat{e}^1+𝐤\widehat{e}^2))},\hfill & \text{for }\alpha \beta \text{.}\hfill \end{array}$$
(17)
In the liquid state we have $`\overline{\mathrm{\Omega }}=0`$, and therefore $`R(𝐤\widehat{e}^\alpha )R(𝐤\widehat{e}^\beta )=0`$ (for $`\alpha \beta `$). However, in the amorphous solid state $`\overline{\mathrm{\Omega }}(𝐤_1\widehat{e}^1+𝐤_2\widehat{e}^2)=q\delta _{𝐤_1+𝐤_2,\mathrm{𝟎}}w(k_1^2+k_2^2)0`$, and therefore $`R(𝐤\widehat{e}^\alpha )R(𝐤\widehat{e}^\beta )0`$ (for $`\alpha \beta `$). Here, the number $`q`$ is the gel fraction and the function $`w(|\widehat{k}|^2)`$, which decays rapidly with increasing wavevector magnitude on the characteristic wavevector scale $`\tau ^\nu `$ , encodes the distribution of localization lengths. The simplest setting for the density-density correlator emerges near the VT, where $`q`$ is small and $`w(|\widehat{k}|^2)`$ is negligible unless $`|\widehat{k}|\tau ^\nu `$. In this regime, by making use of Eq. (12) we find that

$$\left[\rho (𝐤)_\chi \rho (𝐤)_\chi \right]=\{\begin{array}{cc}0,\hfill & \text{liquid state;}\hfill \\ (Nhr^4/2)\overline{\mathrm{\Omega }}(𝐤\widehat{e}^1+𝐤\widehat{e}^2)=(Nhr^4/2)\tau ^\beta w(k^2\tau ^{2\nu }),\hfill & \text{amorphous solid state.}\hfill \end{array}$$
(18)
On the other hand, the diagonal correlator $`\left[\rho (𝐤)\rho (𝐤)_\chi \right]`$ does not vary with $`\tau `$ (and hence varies smoothly with the physical constraint density).

Deeper into the amorphous solid state, the order parameter $`\overline{\mathrm{\Omega }}`$ does not decay so rapidly with $`k`$ and hence the quantity $`\left[\rho (𝐤)_\chi \rho (𝐤)_\chi \right]`$ should remain appreciable (and thus experimentally accessible) over a wider range of $`k`$. Now, we expect Eq. (17) to remain valid, provided the coupling $`h`$ is small and both the wavevector dependence of $`h`$ and the finer wavevector dependence of 1RS bare correlator are incorporated. (We have omitted the wavevector dependence of $`h`$ so as to simplify our presentation.) Under these circumstances, the wavevector dependence of the replica-off-diagonal correlator has the possibility of exhibiting additional features, representative of the ordinary density-density correlator $`\left[\rho (𝐤)\rho (𝐤)_\chi \right]`$, superposed on the decaying trend due to the factor $`w`$ (i.e. due to random monomer localization) .

## IV Inherited criticality of density correlators

In the HRS field theory, the VT is signaled in two ways: (i) via the emergence of a nonzero order parameter, and (ii) via the divergence of the correlation length of order-parameter fluctuations. We have already studied the replica-off-diagonal density correlator, which is closely related to the order parameter and becomes nonzero upon entering the amorphous solid state. We now examine the four-field density correlator $`[\rho (𝐤)\rho (𝐤)_\chi \rho (𝐩)\rho (𝐩)_\chi ],`$ which has the property that it becomes long-ranged at the VT.

We calculate the correlator mentioned in the previous sentence at the tree level (with respect to $`h`$ vertices) in the liquid state and at the VT itself: the Feynman diagram shown on Fig. 1 is the only contribution, and gives

$`[\rho (𝐤)\rho (𝐤)_\chi \rho (𝐩)\rho (𝐩)_\chi ]=\underset{n0}{lim}R(𝐤\widehat{e}^\alpha )R(𝐩\widehat{e}^\beta )R(𝐤\widehat{e}^\alpha )R(𝐩\widehat{e}^\beta )`$ (19)
$`(h/N)^2\left\{R(𝐤\widehat{e}^\alpha )R(𝐤\widehat{e}^\alpha )^{_n^{1\mathrm{R}\mathrm{S}}}\right\}^2\left\{R(𝐩\widehat{e}^\beta )R(𝐩\widehat{e}^\beta )^{_n^{1\mathrm{R}\mathrm{S}}}\right\}^2\mathrm{\Omega }(𝐤\widehat{e}^\alpha 𝐩\widehat{e}^\beta )\mathrm{\Omega }(𝐤\widehat{e}^\alpha +𝐩\widehat{e}^\beta )^{_n^{\mathrm{HRS}}}.`$ (20)
As anticipated, this density correlator becomes long-ranged at the VT, due to the factor of the HRS order-parameter correlator $`\mathrm{\Omega }\mathrm{\Omega }^{_n^{\mathrm{HRS}}}`$ which, itself, becomes long-ranged at the VT.

## V Discussion and conclusions

We have studied density-sector correlators that furnish analogs of the two principal order-parameter signatures of the VT: the off-diagonal density correlator $`[\rho (𝐪)_\chi \rho (𝐪)_\chi ]`$, which becomes nonzero as the amorphous solid state is entered; and the four-field density correlator $`[\rho (𝐤)\rho (𝐤)_\chi \rho (𝐩)\rho (𝐩)_\chi ]`$, which becomes long-ranged at the VT. We have shown that these density correlators provide useful information about both the emergent amorphous solid state and the critical properties of the transition itself. They provide schemes for accessing experimentally the kinds of quantities that have been found useful in theoretical investigations of the liquid, critical and amorphous solid states, e.g., of vulcanized matter. We are not aware of any explorations of such signatures in the density correlators via percolation/gelation approaches to the VT.

Although, as we have seen, the off-diagonal density correlator $`[\rho (𝐪)_\chi \rho (𝐪)_\chi ]`$ is closely related to the order parameter of the VT, its non-zero value being induced by a non-zero order parameter, the off-diagonal density correlator can be used to diagnose a more general class of systems. By looking at the microscopic definition of the order parameter for the VT, Eq. (1) (especially for the special case in which only two thermal averages are involved), we see that it involves only a single summation over monomers and, therefore, the order parameter cannot be expressed in terms of local monomer densities. In essence, the order parameter signals the amorphous solid phase via its detection of all individual monomers that are localized (and, owing to the explicit crosslinks, distinguishable). On the other hand, the off-diagonal density correlator $`[\rho (𝐪)_\chi \rho (𝐪)_\chi ]`$ signals the amorphous solid state via the detection of the frozen structure of the local density fluctuations. In RCMSs, the localization of monomers invariably induces the freezing of this structure, so these two quantities are equivalent. However in systems such as glasses, the (local density) structure is, presumably, frozen but each individual particle is able to wander throughout the system, given enough time, and therefore all particles retain their indistinguishability . A quantity essentially identical to the off-diagonal correlator considered here has been employed by Mezard and Parisi  in the context of their theoretical approach to glassy systems. A similar quantity is employed in the diagnosis of the freezing-in of structure in colloidal glassy systems and gel systems in the dynamical light scattering experiments of Pusey and Van Megen and collaborators

Vulcanized matter certainly differs from glassy systems, inasmuch as it possesses explicit quenched disorder in the form of permanent random crosslinks. Because of this, it affords a framework in which the off-diagonal density correlator and other density correlators are directly calculable in a well controlled way, both near the transition and in the amorphous solid state. Despite the difference with glassy systems, we hope that results such as those presented here in the setting of vulcanized matter will not only be useful but also shed some light on the more difficult problem of glassy systems.

## Acknowledgments

We thank Avi Halperin, Vincent Liu, Marc Mézard, José María Román and, especially, Eduardo Fradkin for useful discussions. This work was supported by the U.S. National Science Foundation through grant DMR99-75187.


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# Anisotropic Magnetoconductance in Quench-Condensed Ultrathin Beryllium Films

## Abstract

Near the superconductor-insulator (S-I) transition, quench-condensed ultrathin Be films show a large magnetoconductance which is highly anisotropic in the direction of the applied field. Film conductance can drop as much as seven orders of magnitude in a weak perpendicular field ($``$ 1 T), but is insensitive to a parallel field in the same field range. We believe that this negative magnetoconductance is due to the field de-phasing of the superconducting pair wavefunction. This idea enables us to extract the finite superconducting phase coherence length, Lϕ, in nearly superconducting films. Our data indicates that this local phase coherence persists even in highly insulating films in the vicinity of the S-I transition.

The superconductor-insulator (S-I) transition remains a controversial subject after nearly two decades of intense research. Experimental systems have generally been grouped into two seemingly different categories, displaying somewhat different features. These are granular versus uniform films. In apparently granular films , the transition temperature, Tc, and the energy gap, $`\mathrm{\Delta }`$, for the individual grains are essentially constant throughout the S-I transition . It is well established that superconductivity is destroyed by the breakdown of long-range phase coherence between the grains . Granular films tend to lose their zero resistance state at a normal state sheet resistance, RN, that is close to the quantum pair resistance, RQ = h/(2e)2 $``$ 6.5 k$`\mathrm{\Omega }`$. In addition, granular films display quasireentrance in films not far from being superconducting: film resistance initially drops as the temperature is cooled below Tc, but eventually increases at low temperatures. A truly insulating state is not seen in granular films until RN $``$ RQ. Films considered to be uniformly disordered, such as quench-condensed Bi/Ge and Pb/Ge films , amorphous InOx films , and $`\mathrm{a}`$-MoGe films , undergo a much sharper S-I transition. On the superconducting side, Tc decreases with decreasing film thickness, approaching zero at the S-I transition. Tunneling experiments have suggested  that in Bi/Ge and Pb/Ge films the superconducting gap, $`\mathrm{\Delta }`$, decreases with decreasing film thickness until the pair wavefunction, $`\mathrm{\Delta }^{1/2}`$e, with $`\varphi `$ being the phase of the order parameter, vanishes and the film becomes insulating. These results suggest that the S-I transition is driven by the vanishing of the superconducting gap. In the alternative ”dirty-boson” model , superconductivity is suppressed by $`\mathrm{p}\mathrm{h}\mathrm{a}\mathrm{s}\mathrm{e}`$ fluctuations, and the Cooper pairs persist even on the insulating side of the transition. In recent years, the ”dirty-boson” model has been applied nearly exclusively to explain the scaling analyses of film resistance in the disorder-driven and field-driven S-I transitions in uniform films , although the existence of Cooper pairs in the insulating states of these films has yet to be demonstrated. The ”dirty-boson” model is, in fact, expected to describe best the S-I transition in granular films, since the amplitude of the order parameter is well defined on both side of the S-I transition in granular films.

The key concept of the ”dirty-boson” model is that phase fluctuations drive a continuous S-I transition. Thus, in the vicinity of the S-I transition, there should exist a finite superconducting phase coherence length, Lϕ, even on the insulating side of the transition. This Lϕ should scale with the correlation length of the transition and should diverge approaching the transition. In this Letter, we report on magnetoconductance (MC) measurements in the vicinity of the S-I transition in quench-condensed ultrathin Be films. As we argue below, this MC study provides the first direct measurement of Lϕ in insulating films. We have observed that, for a given insulating film, Lϕ drops as temperature is lowered. This underscores the competition between localization and superconductivity. Approaching the superconducting state with increasing film thickness, we have found Lϕ to grow drastically.

Our ultrathin Be films were quench-condensed onto bare glass substrates which were held near 20 K during the evaporations. We chose Be mainly for two reasons. First, earlier studies have suggested  that quench-condensed Be films are nearly amorphous. Scanning force microscopy studies of our Be films, after warming up to room temperature, have found no observable granular structure down to 1 nm. This indicates that the length scale of disorder in these Be films must be much smaller than the typical grain size in apparently granular films. Second, Be has a very weak spin-orbit coupling . As a result, a magnetic field applied parallel to the film plane, H, couples to electron spin only and it does not couple to the orbital motion of the electrons. However, a perpendicular field, H, couples to both. Thus the MC

can be highly anisotropic in the direction of the applied field. In our Be films, the MC is negative and varies as much as seven orders of magnitude in weak H up to 1 T, but it is insensitive to H in the same field regime. The low-field MC in our films is thus clearly an orbital effect. We, therefore, believe that this negative and highly aniostropic MC provides a direct measurement of the superconducting phase coherence length, Lϕ, as was suggested by Barber and Dynes  in a MC study of superconducting granular Pb films. This method can eventually be used to measure the divergence of Lϕ as films cross the S-I transition with varying film thickness.

It should be pointed out that the length scale of the disorder in films considered uniformly disordered is still not understood. Even if microscopy techniques fail to reveal any granular structure, there still can exist metallic clusters, which can support superconductivity and which are connected electrically by relatively narrow and insulating or metallic links. For example, the Ge underlayer in Bi/Ge and Pb/Ge films may produce tunneling channels connecting the superconducting clusters. Recently, Kapitulnik and collaborators  have proposed that, near the S-I transition in $`\mathrm{a}`$-MoGe, there exist both insulating and superconducting puddles, with transport being dominated by tunneling or hopping between them. Presumably, the typical size of the superconducting puddles grows approaching the S-I transition and eventually become the longest length scale of the system. Another example is the InOx films studied by Hebard $`\mathrm{e}\mathrm{t}`$ $`\mathrm{a}\mathrm{l}.`$ , which are believed to be amorphous, yet they display the quasireentrant behavior of granular films. Thus it is not clear as to what are the fundamental differences between the S-I transitions observed in uniform and granular films, other than that the different morphologies may lead to different universality classes of the transitions.

The details regarding our quench-condensation appa-

ratus, a rotating sample stage, as well as 4-terminal dc I-V measurements from which the film sheet resistance, R, was obtained, have been described elsewhere . In Fig. 1, we show the temperature dependence of R for one film section deposited on a bare glass substrate following successive deposition steps to increase film thickness. The film changed its behavior from insulating to superconducting when R at 20 K was reduced to below 10 k$`\mathrm{\Omega }`$/$`\mathrm{}`$ with increasing thickness. Film $`\mathrm{\#}`$10 in Fig. 1, which was superconducting with a Tc $``$ 6 K, had a critical field Hc above the 10-T field our magnet could reach at 4.2 K. Thus the Hc is not far below the spin-paramagnetic limit , which we estimated  to be $`\sqrt{2}\mathrm{\Delta }`$/g$`\mu _B`$ $``$ 11.2 T, where g $``$ 2 is the Land$`\stackrel{´}{e}`$ g-factor, $`\mu _B`$ is the Bohr magneton, and $`\mathrm{\Delta }`$ = 0.92 mV is the superconducting gap for Film $`\mathrm{\#}`$10. Early studies  estimated that the critical field was 18 $``$ 20 T in quench-condensed Be films of Tc = 8 $``$ 10 K, suggesting that these films were highly disordered with a very short penetration depth. The data in Fig. 1 do show the quasireentrant behavior, such as in Film $`\mathrm{\#}`$7, which is typically seen in granular films. However, this quasireentrance is seen in a range of RN that is much narrower than in the case of typical granular films . In addition, the Tc of these Be films appears to increase significantly with increasing film thickness, which is typically seen in uniform films. Thus these Be films show certain properties of both uniform and granular films.

In Fig. 2(a), we show the MC measured in H at a

number of temperatures. In the low-field regime below 1 T, the MC is $`\mathrm{n}\mathrm{e}\mathrm{g}\mathrm{a}\mathrm{t}\mathrm{i}\mathrm{v}\mathrm{e}`$ and varies as much as seven orders of magnitude. This can not be due to weak-localization , which should lead to a $`\mathrm{p}\mathrm{o}\mathrm{s}\mathrm{i}\mathrm{t}\mathrm{i}\mathrm{v}\mathrm{e}`$ and relatively small MC in weak spin-orbit materials such as Be. In H, film conductance was found to be insensitive to the field below 1 T, as shown in Fig. 2(b). Such highly anisotropic behavior indicates that the MC in H is an orbital effect. We believe that this negative MC in the low H regime arises as the superconducting phase coherence is suppressed when H exceeds the crossover value H that produces one flux quanta, $`\mathrm{\Phi }_0`$ = h/2e, in a coherent area, or when L$`{}_{}{}^{2}{}_{\varphi }{}^{}`$H $``$ $`\mathrm{\Phi }_0`$. Determining this crossover field H when the conductance drops from its zero-field value, thus provides a measurement of Lϕ. A few years ago, Barber and Dynes  made this argument to calculate Lϕ in the descending resistance tail of superconducting granular Pb films, showing that for a superconducting film Lϕ increases with decreasing temperature. In our non-superconducting films $`\mathrm{\#}`$7 and $`\mathrm{\#}`$8, the data plotted on a logarithmic field scale in Fig. 2(b) show that, at 100 mK, H was near 0.002 T for Film $`\mathrm{\#}`$8 and 0.1 T for Film $`\mathrm{\#}`$7, as indicate by the arrows in Fig. 2(b). This translates into a coherence length, Lϕ, at 100 mK of about 1.0 $`\mu `$m for Film $`\mathrm{\#}`$8 and 0.14 $`\mu `$m for Film $`\mathrm{\#}`$7. We therefore see a growing Lϕ as the films approach the superconducting state with increasing thickness. We note that the drop in conductance at high H, seen in Fig. 2(b), is likely due to the suppression of the amplitude of the superconducting order parameter as the H approaches the spin-paramagnetic limit.

Not only did we observe Lϕ to vary with film thickness, but it varied with temperature as well. In the temperature range in which R decreases with decreasing temperature, we observed that the MC peak was sharper at lower temperatures, indicating an increasing Lϕ with decreasing temperature. Such behavior is identical to that

observed by Barber and Dynes . It is due to the suppression of thermal fluctuations with lowering temperature. However, we have also observed, for the first time, that the MC peak is broader at lower temperatures in the quasireentrant regime where R increases with decreasing temperature, as we show in Fig. 3 (a). Such behavior is seen in all quasireentrant films similar to Film $`\mathrm{\#}`$ 7. Using the crossover field values, H, obtained from the data in Fig. 3 (a), we find a reduction of Lϕ with decreasing temperature in this temperature range, as shown in Fig. 3 (b). We believe that this observation demonstrates the suppression of the superconducting phase coherence as localization effects are enhanced at lower temperatures.

The above proposal that the MC probes the superconducting phase coherence is further supported by the nonlinear I-V curves we have measured near the S-I transition. Insulating and nearly superconducting films near the S-I transition each has a distinct type of I-V curve . In the low bias regime, the I-V curves of nearly superconducting films show the supercurrent-type behavior: the I-V curves have a downward curvature; while the I-V curves of insulating films show the Coulomb-blockade-like behavior: the I-V curves have an upward curvature. The supercurrent-type behavior indicates the existence of a small supercurrent associated with local superconducting regions. There have been observations that the I-V curves evolve from the Coulomb-blockade-type to the supercurrent-type as the films cross the transition from the insulating side . We have seen the same type of behavior in our films. We have also observed that, in nearly superconducting films, the I-V curves changed from the supercurrent-type to the Coulomb-blockade-type as the conductance of the films is suppressed by a weak H, as shown in the inset in the top-left corner of Fig. 4. This is therefore additional evidence that the application of H suppresses the superconducting fluctuations.

This negative MC and supercurrent-type I-V persisted even in much more insulating films such as Film $`\mathrm{\#}`$6, which did not show any quasireentrant behavior. In this case, the supercurrent-type I-V could only be observed in a narrow temperature range between 0.8 $``$ 1.2 K. In the main part of Fig. 4, we plot the I-V curves measured at 1.05 K on Film $`\mathrm{\#}`$6, for a number of perpendicular field values. Although the effect was much weaker in Film $`\mathrm{\#}`$6 than in less insulating films $`\mathrm{\#}`$7 and $`\mathrm{\#}`$8, we can see clearly that, below a bias voltage of 15 mV, the curvature of the I-V curves changes from downward to upward with a increasing perpendicular field. However, as shown on a higher bias scale in the inset in the low-right corner of Fig. 4, the I-V curves always show an upward curvature regardless of the magnetic field, indicating the insulating nature of Film $`\mathrm{\#}`$6. Thus although Films $`\mathrm{\#}`$6 was very insulating, there still existed a finite Lϕ, which resulted in an observable supercurrent-type I-V in zero-field at temperatures not so low that the effect is completely suppressed by localization.

In conclusion, we have directly observed for the first time the finite superconducting phase coherence length Lϕ on the insulating side of the S-I transition. Our quench-condensed Be films show both the quasireentrant behavior of granular films and the varying Tc usually seen in uniformly disordered films. Scanning force microscopy studies have shown that the length scale of disorder is much shorter in these Be films than that of apparently granular films. The MC is negative, large, and highly anisotropic in the direction of the field. Our results demonstrate that this MC gives a direct probe of the length scale associated with the S-I transition. In nearly insulating films, Lϕ is observed to $`\mathrm{d}\mathrm{e}\mathrm{c}\mathrm{r}\mathrm{e}\mathrm{a}\mathrm{s}\mathrm{e}`$ with $`\mathrm{d}\mathrm{e}\mathrm{c}\mathrm{r}\mathrm{e}\mathrm{a}\mathrm{s}\mathrm{i}\mathrm{n}\mathrm{g}`$ temperature, highlighting the competition between localization and superconductivity. With increasing film thickness, we expect Lϕ to grow and to diverge as the films eventually develop a global superconducting phase with zero resistance.

We gratefully acknowledge numerous invaluable discussions with S. Teitel, Y. Shapir, Y. Gao, and P. Adams. We thank S. Zorba and Y. Gao who performed scanning force microscopy studies of our quench-condensed Be films.


text:
# Single-mode delay time statistics for scattering by a chaotic cavity

## I Introduction

Microwave cavities have proven to be a good experimental testing ground for theories of chaotic scattering. Much work has been done on static scattering properties, but recently dynamic features have been measured as well. A key dynamical observable, introduced by Genack and coworkers, is the frequency derivative $`\varphi ^{}=\mathrm{d}\varphi /\mathrm{d}\omega `$ of the phase of the wave amplitude measured in a single speckle of the transmitted or reflected wave. Because one speckle corresponds to one element of the scattering matrix, and because $`\varphi ^{}`$ has the dimension of time, this quantity is called the single-channel or single-mode delay time. It is a linear superposition of the Wigner-Smith delay times introduced in nuclear physics.

The probability distribution of the Wigner-Smith delay times for scattering by a chaotic cavity is known. The purpose of this paper is to derive from that the distribution $`P(\varphi ^{})`$ of the single-mode delay time. The calculation follows closely our previous calculation of $`P(\varphi ^{})`$ for reflection from a disordered waveguide in the localized regime. The absence of localization in a chaotic cavity is a significant simplification. For a small number of modes $`N`$ connecting the cavity to the outside we can calculate $`P(\varphi ^{})`$ exactly, while for $`N1`$ we can use perturbation theory in $`1/N`$. The large-$`N`$ distribution has the same form as that following from diffusion theory in a disordered waveguide, but for small $`N`$ the distribution is qualitatively different. In particular, there is a marked distinction between the distribution in transmission and in reflection.

## II Formulation of the problem

The geometry studied is shown schematically in Figure 1. It consists of an $`N`$-mode waveguide connected at one end to a chaotic cavity. Reflections at the connection between waveguide and cavity are neglected (ideal impedance matching). The $`N`$ modes may be divided among different waveguides, for example, $`N=2`$ could refer to two single-mode waveguides. The cavity may contain a ferri-magnetic element as in Refs. , in which case time-reversal symmetry is broken. The symmetry index $`\beta =1`$ $`(2)`$ indicates the presence (absence) of time-reversal symmetry. We assume a single polarization for simplicity, as in the microwave experiments in a planar cavity.

The dynamical observable is the correlator $`\rho `$ of an element of the scattering matrix $`S(\omega )`$ at two nearby frequencies,

$$\rho =S_{nm}(\omega +\frac{1}{2}\delta \omega )S_{nm}^{}(\omega \frac{1}{2}\delta \omega ).$$
(1)
The indices $`n`$ and $`m`$ indicate the detected outgoing mode and the incident mode, respectively. The single-mode delay time $`\varphi ^{}`$ is defined by

$$\varphi ^{}=\underset{\delta \omega 0}{lim}\frac{\mathrm{Im}\rho }{\delta \omega I},$$
(2)
with $`I=|S_{nm}(\omega )|^2`$ the intensity of the scattered wave in mode $`n`$ for unit incident intensity in mode $`m`$. If we write the scattering amplitude $`S_{nm}=\sqrt{I}\mathrm{e}^{i\varphi }`$ in terms of amplitude and phase, then $`\varphi ^{}=\mathrm{d}\varphi /\mathrm{d}\omega `$. We will investigate the distribution of $`\varphi ^{}`$ in an ensemble of chaotic cavities having slightly different shape, at a given mean frequency interval $`\mathrm{\Delta }`$ between the cavity modes. For notational convenience, we choose units of time such that $`2\pi /\mathrm{\Delta }1`$.

The single-mode delay times are linearly related to the Wigner-Smith  delay times $`\tau _1,\tau _2,\mathrm{},\tau _N`$, which are the eigenvalues of the matrix

$$Q=iS^{}\frac{\mathrm{d}S}{\mathrm{d}\omega }=U^{}\mathrm{diag}(\tau _1,\mathrm{},\tau _N)U.$$
(3)
To see this, we first expand the scattering matrix linearly in $`\delta \omega `$,

$$S(\omega \pm \frac{1}{2}\delta \omega )=V^\mathrm{T}U\pm \frac{1}{2}i\delta \omega V^\mathrm{T}\mathrm{diag}(\tau _1,\mathrm{},\tau _N)U.$$
(4)
Since $`S`$ is symmetric for $`\beta =1`$, one then has $`V=U`$. For $`\beta =2`$, $`V`$ and $`U`$ are statistically independent. Combination of Eqs. (1), (2), and (4) leads to

$`I=|{\displaystyle \underset{i}{}}u_iv_i|^2,\varphi ^{}=\mathrm{Re}{\displaystyle \frac{_i\tau _iu_iv_i}{_ju_jv_j}},`$ (5)
$`u_i=U_{im},v_i=V_{in}.`$ (6)
The distribution of the Wigner-Smith delay times for a chaotic cavity was calculated in Ref. . It is a Laguerre ensemble in the rates $`\mu _i=1/\tau _i`$,

$`P(\mu _1,\mathrm{},\mu _N){\displaystyle \underset{i<j}{}}|\mu _i\mu _j|^\beta {\displaystyle \underset{k}{}}\mu _k^{\beta N/2}\mathrm{exp}({\displaystyle \frac{1}{2}}\beta \mu _k)\theta (\mu _k).`$ (7)
The step function $`\theta (x)=1`$ for $`x>0`$ and $`\theta (x)=0`$ for $`x<0`$. It follows from Eq. (7) that $`_i\tau _i=1`$, a result that was known previously.

To calculate the joint distribution $`P(I,\varphi ^{})`$ from Eq. (5), we also need the distribution of the coefficients $`u_i`$ and $`v_i`$. This follows from the Wigner conjecture, proven in Ref. , according to which the matrices $`U`$ and $`V`$ are uniformly distributed in the unitary group. The calculation for small $`N`$ is now a straightforward integration, see Sec. III. For large $`N`$ we can use perturbation theory, see Sec. IV.

Because of the uniform distribution of $`U`$ and $`V`$, independent of the $`\tau _i`$’s, we can evaluate the average of $`\varphi ^{}`$ directly for any $`N`$,

$$\varphi ^{}=\mathrm{Re}\underset{i}{}\tau _i\frac{u_iv_i}{_ju_jv_j}=\underset{i}{}\tau _i\frac{1}{N}=\frac{1}{N}.$$
(8)
We define the rescaled variable $`\widehat{\varphi ^{}}=\varphi ^{}/\varphi ^{}=N\varphi ^{}`$, that we will use in the next sections.

## III Small number of modes

For $`N=1`$ there is no difference between the Wigner-Smith delay time and the single-mode delay time. In that case $`I=1`$ and $`\widehat{\varphi ^{}}=\varphi ^{}`$ is distributed according to

$$P(\widehat{\varphi ^{}})=c_\beta \widehat{\varphi ^{}}^{2\beta /2}\mathrm{exp}(\frac{1}{2}\beta /\widehat{\varphi ^{}})\theta (\widehat{\varphi ^{}}).$$
(9)
The normalization coefficient $`c_\beta `$ equals $`(2\pi )^{1/2}`$ for $`\beta =1`$ and $`1`$ for $`\beta =2`$.

Now we turn to the case $`N=2`$. By writing out the summation in Eq. (5) for $`I`$ and $`\varphi ^{}`$, one obtains $`\varphi ^{}=\tau _++\alpha \tau _{}`$ with $`\tau _\pm =\frac{1}{2}(\tau _1\pm \tau _2)`$ and

$`I=|u_1|^2|v_1|^2+|u_2|^2|v_2|^2+u_1u_2^{}v_1v_2^{}+u_1^{}u_2v_1^{}v_2,`$ (10)
$`\alpha =(|u_1|^2|v_1|^2|u_2|^2|v_2|^2)/I.`$ (11)
To find the joint distribution $`P(I,\alpha )`$ we parametrize $`U`$ in terms of $`4`$ independent angles,

$$U=\left(\begin{array}{cc}\mathrm{cos}\gamma \mathrm{exp}(i\alpha _1)& \mathrm{sin}\gamma \mathrm{exp}(i\alpha _1i\alpha _2)\\ \mathrm{sin}\gamma \mathrm{exp}(i\alpha _3+i\alpha _2)& \mathrm{cos}\gamma \mathrm{exp}(i\alpha _3)\end{array}\right),$$
(12)
with $`\alpha _i(0,2\pi )`$ and $`\gamma (0,\pi /2)`$. The invariant measure $`\mathrm{d}\mu |\mathrm{Det}g|\mathrm{d}\gamma _i\mathrm{d}\alpha _i`$ in the unitary group follows from the metric tensor $`g`$, defined by

$$\mathrm{Tr}\mathrm{d}U\mathrm{d}U^{}=\underset{i,j}{}g_{ij}\mathrm{d}x_i\mathrm{d}x_j,\{x_i\}=\{\gamma ,\alpha _1,\alpha _2,\alpha _3\}.$$
(13)
The result is

$$\mathrm{d}\mu \mathrm{sin}2\gamma \mathrm{d}\gamma \underset{i}{}\mathrm{d}\alpha _i.$$
(14)
The joint distribution function $`P(\tau _+,\tau _{})`$ follows from Eq. (7). For $`\beta =1`$ one has

$$P(\tau _+,\tau _{})=\frac{1}{12}|\tau _{}|(\tau _+^2\tau _{}^2)^4\mathrm{exp}\left(\tau _+(\tau _+^2\tau _{}^2)^1\right)\theta (\tau _+|\tau _{}|),$$
(15)
while for $`\beta =2`$

$$P(\tau _+,\tau _{})=\frac{1}{3}\tau _{}^2(\tau _+^2\tau _{}^2)^6\mathrm{exp}\left(2\tau _+(\tau _+^2\tau _{}^2)^1\right)\theta (\tau _+|\tau _{}|).$$
(16)
First we consider the case $`\beta =1`$, $`nm`$. Because of the unitarity of $`U`$, one has $`|v_1|^2=|u_2|^2`$ and $`|v_2|^2=|u_1|^2`$. Therefore $`\alpha =0`$ and $`\varphi ^{}=\tau _+`$, so $`\varphi ^{}`$ is independent of $`I`$. Integration of Eq. (15) over $`\tau _{}`$ results in

$$P(\widehat{\varphi ^{}})=\frac{2}{3}\widehat{\varphi ^{}}^5(\widehat{\varphi ^{}}^2+2\widehat{\varphi ^{}}+2)\mathrm{exp}(2/\widehat{\varphi ^{}})\theta (\widehat{\varphi ^{}}).$$
(17)
In this case (as well as in the case $`N=1`$), $`\widehat{\varphi ^{}}`$ can take on only positive values, but this is atypical, as we will see shortly. From Eqs. (10) and (12) we find the relation between $`I`$ and the parametrization of $`U`$,

$$I=\mathrm{sin}^22\gamma \mathrm{sin}^2(\alpha _3\alpha _1\alpha _2).$$
(18)
The distribution of $`I`$ resulting from the measure (14) is

$$P(I)=\frac{1}{2}I^{1/2}\theta (I)\theta (1I),$$
(19)
in agreement with Refs. .

For the case $`N=2`$, $`\beta =1`$, $`n=m`$ we use that $`u_1=v_1`$, $`u_2=v_2`$ and obtain the parametrization

$`I=1\mathrm{sin}^22\gamma \mathrm{sin}^2(\alpha _3\alpha _1\alpha _2),`$ (20)
$`\alpha =(\mathrm{cos}2\gamma )/I.`$ (21)
The distribution $`P(I,\alpha )`$ resulting from the measure (14) is

$$P(I,\alpha )=\frac{1}{2\pi }I^{1/2}(1I)^{1/2}(1I\alpha ^2)^{1/2}\theta (I)\theta (1I)\theta (1I\alpha ^2).$$
(22)
The joint distribution of $`I`$ and $`\widehat{\varphi ^{}}=2\varphi ^{}`$ takes the form

$$P(I,\widehat{\varphi ^{}})=_0^{\mathrm{}}d\tau _{}_\tau _{}^{\mathrm{}}d\tau _+P(\tau _+,\tau _{})P\left(I,\alpha =\frac{\widehat{\varphi ^{}}/2\tau _+}{\tau _{}}\right)\frac{1}{\tau _{}}.$$
(23)
The distribution of $`I`$ following from integration of $`P(I,\alpha )`$ over $`\alpha `$ is given by Eq. (19) with $`I1I`$, as it should. The integrations over $`\tau _+,\tau _{}`$, and $`I`$, needed to obtain $`P(\widehat{\varphi ^{}})`$ can be evaluated numerically, see Fig. 2. Notice that $`P(\widehat{\varphi ^{}})`$ has a tail towards negative values of $`\widehat{\varphi ^{}}`$.

For $`N=2,\beta =2`$ it doesn’t matter whether $`n`$ and $`m`$ are equal or not. Parametrization of both $`U`$ and $`V`$ leads to

$`I=(1x_1)(1x_2)+x_1x_2+2\sqrt{(1x_1)(1x_2)x_1x_2}\mathrm{cos}\eta ,`$ (24)
$`\alpha =(1x_1x_2)/I,`$ (25)
with a measure $`\mathrm{d}\mu \mathrm{d}x_1\mathrm{d}x_2\mathrm{d}\eta `$ and $`x_1,x_2(0,1)`$, $`\eta (0,\pi )`$. The joint distribution $`P(I,\alpha )`$ is now given by

$$P(I,\alpha )=\frac{1}{2}I^{1/2}\theta (I)\theta (1I)\theta (1I\alpha ^2).$$
(26)
Integration over $`\alpha `$ leads to

$$P(I)=\theta (I)\theta (1I).$$
(27)
The distribution $`P(I,\widehat{\varphi ^{}})`$ follows upon insertion of Eqs. (16) and (26) into Eq. (23). Numerical integration yields the distribution $`P(\widehat{\varphi ^{}})`$ plotted in Fig. 3. As in the previous case, there is a tail towards negative $`\widehat{\varphi ^{}}`$.

## IV Large number of modes

We now calculate the joint distribution $`P(I,\varphi ^{})`$ for $`N1`$. First the case $`nm`$ will be considered, when there is no distinction between $`\beta =1`$ and $`\beta =2`$. In the large $`N`$-limit the vectors $`𝐮`$ and $`𝐯`$ become uncorrelated and their elements become independent Gaussian numbers with zero mean and variance $`1/N`$. We first average over $`𝐯`$, following Ref. . We introduce the weighted delay time $`W=I\varphi ^{}`$. The Fourier transform of $`P(I,W)`$ is given by $`\chi (p,q)=\mathrm{exp}(ipI+iqW)`$. The average over $`𝐯`$ is a Gaussian integration, that gives

$`\chi (p,q)=\mathrm{det}(1iH/N)^1,`$ (28)
$`H=p\text{u}^{}\text{u}^\mathrm{T}+{\displaystyle \frac{1}{2}}q(\overline{\text{u}}^{}\text{u}^\mathrm{T}+\text{u}^{}\overline{\text{u}}^\mathrm{T}),`$ (29)
where $`\overline{u}_i=u_i\tau _i`$. The matrix $`H`$ has only two nonzero eigenvalues,

$`\lambda _\pm ={\displaystyle \frac{1}{2}}\left(qB_1+p\pm \sqrt{2pqB_1+q^2B_2+p^2}\right),`$ (30)
$`B_k={\displaystyle \underset{i}{}}|u_i|^2\tau _i^k.`$ (31)
Performing the inverse Fourier transforms and returning to the variables $`\varphi ^{}`$ and $`I`$ leads to

$$P(I,\varphi ^{})=(N^3I/\pi )^{1/2}\mathrm{exp}(NI)(B_2B_1^2)^{1/2}\mathrm{exp}\left(NI\frac{(\varphi ^{}B_1)^2}{B_2B_1^2}\right)\theta (I).$$
(32)
The averages over $`u_i`$ and $`\tau _i`$ still have to be performed.

Up to now the derivation is the same as for the disordered waveguide in the localized regime, the only difference being the different distribution of the Wigner-Smith delay times $`\tau _i`$. The absence of localization in a chaotic cavity greatly simplifies the subsequent calculation in our present case. While in the localized waveguide anomalously large $`\tau _i`$’s lead to large fluctuations in $`B_1`$ and $`B_2`$, in the chaotic cavity the term $`\mu _k^{\beta N/2}`$ in Eq. (7) suppresses large delay times. Fluctuations in $`B_k`$ are smaller than the mean by a factor $`1/\sqrt{N}`$. For $`N1`$ we may therefore replace $`B_k`$ in Eq. (32) by $`B_k`$.

To calculate the average of $`B_1`$ and $`B_2`$ we need the density $`\rho (\tau )=_i\delta (\tau \tau _i)`$ of the delay times. It is given by

$$\rho (\tau )=\frac{N}{2\pi \tau ^2}\sqrt{(\tau _+\tau )(\tau \tau _{})},\tau _\pm =\frac{3\pm \sqrt{8}}{N},$$
(33)
for $`\tau `$ inside the interval $`(\tau _{},\tau _+)`$. The density is zero outside this interval. The resulting averages are $`B_1=N^1`$ and $`B_2=2N^2`$, which leads to

$$P(I,\widehat{\varphi ^{}})=(N^3I/\pi )^{1/2}\mathrm{exp}\left(NI\left[1+(\widehat{\varphi ^{}}1)^2\right]\right)\theta (I).$$
(34)
(Recall that $`\widehat{\varphi ^{}}=\varphi ^{}/\varphi ^{}=N\varphi ^{}`$.) Integration over $`\widehat{\varphi ^{}}`$ or $`I`$ gives

$`P(I)`$ $`=`$ $`N\mathrm{exp}(NI)\theta (I),`$ (35)
$`P(\widehat{\varphi ^{}})`$ $`=`$ $`{\displaystyle \frac{1}{2}}\left[1+(\widehat{\varphi ^{}}1)^2\right]^{3/2}.`$ (36)
This distribution of $`I`$ and $`\widehat{\varphi ^{}}`$ has the same form as that of a disordered waveguide in the diffusive regime .

We next turn to the case $`n=m`$ and $`\beta =1`$. (For $`\beta =2`$ there is no difference between $`n=m`$ and $`nm`$.) Since $`u_i=v_i`$ in Eq. (5) we have

$$I=|C_0|^2,\varphi ^{}=\mathrm{Re}\frac{C_1}{C_0},C_k=\underset{i}{}\tau _i^ku_i^2.$$
(37)
The joint distribution $`P(C_0,C_1)`$ has the Fourier transform

$$\chi (p_0,p_1,q_0,q_1)=\mathrm{exp}(ip_0\mathrm{Re}C_0+iq_0\mathrm{Im}C_0+ip_1\mathrm{Re}C_1+iq_1\mathrm{Im}C_1).$$
(38)
Averaging over $`𝐮`$ we find

$`\chi (p_0,p_1,q_0,q_1)=\mathrm{exp}(L),`$ (39)
$`L={\displaystyle \frac{1}{2}}{\displaystyle \underset{i}{}}\mathrm{ln}\left[1+N^2(p_0+p_1\tau _i)^2+N^2(q_0+q_1\tau _i)^2\right].`$ (40)
Fluctuations in $`L`$ are smaller than the average by a factor $`1/N`$. We may therefore approximate $`\mathrm{exp}(L)\mathrm{exp}L`$. Because $`N^2(p_0+p_1\tau _i)^2+N^2(q_0+q_1\tau _i)^2`$ is of order $`1/N`$, we may expand the logarithm in Eq. (40). The average follows upon integration with the density (33),

$$L=\frac{p_0^2+q_0^2}{2N}+\frac{p_1^2+q_1^2}{N^3}+\frac{p_0p_1+q_0q_1}{N^2}.$$
(41)
Inverse Fourier transformation gives

$$P(C_0,C_1)=\frac{N^4}{(2\pi )^2}\mathrm{exp}(N|C_0|^2\frac{1}{2}N^3|C_1|^2+N^2\mathrm{Re}C_0C_1^{}).$$
(42)
The resulting distribution of $`\widehat{\varphi ^{}}`$ and $`I`$ is

$$P(I,\widehat{\varphi ^{}})=(N^3I/2\pi )^{1/2}\mathrm{exp}\left(\frac{1}{2}NI\left[1+(\widehat{\varphi ^{}}1)^2\right]\right)\theta (I).$$
(43)
It is the same as the distribution (34) for $`nm`$, apart from the rescaling of $`I`$ by a factor of $`2`$ as a result of coherent backscattering.

The distribution (36) of $`\widehat{\varphi ^{}}`$ for $`N1`$ is included in Figs. 2 and 3 for comparison with the small $`N`$-results.

## V Numerical check

We can check our analytical calculations by performing a Monte Carlo average over the Laguerre ensemble for the $`\tau _i`$’s and the unitary group for the $`u_i`$’s and $`v_i`$’s. For the average over the unitary group we generate a large number of complex Hermitian $`N\times N`$ matrices $`H`$. The real and imaginary part of the off-diagonal elements are independently Gaussian distributed with zero mean and unit variance. The real diagonal elements are independently Gaussian distributed with zero mean and variance 2. We diagonalize $`H`$, order the eigenvalues from large to small, and multiply the $`n`$-th normalized eigenvector by a random phase factor $`\mathrm{e}^{i\alpha _n}`$, with $`\alpha _n`$ chosen uniformly from $`(0,2\pi )`$. The resulting matrix of eigenvectors is uniformly distributed in the unitary group.

The Laguerre ensemble (7) for the rates $`\mu _i=1/\tau _i`$ can be generated by a random matrix of the Wishart type . Consider a $`N\times (2N1+2/\beta )`$ matrix $`X`$, where $`X`$ is real for $`\beta =1`$ and complex for $`\beta =2`$. (The matrix $`X`$ is neither symmetric nor Hermitian.) The matrix elements are Gaussian distributed with zero mean and variance $`|x_{nm}|^2=1`$. The joint probability distribution of the eigenvalues of the matrix $`XX^{}`$ is then given by Eq. (7). The results of our numerical check are included in Figs. 2 and 3. The large-$`N`$ limit is represented by $`N=400`$, $`nm`$. The analytical curves agree well with the numerical data.

## VI Conclusion

We have investigated the statistics of the single-mode delay time $`\varphi ^{}`$ for chaotic scattering. For a large number $`N`$ of scattering channels the distribution has the same form as for diffusive scattering, but for small $`N`$ the distribution is different. The case $`N=2`$ is of particular interest, representing a cavity connected to two single-mode waveguides. For preserved time-reversal symmetry and detection in transmission ($`\beta =1,nm`$), we find that $`\varphi ^{}`$ can take on only positive values, similarly to the Wigner-Smith delay times. In contrast, for detection in reflection (or for broken time-reversal symmetry) the distribution acquires a tail towards negative $`\varphi ^{}`$. These theoretical predictions are amenable to experimental test in the microwave cavities of current interest.

Acknowledgements

We thank P.W. Brouwer and M. Patra for valuable advice. This research was supported by the “Nederlandse organisatie voor Wetenschappelijk Onderzoek” (NWO) and by the “Stichting voor Fundamenteel Onderzoek der Materie” (FOM).


text:
# Quantum Zeno-like effect and spectra of particles in cascade transition

## 1 Introduction

The term “quantum Zeno paradox” had been introduced in . It was argued there that an unstable particle which was continuously observed in order to see whether it decays would never be found to decay (for review see ). In the present paper we restrict our consideration to the special case of continuous waiting-mode (or negative result) observations of spontaneous decay. An example of such measurements is a registration, by a permanently presented detector, of particles emitted during quantum state decay. Until the detector is “discharged”, we continuously obtain information that the system is in the initial excited state. Another interesting example of waiting-mode observation of spontaneous decay one can find in . It was shown  that in the general case decay may be “frozen” by continuous waiting-mode observation only at the limit of infinitely fast reaction of measuring device on event of decay (infinitely short decoherence time). However, in case of realistic decoherence time the decay may be perturbed in various directions: it may be either slowed down or fastened. The sign of the effect depends on details of transition matrix elements behavior and on transition energy. This is a quantum Zeno effect, not a paradox. Thus, in our definition, the quantum Zeno effect is any influence of continuous measurement to probability of decay. At the limit of infinitely fast measuring device quantum Zeno effect means “freezing” of decay. Qualitatively, the complicated behavior of quantum Zeno effect may be related to a complicated behavior of initial part of decay curve. We will discuss this relation in more details elsewhere.

It is a difficult problem to determine how a permanently presented detector affects on the probability of decay in realistic situations . But the kinematics of this process are very similar to those of a group of phenomena which was called quantum Zeno-like effects . All these phenomena (including above mentioned observation) are described by the same general equation for perturbation of decay probability . Also, these phenomena has a common main feature: The final state of decay could not be considered as stable, but further transition to other orthogonal states occur. Just these transitions perturb the decay constant. The consideration of some of Zeno-like effects turns out to be much simpler than the genuine Zeno effect. So, it is reasonable to begin with more simple problems.

Systems that show Zeno-like effects differ from each other by the reason of transition from final state of decay. The system with forced resonance transition from the final state of decay was studied in . The analogous system was considered as a particular case of a general Zeno-like system in . M. B. Mensky  was the first who proposed to consider a spontaneously decaying system with a spontaneously decaying final state as the system demonstrating quantum Zeno or Zeno-like effect. A simple example of such a system is the system with two-step spontaneous cascade transition. Such systems are the subject of the present paper.

Let $`X`$ be a three-level system (for example, atom or atomic nucleus) with states $`|x_0`$, $`|x_1`$, $`|x_2`$ and eigenenergies $`\omega _0^x`$, $`\omega _1^x`$, $`\omega _2^x`$ respectively (it is assumed $`\mathrm{}=1`$ hereafter). Suppose that system $`X`$ was prepared in state $`|x_0`$ at the initial moment of time $`t=0`$. State $`|x_0`$ is unstable and decays spontaneously to state $`|x_1`$ due to interaction with another system (“field”). The latter system has a continuous spectrum of states. Let state $`|x_1`$ be also unstable. System $`X`$ further decays from state $`|x_1`$ to final stable state $`|x_2`$. We suppose for simplicity that direct transition from state $`|x_0`$ to $`|x_2`$ is forbidden. Such a system exhibits cascade spontaneous transition from state $`|x_0`$ to state $`|x_2`$ through intermediate state $`|x_1`$. This phenomenon was studied in some details many years ago  and was discussed in classical monographs . A new property of cascade transition that was pointed out in  was that the instability of level $`|x_1`$ should affect the life-time of level $`|x_0`$.

It was noted in  that during cascade transition the second fast transition $`|x_1|x_2`$ after decay of initial state $`|x_0`$ to $`|x_1`$ was similar to waiting-mode observation of first decay $`|x_0|x_1`$. The main difference of the second transition from a genuine continuous measurement is that it is not possible to switch off the interaction causing the second transition, but it is possible to stop a measurement. Hence, the perturbation of decay rate of transition $`|x_0|x_1`$ by instability of state $`|x_1`$ may be attributed to quantum Zeno-like effect. We use the term quantum Zeno effect as synonym for quantum Zeno-like effect throughout the present paper.

The formula for decay rate of state $`|x_0`$ perturbed by instability of state $`|x_1`$ was derived in . With notations analogous to those in our paper, this formula reads as

$$\stackrel{~}{\mathrm{\Gamma }}_0=2\pi _0^{\mathrm{}}𝑑\omega 𝒱(\omega )\frac{1}{\pi }\frac{\lambda _1}{\lambda _1^2+(\omega \omega _{01}+\mu _1)^2}.$$
(1)
Here $`\omega _{01}=\omega _0^x\omega _1^x`$; $`𝒱(\omega )`$ is the sum of all square modula of transition matrix elements related to the same energy $`\omega `$ of emitted particle; $`\lambda _1`$ is the real part of decay constant of level $`|x_1`$; $`\mu _1`$ is the contribution to radiation shift of level $`|x_1`$ from discrete level $`|x_2`$ . We shall hereafter mention similar energy shifts as radiation shifts simply. The complex decay constant $`\gamma _1`$ of level $`|x_1`$ is $`\gamma _1=\lambda _1+i\mu _1`$ if the system was prepared in state $`|x_1`$. At the limit of $`\lambda _10`$ Eq. (1) transforms into conventional Fermi’s Golden rule:

$$\mathrm{\Gamma }_0=2\pi 𝒱(\omega _{01}\mu _1),$$
(2)
but wherein transition energy is corrected by radiation shift of level $`|x_1`$. However, deviation of perturbed probability $`\stackrel{~}{\mathrm{\Gamma }}_0`$ from unperturbed value $`\mathrm{\Gamma }_0`$ exists, if $`\lambda _10`$. Just this phenomenon is considered as quantum Zeno effect in . It is easily seen from Eq. (1) that Zeno effect is strong if $`\lambda _1`$ is comparable with $`\omega _{01}`$ by its value. If formally $`\lambda _1\mathrm{}`$ we obtain $`\stackrel{~}{\mathrm{\Gamma }}_0=0`$. This is pure “quantum Zeno paradox”.

It is possible to make an interesting conclusion from Eq. (1). Suppose $`\omega _{01}\mu _1<0`$. Then Golden rule Eq. (2) predicts zero probability of decay of level $`|x_0`$ since $`𝒱(\omega )0`$ for $`\omega <0`$. There are no field quanta with negative energy. However, Eq. (1) shows that perturbed value of probability of decay $`\stackrel{~}{\mathrm{\Gamma }}_0`$ is grater than zero in this situation generally. This phenomenon is a special case of quantum Zeno effect. Hence, the transition from lower ($`|x_0`$) to upper ($`|x_1`$) level is possible, and positive energy quanta should be emitted in such a process. So, an important question arises: What are the spectra of quanta emitted during transitions $`|x_0|x_1`$ and $`|x_1|x_2`$ in this unusual situation? Also, what are these spectra in the general case when transition energy $`\omega _{01}`$ is comparable with decay constant $`\lambda _1`$ of level $`|x_1`$? Obviously, these spectra cannot be Lorentzian-shape peaks.

Eq. (1) was derived on the base of the second order perturbation theory in . The spectra of emitted particles can not be calculated by this method. So, the present paper includes two aims. Firstly, we derive no-decay amplitude of initial state $`|x_0`$ and probability $`\stackrel{~}{\mathrm{\Gamma }}_0`$ by nonperturbative method which is based on direct transition from non-Markovian evolution equations to Markovian approximation. Secondly, we obtain all spectra of interest from our nonperturbative solution of Shrödinger equation: mutual energy distribution of particles emitted in the first and second transitions, spectra of particles emitted in the first and second transitions separately, and distribution of the sum of energy of first and second emitted particles. Some of these spectra was determined early , but those results are not related to the conditions $`\omega _{01}\lambda _1`$ or $`\omega _{01}<0`$.

This paper is organized as follows. In Section 2 we discuss the Markovian approximation for a spontaneous exponential decay in two-level system. In Section 3 we use the formalism developed in Section 2 for description of cascade transition in a three-level system and obtain our main results: perturbed values of decay constant and radiation shift of level $`|x_0`$ and spectra of particles. Finally, some features of these results are discussed in Section 4 and conclusions are drawn.

## 2 Markovian approximation in two-level problem

We consider a model of spontaneous transition of a general type. Let $`X`$ be a two-level system $`(|x_0,|x_1)`$. System $`X`$ interacts with another system $`F`$ (field). System $`F`$ has a ground state $`|f_0`$ and continuous spectrum of exited states $`|y_\eta `$, where $`\eta `$ is the index of state in the continuous spectrum. Since we discuss in Section 3 a field with quanta of two different kinds, we use the notation $`|y`$ for field quanta instead of $`|f`$. The continuous spectrum states are normalized by condition $`y_\eta |y_\eta ^{}=\delta (\eta \eta ^{}).`$ Let the initial state of the combined system $`XF`$ at time $`t=0`$ be

$$|\mathrm{\Psi }(0)=|x_0|f_0|x_0f_0.$$

The Hamiltonian of system is

$$H=H_0+V$$

where $`H_0`$ is a “free” Hamiltonian

$$H_0=\omega _0^x|x_0x_0|+\omega _1^x|x_1x_1|+\omega _\eta ^yb_\eta ^+b_\eta 𝑑\eta $$

and $`V`$ is an interaction between $`X`$ and $`F`$:

$$V=\left[v(\eta )b_\eta ^+|x_1x_0|+v^{}(\eta )b_\eta |x_0x_1|\right]𝑑\eta .$$
(3)
In Eq. (3) $`b_\eta ^+`$ is the creation operator for state $`|y_\eta `$. It does not matter what is the commutation relation for operators $`b_\eta `$: either $`[b_\eta ,b_\eta ^{}^+]_{}=\delta (\eta \eta ^{})`$ or $`[b_\eta ,b_\eta ^{}^+]_+=\delta (\eta \eta ^{})`$. It is easy to see that $`v(\eta )`$ is a matrix element of transition: $`v(\eta )=x_1y_\eta |V|x_0f_0`$.

To solve the Shrödinger equation

$$|\dot{\mathrm{\Psi }}(t)=i(H_0+V)|\mathrm{\Psi }(t)$$
(4)
we use the ansatz

$$|\mathrm{\Psi }(t)=|x_0f_0a_0(t)e^{i\omega _0^xt}+𝑑\eta |x_1y_\eta a_{1\eta }(t)e^{i(\omega _1^x+\omega _\eta ^y)t}.$$
(5)
Substituting Eq. (5) for $`|\mathrm{\Psi }(t)`$ in Eq. (4) we obtain the system of equations:

$`\dot{a}_0(t)`$ $`=`$ $`i{\displaystyle 𝑑\eta v^{}(\eta )e^{i(\omega _\eta ^y\omega _{01})t}a_{1\eta }(t)}`$ (6)
$`\dot{a}_{1\eta }(t)`$ $`=`$ $`iv(\eta )e^{i(\omega _\eta ^y\omega _{01})t}a_0(t).`$ (7)
Eq. (7) can be solved for coefficients $`a_{1\eta }`$. Substituting the solution for $`a_{1\eta }`$ in Eq. (6) we get the equation for coefficient $`a_0(t)`$:

$$\dot{a}_0(t)=_0^ta_0(t_1)q_0(tt_1)𝑑t_1,$$
(8)
where

$$q_0(\tau )=|v(\eta )|^2e^{i(\omega _\eta ^y\omega _{01})\tau }𝑑\eta .$$
(9)
The amplitude $`a_0(t)`$ is a solution of non-Markovian equation (8): the derivative of $`\dot{a}_0`$ at the moment of time $`t`$ is expressed through all values of $`a_0`$ for all moments of time from $`0`$ to $`t`$.

A. Sudbery  proposed qualitative arguments that the function $`q_0(\tau )`$ in Eq. (8) was a very narrow peak around value $`\tau =0`$ for usual decay systems. Besides, it is possible to understand why it should be the case if we consider the behavior of function $`v(\eta )`$.

The index $`\eta `$ of state $`|y_\eta `$ can be represented as the eigenenergy of the state $`\omega ^y`$ and the degeneration index $`\alpha ^y`$: $`\eta =\{\omega ^y,\alpha ^y\}`$. Then Eq. (9) can be rewritten as

$$q_0(\tau )=e^{i\omega _{01}\tau }_0^{\mathrm{}}𝒱(\omega ^y)e^{i\omega ^y\tau }𝑑\omega ^y,$$
(10)
where

$$𝒱(\omega ^y)=|v(\omega ^y,\alpha ^y)|^2𝑑\alpha ^y.$$
(11)
The integral in Eq. (11) means a sum for discrete indexes. Eq. (10) shows that the function $`q_0(\tau )`$ is a Fourier transform of function $`𝒱(\omega ^y)`$ up to factor $`\mathrm{exp}(i\omega _{01}\tau )`$ which is equal to one by module. The function $`𝒱(\omega ^y)`$ is very wide for usual decay systems. For example, in the case of electromagnetic 2P-1S transition of hydrogen atom, the value $`\mathrm{\Lambda }`$ of natural cut-off of function $`𝒱(\omega ^y)`$ is $`\mathrm{\Lambda }=\frac{3}{2}\alpha m_e5.610^3`$ eV, where $`\alpha `$ is the fine structure constant and $`m_e`$ is the electron mass . The value of $`\mathrm{\Lambda }`$ is much greater than the energy of 2P-1S transition. The Fourier transform of wide real non-negative function $`𝒱(\omega ^y)`$ is a narrow peak near $`\tau =0`$. Consequently, the function $`q_0(\tau )`$ is a narrow peak near $`\tau =0`$ too. The width of this peak is about $`\tau _{Zen}=1/\mathrm{\Lambda }`$. Suppose $`a_0(t)`$ to vary slowly during time intervals of the order of $`1/\omega _{01}`$ for times $`t1/\omega _{01}`$. Then, for the same times, $`a_0(t)`$ is approximately constant during the time interval of order $`\tau _{Zen}`$ and the function $`a_0(tt_1)`$ may be moved out from the integral in Eq. (8) at time $`t`$. Making also the variable change $`\tau =tt_1`$ we rewrite Eq. (8) as

$$\dot{a}_0(t)=a_0(t)_0^tq_0(\tau )𝑑\tau .$$
(12)
Therefore, we obtain an approximate Markovian equation (12) for $`a_0(t)`$ instead of non-Markovian equation (8). Recall that Eq. (12) is valid only for $`t>>1/\omega _{01}`$. It is not difficult to calculate the integral in r.h.s. of Eq. (12) using Eq. (10):

$$_0^tq_0(\tau )𝑑\tau =_0^{\mathrm{}}𝒱(\omega ^y)\left[\frac{\mathrm{sin}(\omega ^y\omega _{01})t}{\omega ^y\omega _{01}}i\frac{1\mathrm{cos}(\omega ^y\omega _{01})t}{\omega ^y\omega _{01}}\right]𝑑\omega ^y.$$
(13)
Suppose $`𝒱(\omega ^y)`$ is sufficiently smooth. Then it is seen that the integral in the r.h.s. of Eq. (13) does not depend on time for $`t>>1/\omega _{01}`$. Hence, we can change the upper limit of integral from $`t`$ to infinity and find that

$$_0^{\mathrm{}}q_0(\tau )𝑑\tau =\gamma _0=\lambda _0+i\mu _0,$$

where

$`\lambda _0`$ $`=`$ $`\mathrm{Re}\gamma _0=\pi 𝒱(\omega _{01})`$
$`\mu _0`$ $`=`$ $`\mathrm{Im}\gamma _0=P{\displaystyle _0^{\mathrm{}}}{\displaystyle \frac{𝒱(\omega ^y)}{\omega ^y\omega _{01}}}𝑑\omega ^y.`$ (14)
Here $`P`$ denotes the principal value of an integral.

Eq. (12) reads now as $`\dot{a}_0(t)=\gamma _0a_0(t)`$ and has the solution $`a_0(t)=\mathrm{exp}(\gamma _0t)`$. This is the usual exponential decay law. The real part of $`\gamma _0`$ determines the probability of decay per unit of time $`\mathrm{\Gamma }_0=2\mathrm{R}\mathrm{e}\gamma _0=2\pi 𝒱(\omega _{01})`$; the imaginary part of $`\gamma _0`$ is the radiation shift of level $`|x_0`$.

## 3 Decay constants, radiation shifts, and spectra in two-step cascade transition

We consider three-level system $`X`$ with cascade transition $`|x_0|x_1|x_2`$ in this section. The transitions result from interaction of system $`X`$ with another system $`F`$ (field). Suppose that two different types of quanta are emitted during the first and during the second transition. The quanta $`|y_\eta `$ are created during transition $`|x_0|x_1`$ and the quanta $`|z_\zeta `$ are created during transition $`|x_1|x_2`$. The $`y`$ and $`z`$ quanta have creation operators $`b_\eta ^+`$ and $`c_\zeta ^+`$, respectively. We admit that for all $`\eta `$ and $`\zeta `$ the operators $`b_\eta `$ and $`c_\zeta `$ satisfy the relation

$$[b_\eta ,c_\zeta ^+]_{}=0,[b_\eta ,c_\zeta ]_{}=0.$$
(15)
Eq. (15) represents the meaning of difference between particles $`y`$ and $`z`$. Operators $`b_\eta `$ may be either Bozonic or Fermionic type, the same is true for operators $`c_\zeta `$. The statistics type of $`y`$ and $`z`$ particles may be different from each other. For example, we may consider cascade nuclear transition when an atomic electron is emitted in the fist transition (the inner nuclear conversion phenomenon) and electromagnetic quantum is emitted in the second one. Our model is correct for this case. We also can consider a cascade electromagnetic transition, but the energy of the first transition is much less than the energy of the second one. In this case Eq. (15) is not strictly true for all quanta of such cascade transition, but our model may be accounted as a good approximation in this case as well. The generalization to the case when we cannot distinguish between quanta emitted in the first transition and in the second transition is not straightforward and is not discussed here.

The Hamiltonian of the system $`XF`$ is

$$H=H_0+V+W,$$

where

$`H_0`$ $`=`$ $`{\displaystyle \underset{\xi =0}{\overset{2}{}}}\omega _\xi ^x|x_\xi x_\xi |+{\displaystyle 𝑑\eta \omega _\eta ^yb_\eta ^+b_\eta }+{\displaystyle 𝑑\zeta \omega _\zeta ^zc_\zeta ^+c_\zeta },`$ (16)
$`V`$ $`=`$ $`{\displaystyle 𝑑\eta \left[v(\eta )b_\eta ^+|x_1x_0|+v^{}(\eta )b_\eta |x_0x_1|\right]},`$ (17)
$`W`$ $`=`$ $`{\displaystyle 𝑑\zeta \left[w(\zeta )c_\zeta ^+|x_2x_1|+w^{}(\zeta )c_\zeta |x_1x_2|\right]}.`$ (18)
The notations in Eqs. (1618) are similar to those of Section 2 and obvious. For initial state $`|\mathrm{\Psi }(0)=|x_0f_0`$ we solve the Shrödinger equation

$$|\dot{\mathrm{\Psi }}(t)=i(H_0+V+W)|\mathrm{\Psi }(t)$$
(19)
using the ansatz

$`|\mathrm{\Psi }(t)`$ $`=`$ $`|x_0f_0a_0(t)e^{i\omega _0^xt}+{\displaystyle 𝑑\eta |x_1y_\eta a_{1\eta }(t)e^{i(\omega _1^x+\omega _\eta ^y)t}}`$ (20)
$`+{\displaystyle 𝑑\eta 𝑑\zeta |x_2y_\eta z_\zeta a_{2\eta \zeta }(t)e^{i(\omega _2^x+\omega _\eta ^y+\omega _\zeta ^z)t}}.`$
Substituting Eq. (20) for $`|\mathrm{\Psi }(t)`$ in Eq. (19) we obtain the system of equations

$`\dot{a}_0(t)`$ $`=`$ $`i{\displaystyle 𝑑\eta v^{}(\eta )e^{i(\omega _\eta ^y\omega _{01})t}a_{1\eta }(t)}`$ (21)
$`\dot{a}_{1\eta }(t)`$ $`=`$ $`iv(\eta )e^{i(\omega _\eta ^y\omega _{01})t}a_0(t)i{\displaystyle 𝑑\zeta w^{}(\zeta )e^{i(\omega _\zeta ^z\omega _{12})t}a_{2\eta \zeta }(t)}`$ (22)
$`\dot{a}_{2\eta \zeta }(t)`$ $`=`$ $`iw(\zeta )e^{i(\omega _\zeta ^z\omega _{12})t}a_{1\eta }(t).`$ (23)
Here $`\omega _{ij}=\omega _i^x\omega _j^x`$. From Eq. (23) we have

$$a_{2\eta \zeta }(t)=iw(\zeta )_0^t𝑑t_1e^{i(\omega _\zeta ^z\omega _{12})t_1}a_{1\eta }(t_1).$$
(24)
Substituting Eq. (24) for $`a_{2\eta \zeta }(t)`$ in Eq. (22), we obtain a non-Markovian equation for coefficients $`a_{1\eta }`$:

$$\dot{a}_{1\eta }(t)=iv(\eta )e^{i(\omega _\eta ^y\omega _{01})t}a_0(t)_0^t𝑑t_1a_{1\eta }(t_1)q_1(tt_1),$$
(25)
where

$`q_1(\tau )`$ $`=`$ $`e^{i\omega _{12}\tau }{\displaystyle 𝒲(\omega ^z)e^{i\omega ^z\tau }𝑑\omega ^z},`$ (26)
$`𝒲(\omega ^z)`$ $`=`$ $`{\displaystyle |w(\omega ^z,\alpha ^z)|^2𝑑\alpha ^z}`$ (27)
and we supposed $`\zeta =\{\omega ^z,\alpha ^z\}`$. The equations (26,27) are quite similar to equations (10,11), Section 2. The only difference is that Eqs. (10,11) are related to transition $`|x_0|x_1`$ but Eqs. (26,27) are related to transition $`|x_1|x_2`$. The integral in r.h.s. of Eq. (25) is similar to the integral in r.h.s. of Eq. (8). Therefore, arguing as in Section 2, we see that Eq. (25) may be changed by approximate Markovian equation

$$\dot{a}_{1\eta }(t)=iv(\eta )e^{i(\omega _\eta ^y\omega _{01})t}a_0(t)\gamma _1a_{1\eta }(t),$$
(28)
where

$`\gamma _1=\lambda _1+i\mu _1={\displaystyle _0^{\mathrm{}}}q_1(\tau )𝑑\tau ,`$
$`\lambda _1=\pi 𝒲(\omega _{12});\mu _1=P{\displaystyle _0^{\mathrm{}}}{\displaystyle \frac{𝒲(\omega ^z)}{\omega ^z\omega _{12}}}𝑑\omega ^z.`$
The solution of Eq. (28) is

$$a_{1\eta }(t)=iv(\eta )_0^te^{\gamma _1(tt_1)}e^{i(\omega _\eta ^y\omega _{01})t_1}a_0(t_1).$$
(29)
Substituting Eq. (29) for $`a_{1\eta }(t)`$ in Eq. (21) we find the equation for amplitude $`a_0(t)`$:

$$\dot{a}_0(t)=_0^ta_0(t_1)\stackrel{~}{q}_0(tt_1)𝑑t_1,$$
(30)
where

$$\stackrel{~}{q}_0(\tau )=e^{\gamma _1\tau }e^{i\omega _{01}\tau }𝒱(\omega ^y)e^{i\omega ^y\tau }𝑑\omega ^y.$$
(31)
The tilde indication of function $`\stackrel{~}{q}_0(\tau )`$ means that this function is related to transition $`|x_0|x_1`$ perturbed by instability of state $`|x_1`$. Further the meaning of tilde will be the same in all cases. Function $`\stackrel{~}{q}_0(\tau )`$ differs from nondisturbed function $`q_0(\tau )`$ Eq. (10) by additional factor $`\mathrm{exp}(\gamma _1\tau )`$. The module of this factor is a decreasing function since $`\mathrm{Re}\gamma _1=\lambda _1>0`$. Consequently, the function $`\stackrel{~}{q}_0(\tau )`$ is a narrow peak near the value $`\tau =0`$ as well as the nondisturbed function $`q_0(\tau )`$ (see Section 2). Hence, we can change the non-Markovian equation (30) to Markovian one

$$\dot{a}_0(t)=\stackrel{~}{\gamma }_0a_0(t),$$
(32)
where

$$\stackrel{~}{\gamma }_0=\stackrel{~}{\lambda }_0+i\stackrel{~}{\mu }_0=_0^{\mathrm{}}\stackrel{~}{q}_0(\tau )𝑑\tau .$$
(33)
It is not difficult to obtain from Eq. (33) and Eq. (31):

$`\stackrel{~}{\lambda }_0`$ $`=`$ $`\pi {\displaystyle _0^{\mathrm{}}}𝒱(\omega ^y){\displaystyle \frac{1}{\pi }}{\displaystyle \frac{\lambda _1}{\lambda _1^2+(\omega ^y\omega _{01}+\mu _1)^2}}𝑑\omega ^y,`$ (34)
$`\stackrel{~}{\mu }_0`$ $`=`$ $`{\displaystyle _0^{\mathrm{}}}𝒱(\omega ^y){\displaystyle \frac{\omega ^y\omega _{01}+\mu _1}{\lambda _1^2+(\omega ^y\omega _{01}+\mu _1)^2}}𝑑\omega ^y.`$ (35)
Solving Eq. (32), we get

$$a_0(t)=e^{\stackrel{~}{\gamma }_0t}.$$
(36)
It follows from Eq. (36) that $`\stackrel{~}{\gamma }_0`$ is the complex decay constant of state $`|x_0`$. Decay constant is perturbed by instability of state $`|x_1`$. Thus, the probability of decay per unit of time is $`\stackrel{~}{\mathrm{\Gamma }}_0=2\mathrm{R}\mathrm{e}\stackrel{~}{\gamma }_0=2\stackrel{~}{\lambda }_0`$. This value coincides with the result obtained early in  by perturbation method (comp. Eq. (1) and Eq. (34)).

Now let us find the spectra of particles $`y`$ and $`z`$ created during the first and second transitions of system $`X`$. These spectra are defined by values $`|a_{1\eta }(t)|^2`$ and $`|a_{2\eta \zeta }(t)|^2`$ as $`t\mathrm{}`$. Substituting Eq. (36) for $`a_0(t)`$ in Eq. (29), we obtain

$$a_{1\eta }(t)=iv(\eta )\frac{e^{[i(\omega _\eta ^y\omega _{01})\stackrel{~}{\gamma }_0]t}e^{\gamma _1t}}{i(\omega _\eta ^y\omega _{01})+\gamma _1\stackrel{~}{\gamma }_0}.$$
(37)
It is readily seen that

$$\underset{t\mathrm{}}{lim}|a_{1\eta }(t)|^2=0.$$

This means that coefficients $`a_{1\eta }(t)`$ do not contribute to spectra of particles. This could be expected because these coefficients relate to intermediate state of the system.

Substituting Eq. (37) for $`a_{1\eta }(t)`$ in Eq. (24), we get the expression for $`a_{2\eta \zeta }(t)`$:

$`a_{2\eta \zeta }(t)`$ $`=`$ $`{\displaystyle \frac{v(\eta )w(\zeta )}{i(\omega _\eta ^y\omega _{01})+\gamma _1\stackrel{~}{\gamma }_0}}`$ (38)
$`\times \left\{{\displaystyle \frac{e^{[i(\omega _\eta ^y+\omega _\zeta ^z\omega _{02})\stackrel{~}{\gamma }_0]t}1}{i(\omega _\eta ^y+\omega _\zeta ^z\omega _{02})\stackrel{~}{\gamma }_0}}{\displaystyle \frac{e^{[i(\omega _\zeta ^z\omega _{12})\gamma _1]t}1}{i(\omega _\zeta ^z\omega _{12})\gamma _1}}\right\}.`$
It is easy to obtain from Eq. (38) that the limit of $`a_{2\eta \zeta }(t)`$ as $`t\mathrm{}`$ is

$$a_{2\eta \zeta }(\mathrm{})=\frac{v(\eta )w(\zeta )}{[i(\omega _\eta ^y+\omega _\zeta ^z\omega _{02})\stackrel{~}{\gamma }_0][i(\omega _\zeta ^z\omega _{12})\gamma _1]}.$$
(39)
Now we can calculate mutual distribution of energy of particles $`y`$ and $`z`$:

$$p(\omega ^y,\omega ^z)=𝑑\alpha ^y𝑑\alpha ^z|a_{2;\omega ^y\alpha ^y;\omega ^z\alpha ^z}(\mathrm{})|^2.$$
(40)
¿From Eq. (39) and Eq. (40) we get

$$p(\omega ^y,\omega ^z)=\frac{𝒱(\omega ^y)𝒲(\omega ^z)}{[\stackrel{~}{\lambda }_0^2+(\omega ^y+\omega ^z\overline{\omega }_{02})^2][\lambda _1^2+(\omega ^z\overline{\omega }_{12})^2]}.$$
(41)
where $`\overline{\omega }_{02}`$ and $`\overline{\omega }_{12}`$ are the corrected values of transition energies

$$\overline{\omega }_{02}=(\omega _0^x+\stackrel{~}{\mu }_0)\omega _2^x;\overline{\omega }_{12}=(\omega _1^x+\mu _1)\omega _2^x.$$

Let us note that the energy $`\omega _0^x`$ is corrected by perturbed value of radiation shift $`\stackrel{~}{\mu }_0`$ defined by Eq. (35) instead of unperturbed radiation shift Eq. (14).

The spectrum of particles $`y`$ created in the first transition is defined by

$$p_y(\omega ^y)=_0^+\mathrm{}p(\omega ^y,\omega ^z)𝑑\omega ^z=_{\mathrm{}}^+\mathrm{}p(\omega ^y,\omega ^z)𝑑\omega ^z.$$
(42)
We change the lower limit of integral in Eq. (42) from 0 to $`\mathrm{}`$ since $`𝒲(\omega ^z)=0`$ for all $`\omega ^z<0`$. It is possible to calculate the integral Eq. (42) analytically only if the function $`𝒲(\omega ^z)`$ is known. In the general case we have to introduce some approximation. Suppose that $`|\omega _{01}|\omega _{12}`$, $`\omega ^y\omega _{12}`$, and $`𝒲(\omega ^z)`$ is a sufficiently smooth function:

$$𝒲(\omega ^y+\overline{\omega }_{02})𝒲(\overline{\omega }_{12})𝒲(\omega _{12}).$$
(43)
Then we can rewrite Eq. (42) as

$$p_y(\omega ^y)=𝒱(\omega ^y)𝒲(\omega _{12})_{\mathrm{}}^+\mathrm{}\frac{d\omega ^z}{[\stackrel{~}{\lambda }_0^2+(\omega ^y+\omega ^z\overline{\omega }_{02})^2][\lambda _1^2+(\omega ^z\overline{\omega }_{12})^2]}.$$
(44)
It is not hard to calculate the integral in Eq. (44) by residue theory. We obtain:

$$p_y(\omega ^y)=\frac{\pi 𝒱(\omega ^y)}{\stackrel{~}{\lambda }_0}\left[\frac{1}{\pi }\frac{\stackrel{~}{\lambda }_0+\lambda _1}{(\stackrel{~}{\lambda }_0+\lambda _1)^2+(\omega ^y\overline{\omega }_{01})^2}\right],$$
(45)
where $`\overline{\omega }_{01}=(\omega _0^x+\stackrel{~}{\mu }_0)(\omega _1^x+\mu _1)`$ is the corrected energy of transition $`|x_0|x_1`$.

The spectrum of particles $`z`$ is

$`p_z(\omega ^z)`$ $`=`$ $`{\displaystyle _0^+\mathrm{}}p(\omega ^y,\omega ^z)𝑑\omega ^y`$ (46)
$`=`$ $`{\displaystyle \frac{𝒲(\omega ^z)}{\lambda _1^2+(\omega ^z\overline{\omega }_{12})^2}}{\displaystyle _{\mathrm{}}^+\mathrm{}}{\displaystyle \frac{𝒱(\omega ^y)d\omega ^y}{\stackrel{~}{\lambda }_0^2+(\omega ^y+\omega ^z\overline{\omega }_{02})^2}}.`$
Suppose $`𝒱(\omega ^y)`$ to vary slowly during intervals of order $`\stackrel{~}{\lambda }_0`$ for all $`\omega ^y`$. Then we can move $`𝒱(\omega ^y)`$ out of integral in Eq. (46) for $`\omega ^y=\overline{\omega }_{02}\omega ^z`$. Taking into account also Eq. (43) we have

$$p_z(\omega ^z)=\frac{\pi 𝒱(\overline{\omega }_{02}\omega ^z)}{\stackrel{~}{\lambda }_0}\left[\frac{1}{\pi }\frac{\lambda _1}{\lambda _1^2+(\omega ^z\overline{\omega }_{12})^2}\right].$$
(47)
Let us find the distribution of the sum of energies $`\omega ^y+\omega ^z=\mathrm{\Omega }`$. It can easily be checked that

$$p_{y+z}(\mathrm{\Omega })=_0^\mathrm{\Omega }p(\omega ^y,\mathrm{\Omega }\omega ^y)𝑑\omega ^y.$$
(48)
It follows from Eq. (48) and Eq. (41) with assumption Eq. (43) that

$$p_{y+z}(\mathrm{\Omega })=\frac{S(\mathrm{\Omega })}{\stackrel{~}{\lambda }_0^2+(\mathrm{\Omega }\overline{\omega }_{02})^2},$$
(49)
where

$$S(\mathrm{\Omega })=_0^\mathrm{\Omega }𝒱(\omega ^y)\left[\frac{1}{\pi }\frac{\lambda _1}{\lambda _1^2+(\mathrm{\Omega }\omega ^y\overline{\omega }_{12})^2}\right]𝑑\omega ^y.$$

If $`\lambda _1\stackrel{~}{\lambda }_0`$, function $`S(\mathrm{\Omega })`$ varies slowly in comparison with the pole-like denominator of Eq. (49). Hence, the spectrum of the sum of particle $`y`$ and $`z`$ energies is approximately a narrow Lorentzian-shape peak of width $`\stackrel{~}{\lambda }_0`$ (as could be expected).

## 4 Discussion and conclusions

The main results of the present paper are following:

* Eq. (34) describes perturbed value of the real part of decay constant of level $`|x_0`$ (the initial level of cascade transition). The real part is also the half of decay probability per unit of time of level $`|x_0`$.
* Eq. (35) describes perturbed value of imaginary part of decay constant of level $`|x_0`$. The imaginary part is the perturbed value of radiation shift of level $`|x_0`$.
* Eq. (41) describes mutual energy spectrum of particles of the first and of the second transition of a cascade.
* Eq. (45) describes energy spectrum of the first transition of a cascade.
* Eq. (47) describes energy spectrum of the second transition of a cascade.
* Eq. (49) describes distribution of the sum of particle energies created during the first and the second transitions of a cascade.

We discussed Eq. (1) for perturbed value of decay probability $`\stackrel{~}{\mathrm{\Gamma }}_0`$ in the Introduction. Since $`\stackrel{~}{\mathrm{\Gamma }}_0=2\stackrel{~}{\lambda }_0`$, so this discussion is related to Eq. (34) as well.

Eq. (35) shows that instability of level $`|x_1`$ affects the discrete level contribution to radiation shift of level $`|x_0`$ as well as the probability of decay. Therefore, the well-known formula for radiation shift (14) should be replaced by Eq. (35) if $`\lambda _1`$ is comparable with $`|\omega _{01}|`$. It is easy to see that Eq. (35) transforms into usual Eq. (14) as $`\lambda _10,\mu _10`$. If formally $`\lambda _1\mathrm{}`$, from Eq. (35) we obtain $`\stackrel{~}{\mu }_00`$. This result is similar to $`\stackrel{~}{\lambda }_00`$ as $`\lambda _1\mathrm{}`$, therefore it may be called “an energy-shift quantum Zeno paradox”. Similarly, the perturbation of radiation shift of level $`|x_0`$ by instability of level $`|x_1`$ for realistic values $`\lambda _1`$ may be called “an energy-shift quantum Zeno effect”. Note that it could be expected that “energy-shift quantum Zeno effect” would be presented in waiting-mode observation of decay in the general case, not only in cascade transitions. Thus, the same mechanism that perturbs the probability of decay also perturbs the radiation shift of level.

Let us now discuss the expression for particle spectra emitted during the first transition (Eq. (45)) and during the second transition (Eq. (47)). It is suitable to discuss tree different situations:

$`1^\mathrm{o}`$. If $`\lambda _1\overline{\omega }_{01}`$ and $`\overline{\omega }_{01}>0`$ then it could be considered that function $`𝒱(\omega ^y)`$ to vary very slowly in comparison with the pole-like denominators in Eq. (45) and Eq. (47). Hence, we obtain that the spectra defined by Eqs. (45,47) are usual Lorentzian-shape peaks. The width of the spectra of first transition is $`\stackrel{~}{\lambda }_0+\lambda _1`$, but not $`\stackrel{~}{\lambda }_0`$. These conclusions are quite similar to well-known results , but $`\lambda _0`$ in  is now changed by perturbed value $`\stackrel{~}{\lambda }_0`$.

$`2^\mathrm{o}`$. If $`\lambda _1\overline{\omega }_{01}`$ and $`\overline{\omega }_{01}>0`$, it can not be considered that function $`𝒱(\omega ^y)`$ to vary slowly in comparison with the denominators in Eq. (45) and Eq. (47). Therefore, both the spectra of particles $`y`$ and $`z`$ become strongly deformed Lorentzian peaks.

$`3^\mathrm{o}`$. Finally, suppose $`\overline{\omega }_{01}<0`$. Then the maxima of Lorentzian factors of Eq. (45) and Eq. (47) are positioned in the branch of $`\omega `$ values where $`𝒱(\omega )=0`$. The spectra shapes are defined by the shape of function $`𝒱(\omega )`$ multiplied by the tale of Lorentzian peaks now. Therefore, both spectra $`p_y(\omega ^y)`$ and $`p_z(\omega ^z)`$ are continuous rather than peak-like. The energy of quanta $`y`$ emitted during the first step of cascade transition is positive, of course, in spite of $`\overline{\omega }_{01}<0`$.

Thus, the separate spectra of particles $`y`$ and $`z`$ may be very wide or even continuous. But it follows from Eq. (49) that the energies of particles $`y`$ and $`z`$ remain strongly correlated such that the width of the distribution of sum $`\mathrm{\Omega }=\omega ^y+\omega ^z`$ is equal to $`\stackrel{~}{\lambda }_0`$ in all cases. This is a manifestation of fundamental uncertainty principle for energy and time.

ACKNOWLEDGMENTS

The author acknowledges the fruitful discussions with M. B. Mensky and V. A. Namiot and is grateful to V. A. Aref’ev for the help in preparation of the paper. The work was supported in part by the Russian Foundation of Basic Research, grant 98-01-00161.