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# Field theory description of vacuum replicas

## I Introduction

In this paper we return to the possibility of vacuum replication put forward in a recent work BNR . There it was suggested that at least one vacuum replica could exist in QCD and an explicit example of such a replica was produced for a general class of quark kernels compliant with chiral symmetry (see also oni  where a similar conclusion was made). Here we focus on the problem of quantum field theory formulation of hadronic processes involving such replicas. The paper is organized as follows: In the second section, as an introduction to the issue of vacuum replication, we give some details of the chiral model used to find such replicas, although, as we have already said, the existence of such states does not depend on a given particular model, but seems to be a general feature, found at least on two different approaches. In any case, the formalism we propose to take into account the effect of such replicas in hadronic processes is independent of any particular model — any model dependence is stored in the chiral angle — and therefore we will not dwell too much on model details. In the third section, we briefly discuss how the vacuum replica appears in the theory, how it depends on the dimensionality of the space-time and on the strength and the form of the inter-quark interaction. We follow the original paper BNR . The orthogonality and other properties of various vacuum states are the subject of the fourth section. Section five contains the new formalism necessary to describe the effect of the replica’s new degree of freedom in hadronic processes. Then, in the sixth section, we study propagation of quarks in presence of the replica, deriving and solving a Dyson-Schwinger equation for the single-quark Greens function. Overview of the results, as well as of the perspectives of the suggested method, are the subject of the concluding section of the paper. If not stated otherwise, we consider the chiral limit throughout the paper.

## II The chiral Hamiltonian and the Bogoliubov-Valatin transformation

In this section, we introduce the model and briefly outline the basic ideas needed for the remainder of the paper. We start from the chirally symmetric Hamiltonian,

$`H={\displaystyle d^3x[H_0(\stackrel{}{x})+H_I^{(1)}(\stackrel{}{x})+H_I^{(2)}(\stackrel{}{x})]},`$
$`H_0(\stackrel{}{x})=\psi ^{}(\stackrel{}{x},t)\left(i\stackrel{}{\alpha }\stackrel{}{}\right)\psi (\stackrel{}{x},t),`$ (1)
$`H_I^{(1)}(\stackrel{}{x})={\displaystyle \frac{1}{2}}{\displaystyle d^3y\psi ^{}(\stackrel{}{x},t)\frac{\lambda ^a}{2}\psi (\stackrel{}{x},t)\left[V_0(|\stackrel{}{x}\stackrel{}{y}|)+V_1(|\stackrel{}{x}\stackrel{}{y}|)\right]\psi ^{}(\stackrel{}{y},t)\frac{\lambda ^a}{2}\psi (\stackrel{}{y},t)},`$
$`H_I^{(2)}(\stackrel{}{x})={\displaystyle \frac{1}{2}}{\displaystyle d^3y\psi ^{}(\stackrel{}{x},t)\stackrel{}{\alpha }\frac{\lambda ^a}{2}\psi (\stackrel{}{x},t)V_1(|\stackrel{}{x}\stackrel{}{y}|)\psi ^{}(\stackrel{}{y},t)\stackrel{}{\alpha }\frac{\lambda ^a}{2}\psi (\stackrel{}{y},t)},`$
where $`V_0(|\stackrel{}{x}|)=\sigma _0|\stackrel{}{x}|`$, and $`V_1(|\stackrel{}{x}|)=\frac{\alpha _s}{|\stackrel{}{x}|}\left(1e^{\mathrm{\Lambda }|\stackrel{}{x}|}\right)+U`$. The Hamiltonian (II) belongs to a certain class of quark models having quark kernels ranging from delta-functional NJL  and oscillator-type model ; BR  to a more realistic linear form (see, for example, linear ). Such models, hereafter referred as to NJL-type models, are very successful at describing low-energy hadronic properties, including scattering reactions like $`\pi \pi `$ scattering pp , where Ward identities force the cancellation between two types of scalar contributions: one arising from the exchange of the $`q\overline{q}`$ bound-state sigma, which occurs naturally as a pole in the ladder summation for the scalar sector, and the other from the diffractive (i.e., non-pole dominated) part of the $`\pi \pi `$ T-matrix. The Weinberg $`\pi \pi `$ scattering lengths then come naturally as a consequence of this cancellation. This is a general feature for hadronic scattering, solely governed by chiral symmetry invariance, and, therefore, not restricted to $`\pi \pi `$ scattering or to any particular kernel. In fact the argument can be reversed to prove the need for the existence of sigma as a bound state of $`q\overline{q}`$: any microscopic theory with quarks, possessing chiral symmetry, must contain an effective quark-quark sigma exchange, in order to cancel the scalar contribution arising from the diffractive part (sometimes also termed as the “contact term”) of a given hadron-hadron scattering (like for instance $`\pi \pi `$). It happens that the NJL-type model embodied in Eq. (II) possesses one vacuum replica. For an earlier derivation of the $`\pi \pi `$ Weinberg scattering lengths, in the framework of contact quark kernels, both for the quartic fermion interaction and an $`U(1)_A`$-breaking six quark term, see ref. pointlike . Again, for that particular model, vacuum replicas were shown to occur.

It is therefore remarkable that, across all these different quark kernels, the existence of vacuum replicas should constitute the rule rather than the exception.

On the other hand it is known cahill  that nonlocal-quark-kernel NJL models can be mapped — via a bilocal bosonization — onto a corresponding effective chiral perturbation theory Lagrangian $`_{ChPT}`$. Then from the above discussion on chiral symmetry invariance of NJL models and the role of the $`\sigma `$-meson, the probable nature of the physical $`\sigma `$ emerges: a bare $`q\overline{q}`$ state highly distorted by $`\pi \pi `$ coupled channels. So distorted that $`\sigma `$ “doubling” may take place doubling . The possible existence of a vacuum replica will further complicate this picture. It is the purpose of this paper to evaluate the contribution of such replicas to quark-quark kernels.

In what follows it is enough to assume the existence of one such replica, without needing to resort to any particular model, to be able to work out the consequences of replica existence for hadronic processes. However, in order to illustrate some of the concepts which will be needed, it is convenient to work within a particular model, which we choose to be the one defined in Eq. (II). As we shall see, the results of this paper will be formally independent of this choice, with the model dependence encapsulated in one single function: $`f(\omega )`$.

The four parameters fixing the model (II) are the string tension $`\sigma _0`$, the strong coupling constant $`\alpha _s`$, the ultraviolet cut-off $`\mathrm{\Lambda }`$ and the constant potential $`U`$ which was used to fit for the right value of the chiral condensate. It was argued in BNR  that with the choice of these parameters given in Table I the model is governed by only one scale of order $`300MeV`$ and it naturally possesses both the Coulomb limit for heavy quarks and the chiral limit for massless quarks. The chiral condensate and the constituent quark mass take their standard values,

$$\overline{\psi }\psi =(250MeV)^3,m_{\mathrm{eff}}=\underset{p0}{lim}\sqrt{p^2+m(p)^2}230MeV,$$
(2)
where $`m(p)`$ is the effective dynamical quark mass connected to the dressed-quark dispersive law. The Bogoliubov-Valatin method is used to diagonalize the Hamiltonian in terms of the dressed quarks, and the mass-gap equation for the chiral angle $`\phi (p)`$,

$$\frac{\delta _{\mathrm{vac}}[\phi ]}{\delta \phi (p)}=0,_{\mathrm{vac}}[\phi ]=0|TH[\phi ]|0,$$
(3)
is studied in detail. There are many ways to define the chiral angle, and we choose it to obey the following conditions BR :

$$\frac{\pi }{2}\phi (p)\frac{\pi }{2},\phi (0)=\frac{\pi }{2},\phi (p\mathrm{})0.$$
(4)
The dressed quark field is then

$$\psi (\stackrel{}{x},t)=\underset{\xi =,}{}\frac{d^3p}{(2\pi )^3}e^{i\stackrel{}{p}\stackrel{}{x}}[b_\xi (\stackrel{}{p},t)u_\xi (\stackrel{}{p})+d_\xi ^{}(\stackrel{}{p},t)v_\xi (\stackrel{}{p})],$$
(5)
$$\begin{array}{ccc}\hfill u(\stackrel{}{p})& =& \frac{1}{\sqrt{2}}\left[\sqrt{1+\mathrm{sin}\phi }+\sqrt{1\mathrm{sin}\phi }(\stackrel{}{\alpha }\widehat{\stackrel{}{p}})\right]u(0),\hfill \\ \hfill v(\stackrel{}{p})& =& \frac{1}{\sqrt{2}}\left[\sqrt{1+\mathrm{sin}\phi }\sqrt{1\mathrm{sin}\phi }(\stackrel{}{\alpha }\widehat{\stackrel{}{p}})\right]v(0).\hfill \end{array}$$
(6)
$$b_\xi (\stackrel{}{p},t)=e^{iE_pt}b_\xi (\stackrel{}{p},0),d_\xi (\stackrel{}{p},t)=e^{iE_pt}d_\xi (\stackrel{}{p},0),$$
(7)
with $`E_p`$ being the dressed-quark dispersive law. Notice a very important property of the fermionic field (5). Formally it remains intact under Bogoliubov-Valatin transformation with an arbitrary chiral angle $`\phi (p)`$ since the rotation of the quark amplitudes $`u`$ and $`v`$ is compensated by the contrarotation of the operators $`b`$ and $`d`$. Nevertheless, the definition of the vacuum annihilated by the dressed single-particle operators, as well as the definition of the one-particle state, change drastically, so that the true vacuum, with the minimal vacuum energy, becomes full of strongly correlated $`{}_{}{}^{3}P_{0}^{}`$ quark-antiquark pairs BR ,

$$|\stackrel{~}{0}=S_0|0,S_0=e^{Q_0^{}Q_0},Q_0^{}=\frac{1}{2}\frac{d^3p}{(2\pi )^3}\phi _0(p)C_p^{},$$
(8)
$$C_p^{}=[b_{}^{}(\stackrel{}{p}),b_{}^{}(\stackrel{}{p})]𝔐_{{}_{}{}^{3}P_{0}^{}}\left[\begin{array}{c}d_{}^{}(\stackrel{}{p})\\ d_{}^{}(\stackrel{}{p})\end{array}\right],$$
(9)
with the $`{}_{}{}^{3}P_{0}^{}`$ matrix being

$$\left[𝔐_{{}_{}{}^{3}P_{0}^{}}\right]_{\xi _1\xi _2}=(\sqrt{6})\underset{\xi ,m}{}\left(\begin{array}{ccc}1& 1& 0\\ m& \sigma & 0\end{array}\right)\widehat{\stackrel{}{p}}_{1m}\left(\begin{array}{ccc}1/2& 1/2& 1\\ \xi _1& \xi _2& \sigma \end{array}\right)=[(\stackrel{}{\sigma }\widehat{\stackrel{}{p}})i\sigma _2]_{\xi _1\xi _2},$$
(10)
where $`\sigma `$’s are the $`2\times 2`$ Pauli matrices.

The operator $`C_p`$ creates a $`{}_{}{}^{3}P_{0}^{}`$ quark-antiquark pair with zero total momentum and the relative three-dimensional momentum $`2\stackrel{}{p}`$. The chiral angle $`\phi _0(p)`$ is the solution to the mass-gap equation (3) and it “measures” the weight of the pairs with the given relative momentum, so that the operator $`S_0`$ creates a cloud of correlated pairs, and the BCS vacuum $`|\stackrel{~}{0}`$ has the form of a coherent-like state. The dressed fermionic propagator in this vacuum is given by the expression

$$S(p_0,\stackrel{}{p})=\frac{\mathrm{\Lambda }_+(\stackrel{}{p})\gamma _0}{p_0E_p+i0}+\frac{\mathrm{\Lambda }_{}(\stackrel{}{p})\gamma _0}{p_0+E_pi0},$$
(11)
where the projectors $`\mathrm{\Lambda }_\pm `$ are defined as

$$\mathrm{\Lambda }_\pm (\stackrel{}{p})=\frac{1}{2}[1\pm \gamma _0\mathrm{sin}\phi _0(p)\pm (\stackrel{}{\alpha }\widehat{\stackrel{}{p}})\mathrm{cos}\phi _0(p)].$$
(12)
A crucial statement which makes the model under discussion realistic is that, as said above, it is governed by only one scale, of order $`250÷300MeV`$, which in turn can be dynamically generated, in a self-consistent way, with no other scales appearing (see Table I and the discussion in the reference BNR ).

## III The replica

The question whether the BCS vacuum possesses replicas was addressed in ref. BNR . It was shown that the answer to this question strongly depended on the dimensionality of the space-time, on the form of the potential, and on the strength of the latter. For example, the two-dimensional model for QCD tHooft  was found to possess no replica states at all, regardless of the form of the potential BNR . On the contrary, the four-dimensional potential does support the existence of replicas, provided it is strong enough. It was demonstrated long ago that the oscillator-type potential leads to an infinite tower of solutions to the mass-gap equation Orsay2 . On the other hand, one can numerically check that the pure linear potential fails by a very short margin, to be sufficiently “binding” to hold replicas — in fact it seems to be sitting on the brink of possessing such replicas. Then, it was suggested that the addition of a Coulomb potential — which is both required by phenomenology and by the scale self-consistency needed for the class of models we considered — might do the trick and tip the balance over to the side of potentials sufficiently attractive to possess a replica. Indeed this was the case and the existence of one, and only one, replica was found for the realistic set of parameters given in Table I. The existence of one replica for this class of realistic and scale self-consistent kernels together with the accumulated evidence that vacuum replication is likely to occur in four dimensions BNR ; oni ; Orsay2 , gives us reasons to expect that such a vacuum replication may occur in any realistic model for QCD and, ultimately, be a property of QCD itself. The profiles of the chiral angles for the trivial, ground-state, and replica solutions are given in Fig. 1. Notice that both nontrivial solutions converge to each other in the ultraviolet regime although for large quark momenta — where the physical Fock space must contain gluons and the physics is controlled by perturbative QCD — this class of models ceases to be reliable. Nevertheless, they still contain the key property that for large momenta the quarks should become asymptotically free, and chiral symmetry should be restored, although questions about the nature of this phase transition cannot be answered within the framework of these effective models. On the other hand, in the low energy regime, these models can be shown to possess all kind of good properties and to be able to give a global understanding of low-energy hadronic phenomenology pp .

Therefore by vacuum replication we understand the phenomenon in which the same ultraviolet behaviour, for instance for the quark propagator, bifurcates to different solutions when we go to the low energy domain.

Due to the nonperturbative nature (and nonlinearity) of low energy QCD it is hard to exclude a priori this possibility which, in any case, is the rule rather than the exception for NJL-type models.

## IV Properties of the vacuum

### IV.1 Orthogonality condition

To start let us briefly overview the orthogonality properties of the BCS vacuum defined by Eq. (8).

Using the commutation relations for the quark operators $`b`$ and $`d`$, one can easily find the following representation for the ground-state vacuum BR :

$$|\stackrel{~}{0}=\underset{p}{}\left(\mathrm{cos}^2\frac{\phi _0}{2}+\mathrm{sin}\frac{\phi _0}{2}\mathrm{cos}\frac{\phi _0}{2}C_p^{}+\frac{1}{2}\mathrm{sin}^2\frac{\phi _0}{2}C_p^2\right)|0S_0|0.$$
(13)
If the trivial vacuum is normalized, $`0|0=1`$, then

$$\stackrel{~}{0}|\stackrel{~}{0}=1,0|\stackrel{~}{0}=\underset{p}{}\mathrm{cos}^2\frac{\phi _0}{2}=\mathrm{exp}\left[V\frac{d^3p}{(2\pi )^3}\mathrm{ln}\left(\mathrm{cos}^2\frac{\phi _0}{2}\right)\right]\underset{V\mathrm{}}{}0,$$
(14)
where the substitution $`_pV\frac{d^3p}{(2\pi )^3}`$ was used; $`V`$ being the three-dimensional volume. Therefore, the chirally nonsymmetric vacuum state is orthogonal to the trivial vacuum in the limit of infinite volume of the space. As usual, the Fock space is built over the $`|\stackrel{~}{0}`$ vacuum by repeated application of quark/antiquark creation operators belonging to the set $`\{\stackrel{~}{b}_{}^{}(\stackrel{}{p}),\stackrel{~}{b}_{}^{}(\stackrel{}{p}),\stackrel{~}{d}_{}^{}(\stackrel{}{p}),\stackrel{~}{d}_{}^{}(\stackrel{}{p})\}`$, defined as,

$$\stackrel{~}{b}=S_0bS_0^{},\stackrel{~}{d}=S_0dS_0^{}.$$
(15)
Let us denote this Fock space by $`_{\stackrel{~}{0}}`$. Once we have $`_{\stackrel{~}{0}}`$, we can address more complicated questions, like, for instance, Bethe-Salpeter amplitudes for hadrons and scattering (see ref. pp  for an example and references therein).

For the replica, a relation similar to (13) can be written, with the solution of the mass-gap equation $`\phi _0`$ changed for $`\phi _1`$ (see Fig. 1),

$$|\stackrel{~}{1}=\underset{p}{}\left(\mathrm{cos}^2\frac{\phi _1}{2}+\mathrm{sin}\frac{\phi _1}{2}\mathrm{cos}\frac{\phi _1}{2}C_p^{}+\frac{1}{2}\mathrm{sin}^2\frac{\phi _1}{2}C_p^2\right)|0S_1|0.$$
(16)
Then the orthogonality of the two nontrivial vacuum states can be easily proved after simple algebraic transformations,

$$\stackrel{~}{0}|\stackrel{~}{1}=\underset{p}{}\mathrm{cos}^2\frac{\phi _0\phi _1}{2}=\mathrm{exp}\left[V\frac{d^3p}{(2\pi )^3}\mathrm{ln}\left(\mathrm{cos}^2\frac{\mathrm{\Delta }\phi }{2}\right)\right]\underset{V\mathrm{}}{}0,$$
(17)
where the function $`\mathrm{\Delta }\phi (p)`$ is given in Fig. 2.

Again, in the same fashion as we did for $`_{\stackrel{~}{0}}`$, we can construct a Fock space over $`|\stackrel{~}{1}`$, $`_{\stackrel{~}{1}}`$. The difference is that the creation operators should be given by

$$\stackrel{~}{b}=S_1bS_1^{},\stackrel{~}{d}=S_1dS_1^{},$$
(18)
instead of Eq. (15).

Let us study the unitary operator connecting the ground-state and the replica vacua:

$$|\stackrel{~}{1}=S_1|0=S_1S_0^{}S_0|0=S_1S_0^{}|\stackrel{~}{0}.$$
(19)
Notice that, in order to have everything self-consistent, only operators inherent to the ground-state vacuum must be used in Eq. (19). For this purpose, we use the standard transformation rules for the operators $`b`$ and $`d`$ in different representations to find

$$S_0=\stackrel{~}{S}_0^{}\stackrel{~}{S}_0\stackrel{~}{S}_0=\stackrel{~}{S}_0,S_1=\stackrel{~}{S}_0^{}\stackrel{~}{S}_1\stackrel{~}{S}_0,$$
(20)
where the tilde denotes operators in the ground-state vacuum representation, as opposed to the operators defined in the trivial vacuum, which do not have tildes.

Thus, Eq. (19) can be rewritten as

$$|\stackrel{~}{1}=\stackrel{~}{S}_0^{}\stackrel{~}{S}_1|\stackrel{~}{0}=e^{\mathrm{\Delta }\stackrel{~}{Q}^{}\mathrm{\Delta }\stackrel{~}{Q}}|\stackrel{~}{0}\stackrel{~}{S}|\stackrel{~}{0},$$
(21)
where, similarly to Eq. (8), we have,

$$\mathrm{\Delta }\stackrel{~}{Q}^{}=\frac{1}{2}\frac{d^3p}{(2\pi )^3}\mathrm{\Delta }\phi \stackrel{~}{C}_p^{},$$
(22)
and all operators on the r.h.s. are appropriate for the ground-state vacuum.

There is a crucial difference between the two Fock spaces. The ket $`|\stackrel{~}{1}`$ does not correspond to the lowest energy state, which is $`|\stackrel{~}{0}`$. In fact $`|\stackrel{~}{1}`$ has an energy excess of $`\mathrm{\Delta }_{\mathrm{vac}}`$ per volume unit BNR . On the other hand, in the representation $`_{\stackrel{~}{1}}`$, $`|\stackrel{~}{0}`$ must correspond — see Eqs. (19), (20) — to a coherent-like state, which entails an infinite superposition of quark-antiquark pairs produced by quark/antiquark creation operators consistent within that $`_{\stackrel{~}{1}}`$ Fock space. In general, for a given Hamiltonian, such a state would have a higher energy than the state without quark-antiquark pairs, which in $`_{\stackrel{~}{1}}`$ is $`|\stackrel{~}{1}`$, unless we have for that particular Hamiltonian, in this particular Fock space $`_{\stackrel{~}{1}}`$, a tachyon. This is precisely the case. It is a simple consequence of the general Gell-Mann-Oakes-Renner relation GOR  and the fact that the chiral condensate in $`_{\stackrel{~}{1}}`$ was found in BNR  to have an opposite sign as compared to the chiral condensate in the BCS ($`_{\stackrel{~}{0}}`$) vacuum. Then, in the PCAC regime, whereas the lowest state in the spectrum, the chiral pion, becomes slightly massive, the mass of its replica becomes imaginary, signaling the metastable nature of $`|\stackrel{~}{1}`$. In the remainder of this paper we shall use the Fock space $`_{\stackrel{~}{0}}`$ — where the energy ordering of the states is natural, with $`|\stackrel{~}{0}`$ being the lowest energy state, that is, the vacuum — and will show $`|\stackrel{~}{1}`$ to be a coherent state. From now on, the trivial vacuum will no longer be used, so that we simplify notations omitting tildes and using $`|0`$ and $`|1`$ for the BCS vacuum and the replica, respectively. If not stated explicitly, all field operators are defined for $`_{\stackrel{~}{0}}`$.

With the help of Eq. (21), it is straightforward to reproduce the normalization condition (17) since, in analogy with (13), one has

$`0|1=0|{\displaystyle \underset{p}{}}\left(\mathrm{cos}^2{\displaystyle \frac{\mathrm{\Delta }\phi }{2}}+\mathrm{sin}{\displaystyle \frac{\mathrm{\Delta }\phi }{2}}\mathrm{cos}{\displaystyle \frac{\mathrm{\Delta }\phi }{2}}C_p^{}+{\displaystyle \frac{1}{2}}\mathrm{sin}^2{\displaystyle \frac{\mathrm{\Delta }\phi }{2}}C_p^2\right)|0`$ (23)
$`=\mathrm{exp}\left[V{\displaystyle \frac{d^3p}{(2\pi )^3}\mathrm{ln}\left(\mathrm{cos}^2\frac{\mathrm{\Delta }\phi }{2}\right)}\right]1V{\displaystyle \frac{d^3p}{(2\pi )^3}\left(\frac{\mathrm{\Delta }\phi }{2}\right)^2}+\mathrm{},`$
where, for future references, we expanded the general expression for small $`\mathrm{\Delta }\phi `$. Notice that we can easily include an arbitrary number of colours and flavours by the simple substitution:

$$C_pC_{pcf},\underset{p}{}\underset{pcf}{},\underset{p}{}\underset{pcf}{},$$

with $`c=1\mathrm{}N_C`$ and $`f=1\mathrm{}N_f`$ being the colour and the flavour indices, respectively. Then, the orthogonality condition (23) can be written in the full form as

$$0|1=\mathrm{exp}\left[N_CN_fV\frac{d^3p}{(2\pi )^3}\mathrm{ln}\left(\mathrm{cos}^2\frac{\mathrm{\Delta }\phi }{2}\right)\right]=\mathrm{exp}\left[\mathrm{Sp}\mathrm{ln}(1\mathrm{\Gamma })\right],$$
(24)
where, in the last formula, we used the notations Sp$`=_{pcf}`$, $`\mathrm{\Gamma }=\mathrm{sin}^2\frac{\mathrm{\Delta }\phi }{2}`$ to arrive at the expression reminiscent of fermionic pair creation in the presence of external fields — see Eq. (4.84) of the ref. tb . In other words, the scalar product $`0|1`$ can be written in the form of the matrix element $`0|S|0`$ with the operator $`S[\psi ,\overline{\psi }]=\mathrm{\Delta }Q^{}\mathrm{\Delta }Q`$. In the next section, we discuss in detail the explicit form of such an operator and an effective external field.

### IV.2 Coherent-like states and saturation of unity

As mentioned above, the BCS vacuum as well as the replica have the form of coherent-like states. The simplest example of a coherent state is provided by a one-dimensional nonrelativistic harmonic oscillator with the mass $`m`$ and frequency $`\omega `$. It reads:

$$|z=\frac{1}{\sqrt{2}}e^{\frac{1}{2}|z|^2}e^{za^{}}|0,$$
(25)
with $`|0`$ being the oscillator ground state — the vacuum, and

$$a^{}=\frac{1}{\sqrt{2}}\left(x\sqrt{m\omega }i\frac{p}{\sqrt{m\omega }}\right),$$

where $`x`$ and $`p`$ are the coordinate and the momentum operators, respectively. The complex number $`z`$ parametrizes the coherent state which is normalized, $`z|z=1`$. Although coherent states are not orthogonal to each other,

$$z|z^{}=\mathrm{exp}\left(\frac{1}{2}|z|^2+z^{}z^{}\frac{1}{2}|z^{}|^2\right),$$
(26)
they form an overcomplete set and it is possible to resolve the unity operator in terms of coherent states. In the simple case of the harmonic oscillator, we have

$$\widehat{I}=|z\frac{d^2z}{\pi }z|=|z\frac{dzdz^{}}{2\pi i}z|,$$
(27)
with a simple Jacobean $`J(z,z^{})=1/2\pi i`$. This property of coherent states allows us to use them as an alternative basis of states, which is known to be more appropriate than the one-particle basis in many applications. The problem of propagation of coherent states is discussed in detail in cohs . The state (21) constitutes yet another example of a coherent state. To construct the set of such coherent states, we use the property of the operators $`C_p`$: $`C_p^n|0=0`$ for $`n>2`$, which in turn leads to the compact nonexponential form of the operator $`S`$ (see, for example, Eq. (23)) BR . Then, for each value of the momentum $`p`$, the corresponding Fock space is spanned by three orthogonal states, $`\{|0,C_p^{}[\theta _p]|0,C_p^2[\theta _p]|0\}`$, prompting us to generalize the operator $`C_p^{}`$ of equation (9) to a new operator $`C_p^{}[\theta _p]`$, defined as

$`C_p^{}[\theta _p]=[b_{}^{}(\stackrel{}{p}),b_{}^{}(\stackrel{}{p})]𝔐[\theta _p]\left[\begin{array}{c}d_{}^{}(\stackrel{}{p})\\ d_{}^{}(\stackrel{}{p})\end{array}\right],`$ (30)
$`𝔐[\theta _p]=e^{i(\stackrel{}{\sigma }\widehat{\stackrel{}{p}})\theta _p}𝔐_{{}_{}{}^{3}P_{0}^{}},`$ (31)
where, according to Eq. (10), the scalar coupling $`{}_{}{}^{3}P_{0}^{}`$ matrix is just $`𝔐_{{}_{}{}^{3}P_{0}^{}}=(\stackrel{}{\sigma }\widehat{\stackrel{}{p}})i\sigma _2`$. One can easily check that an analogous matrix for pseudoscalar $`{}_{}{}^{1}S_{0}^{}`$ pairing can be chosen to be $`𝔐_{{}_{}{}^{1}S_{0}^{}}=i\sigma _2`$. It is the spin Salpeter amplitude, in the spin representation, for the pion BR . Therefore the relation (31) can be presented as

$$𝔐[\theta _p]=𝔐_{{}_{}{}^{3}P_{0}^{}}\mathrm{cos}\theta _p+i𝔐_{{}_{}{}^{1}S_{0}^{}}\mathrm{sin}\theta _p,$$
(32)
so that the angle $`\theta _p`$ defines rotations in the two-dimensional plane between the scalar and pseudoscalar quark-antiquark couplings. One can easily check that the set of states

$$|\alpha ,\theta =\underset{p}{}\left(\mathrm{cos}^2\frac{\alpha _p}{2}+\mathrm{sin}\frac{\alpha _p}{2}\mathrm{cos}\frac{\alpha _p}{2}C_p^{}[\theta _p]+\frac{1}{2}\mathrm{sin}^2\frac{\alpha _p}{2}C_p^2[\theta _p]\right)|0=\underset{p}{}|\alpha ,\theta _p$$
(33)
with $`\pi <\alpha _p\pi `$ and $`0\theta _p<2\pi `$ is complete, that is, it is possible to find at least one Jacobean,

$$J(\alpha _p,\theta _p)=\frac{1}{4\pi ^2}\left(32\mathrm{cos}2\alpha _p\right),$$
(34)
as the simplest possibility, to saturate the unity operator, in the given space,

$$\widehat{I}=d[\alpha ]d[\theta ]|\alpha ,\theta J\alpha ,\theta |\underset{p}{}_\pi ^\pi 𝑑\alpha _p_0^{2\pi }𝑑\theta _p|\alpha ,\theta _pJ(\alpha _p,\theta _p)_p\alpha ,\theta |.$$
(35)
Similarly to the case of coherent states (25), the choice (34) is not unique. For example,

$$J^{}(\alpha _p,\theta _p)=J(\alpha _p,\theta _p)+\underset{n=3}{\overset{\mathrm{}}{}}A_n\mathrm{cos}(n\alpha _p)+\underset{n=1}{\overset{\mathrm{}}{}}B_n\mathrm{sin}(n\alpha _p)$$

with arbitrary coefficients $`A_n`$ and $`B_n`$ also supports the condition (35). The replica $`|1`$ corresponds to a specific choice of the parameters, $`\alpha _p=\mathrm{\Delta }\phi (p)`$ and $`\theta _p=0`$. The Fock space built in the usual way over the set $`|\alpha ,\theta `$ constitutes an example of an overcomplete space.

## V Quantum field theory based approach to the replica

In this section, we introduce a systematic approach to the replica state, which can be used to investigate the contribution of the excited vacuum bubbles to hadronic processes.

### V.1 Replica creator as a local operator

Using the explicit form of the quark field (5), one can find that $`\mathrm{\Delta }Q^{}`$ defined in (22) is expressed as

$$\begin{array}{ccc}\hfill \mathrm{\Delta }Q^{}& =& +d^4xf(x_0)\overline{\psi }(\stackrel{}{x},x_0)\left(i\stackrel{}{\alpha }\stackrel{}{}\right)\mathrm{\Lambda }_{}\psi (\stackrel{}{x},x_0),\hfill \\ \hfill \mathrm{\Delta }Q& =& d^4xf(x_0)\overline{\psi }(\stackrel{}{x},x_0)\left(i\stackrel{}{\alpha }\stackrel{}{}\right)\mathrm{\Lambda }_+\psi (\stackrel{}{x},x_0),\hfill \end{array}$$
(36)
if the function $`f(x_0)`$ is even with the Fourier transform being even, $`f(\omega )=f(\omega )`$, and

$$f(2E_p)=\frac{\mathrm{\Delta }\phi (p)}{2p}.$$
(37)
To exemplify the form of the function $`f(\omega )`$, let us use a simple anzatz of the dispersive law,

$$E_p=\frac{\stackrel{}{p}^2}{|\stackrel{}{p}|+\mathrm{\Delta }}\mathrm{\Delta },$$
(38)
which begins at $`E_p=\mathrm{\Delta }`$ $`(\mathrm{\Delta }>0)`$ when $`\stackrel{}{p}=0`$ and tends to the free limit, $`E_p=|\stackrel{}{p}|`$, when $`|\stackrel{}{p}|\mathrm{}`$. The parameter $`\mathrm{\Delta }`$ is generated nonperturbatively and it has the order of the interaction scale (see the discussion in refs. model ; BR  and, for the two-dimensional QCD, in ref. 2d ). The appropriate solution of the equation $`E_p=\omega /2`$ is found analytically to be,

$$p_{}(\omega )=\frac{1}{4}\left[\omega +2\mathrm{\Delta }+\sqrt{(\omega +2\mathrm{\Delta })(\omega +10\mathrm{\Delta })}\right],$$
(39)
if $`\omega 2\mathrm{\Delta }`$, and no solution exists otherwise. Then the function $`f(\omega )`$ takes the form

$$f(\omega )=\frac{\mathrm{\Delta }\phi (p_{}(\omega ))}{2p_{}(\omega )}\theta (2\mathrm{\Delta }+\omega )+\frac{\mathrm{\Delta }\phi (p_{}(\omega ))}{2p_{}(\omega )}\theta (2\mathrm{\Delta }\omega ),$$
(40)
with $`\theta `$ being the Heaviside step-like function. Now we fit the curve for $`\mathrm{\Delta }\phi (p)`$ in Fig. 2,

$$\mathrm{\Delta }\phi (p)=2Lp\mathrm{exp}\left(\frac{p}{\lambda }\right),L\frac{5.6}{\sqrt{\sigma _0}},\lambda 0.29\sqrt{\sigma _0},$$
(41)
and substitute it into Eq. (40) to obtain an expression for $`f(\omega )`$ which turns out to be a function localized in the regions $`|\omega |2\mathrm{\Delta }\sqrt{\sigma _0}`$ with the smearing given by the parameter $`\lambda `$ (for the value of $`\sigma _0=0.135GeV^2`$ given in Table I, $`\lambda 100MeV`$). This defines the most probable size of a $`|1`$-bubble to be $`\nu \sqrt{\sigma _0}/\mathrm{\Delta }_{\mathrm{vac}}`$. Notice that since the volume density of the energy $`\mathrm{\Delta }_{\mathrm{vac}}`$, stored in the bubble containing the replica, is also fixed by the same parameters of the interaction BNR , then the distribution in energies can also be seen as a distribution in volumes, with $`f(\mathrm{\Delta }_{\mathrm{vac}}\times \nu )`$ playing the role of the weight of the contribution for each volume $`\nu `$, so that the volume of a $`|1`$-bubble is fixed by the interaction scale and it is not a free parameter.

Using the relations (36), one can easily find the following representation for the operator $`S=\mathrm{exp}[\mathrm{\Delta }Q^{}\mathrm{\Delta }Q]`$, which relates the ground state and the replica mtk :

$$S_T=T\mathrm{exp}\left[d^4xf(x_0)\overline{\psi }(\stackrel{}{x},x_0)\left(i\stackrel{}{\alpha }\stackrel{}{}\right)\psi (\stackrel{}{x},x_0)\right],$$
(42)
where the projector operators disappear due to the equality $`\mathrm{\Lambda }_++\mathrm{\Lambda }_{}=1`$ and we used time ordering for noncommuting field operators. Eq. (42) is general, the model dependence encapsulated in $`f(x_0)`$. The difference of the chiral angles $`\mathrm{\Delta }\phi `$ being a small localized function (see Fig. 2) allows the average $`\frac{d^3p}{(2\pi )^3}\left(\frac{\mathrm{\Delta }\phi }{2}\right)^2`$ of Eq. (23) to be a perturbative expansion parameter so that, as a result, one can also use a perturbative expansion of $`S_T`$ in the number of insertions of the operator $`(i\stackrel{}{\alpha }\stackrel{}{})`$ multiplied by the function $`f(\omega )`$. In what follows, it is sufficient to truncate this perturbative series at the quadratic term. Contributions of higher order terms could be calculated in the same fashion.

The local operator (42) creating the replica vacuum state, together with the definition (37), is the central object of this paper. It describes the interaction with an external field (see Fig. 3a) of a particular form whose physical meaning is local excitations of the BCS vacuum, that is, fluctuations of the quark-antiquark correlations in the vacuum. In the remainder of the paper we call this vertex f-vertex.

The operators defined by Eqs. (21) and (42) are not identical. The crucial difference between them comes from the time ordering which appears in the definition (42). Indeed, for Eq. (21) and arbitrary time-dependent operators $`𝒪_i(t)`$ one has

$$0|T𝒪_1(t_1)\mathrm{}𝒪_n(t_n)S|0=0|[T𝒪_1(t_1)\mathrm{}𝒪_n(t_n)]\underset{n=0}{\overset{\mathrm{}}{}}\frac{1}{n!}(\mathrm{\Delta }Q^{}\mathrm{\Delta }Q)^n|0,$$
(43)
where all operators creating the excited vacuum stand to the right from the operators $`𝒪`$. On the contrary, with definition (42), one has the possibility to create the replica state at intermediate moments of time:

$$0|T𝒪_1(t_1)\mathrm{}𝒪_n(t_n)S_T|00|𝒪_1(t_1)\mathrm{}𝒪_n(t_n)|0$$

$$+_{t_1}^{\mathrm{}}𝑑tf(t)0|[\overline{\psi }(i\stackrel{}{\alpha }\stackrel{}{})\psi ]_t𝒪_1(t_1)\mathrm{}𝒪_n(t_n)|0$$
(44)
$$+_{t_2}^{t_1}𝑑tf(t)0|𝒪_1(t_1)[\overline{\psi }(i\stackrel{}{\alpha }\stackrel{}{})\psi ]_t𝒪_2(t_2)\mathrm{}𝒪_n(t_n)|0+\mathrm{},$$

where we choose $`t_1>t_2>\mathrm{}>t_n`$. This difference does not play a role if no external operators are involved, as in the case of the vacua orthogonality condition (see Eq. (45) below), but it becomes extremely important for the averages similar to (43), (44). Thus, with the operator (42), we extend the applications of the vacuum replica allowing its creation for finite periods of time during hadronic reactions.

### V.2 Vacua orthogonality revisited

Let us demonstrate how the orthogonality condition (23) appears in the new field-theory approach. From (42) we have,

$$0|1=0|S|0=0|T\mathrm{exp}\left[d^4xf(x_0)\overline{\psi }(\stackrel{}{x},t)\left(i\stackrel{}{\alpha }\stackrel{}{}\right)\psi (\stackrel{}{x},t)\right]|0$$
(45)
$$1+0|d^4xf(x_0)\left[\overline{\psi }\left(i\stackrel{}{\alpha }\stackrel{}{}\right)\psi \right]_x|0$$

$$+\frac{1}{2}d^4xd^4yf(x_0)f(y_0)0|T\left[\overline{\psi }\left(i\stackrel{}{\alpha }\stackrel{}{}\right)\psi \right]_x\left[\overline{\psi }\left(i\stackrel{}{\alpha }\stackrel{}{}\right)\psi \right]_y|0+\mathrm{},$$

where, as explained before, we truncate the expansion at the level $`f^2`$. It is easy to see that the term of order $`f`$ vanishes since $`\overline{v}_\sigma (\stackrel{}{p})(\stackrel{}{\alpha }\stackrel{}{p})v_\sigma ^{}(\stackrel{}{p})=0`$, so that the lowest contribution to (45) is given by the quadratic term. Moreover, it is clear that all terms with odd number of f-vertices vanish. Diagrammatically, the series (45) is given by the sum of many-leg loops with even number of f-vertices (see the lowest term in Fig. 3b). We have,

$$0|1=1+V\frac{d^4p}{(2\pi )^4}\frac{d\omega }{2\pi }f(\omega )f(\omega )\mathrm{Sp}\left[(\stackrel{}{\alpha }\stackrel{}{p})S(p_0,\stackrel{}{p})(\stackrel{}{\alpha }\stackrel{}{p})S(p_0+\omega ,\stackrel{}{p})\right]+\mathrm{}$$
(46)
or, after substitution of the explicit form of the propagator $`S(p_0,\stackrel{}{p})`$ from Eq. (11) and straightforward algebraic calculations,

$$0|1=1V\frac{d^3p}{(2\pi )^3}\left(\frac{\mathrm{\Delta }\phi }{2}\right)^2+\mathrm{},$$
(47)
where the property (37) of the function $`f`$ was also used. The expression (47) coincides with the expansion in Eq. (23). To restore the full form of Eq. (23), notice that the factor of the three-dimensional volume $`V`$ accompanies each fermionic loop in the diagram. Thus, summing all one-loop many-leg diagrams one restores the logarithm $`\mathrm{ln}\left(\mathrm{cos}^2\frac{\mathrm{\Delta }\phi }{2}\right)`$. Now, to arrive at the exponential form, we need only to take into account many-loop disconnected diagrams to reproduce the whole series of terms $`\left[\mathrm{one}\mathrm{loop}\right]^n/n!`$. They sum to yield Eq. (23). The colour and the flavour factors follow immediately from the corresponding traces over the fermionic loops, so that one can easily see that they always accompany the volume $`V`$ and enter in the combination $`N_CN_fV\frac{d^3p}{(2\pi )^3}=\mathrm{Sp}_{pcf}`$. This completes the proof and shows that $`S_T`$ is the quantum-field creator of the replica. It is clear now that normalization of the matrix element of an arbitrary operator $`𝒪`$, in presence of the replica,

$$0|T𝒪S_T|00|T𝒪S_T|0_{\mathrm{normalized}}=\frac{0|T𝒪S_T|0}{0|S_T|0}=0|T𝒪S_T|0_{\mathrm{connected}},$$
(48)
means that only connected diagrams should be considered with Wick contractions between fermionic operators coming from the operator $`𝒪`$ itself and those from the operator $`S_T`$ given by Eq. (42).

## VI Feynman rules in the presence of the replica

In this subsection, we address the question of the quark propagation in the vacuum in the presence of the replica.

From the operator (42) one can easily derive the Feynman rules for the f-vertex (Fig. 3a):

* each f-vertex is to be supplied by the product $`f(\omega )(\stackrel{}{\alpha }\stackrel{}{p})`$, where $`\omega `$ is the energy pumped to the system in this vertex, $`\stackrel{}{p}`$ being the three-dimensional momentum floating into the f-vertex along the fermionic line;
* for each f-vertex one has an integral over the energy $`\omega `$.

However, as it stands, global energy conservation is not satisfied because the operator $`S_T`$ of Eq. (42) does not satisfy time translational invariance. To restore time translational invariance we are forced — very much in the same way as it was done in the instanton case — to consider here a one-dimensional gas of replicas with each of them associated with a particular time origin.

### VI.1 Time translational invariance and time chains of replicas: the f-chain

The function $`f(x_0)`$ defined in Eqs. (37), (39), and (40) describes a localized in time object with the centre at $`x_0^{(0)}=0`$. However, translational invariance in time would require results to be independent of the time origin. To achieve time translational invariance we shall proceed along similar lines as were used in the case of instantons. First, let us generalize the formulae (36)-(42) to describe the f-vertex localized near a nonzero time origin $`x_0^{(0)}`$, $`f(x_0x_0^{(0)})`$. Then, the modified version of the relation (40) takes the form

$$f(\omega )=f^{}(\omega )=\left[\frac{\mathrm{\Delta }\phi (p_{}(\omega ))}{2p_{}(\omega )}\theta (2\mathrm{\Delta }+\omega )+\frac{\mathrm{\Delta }\phi (p_{}(\omega ))}{2p_{}(\omega )}\theta (2\mathrm{\Delta }\omega )\right]e^{i\omega x_0^{(0)}}$$
(49)
with $`p_{}(\omega )`$ being the same solution of the equation $`E_p=\omega /2`$ as in Eq. (37). The operator (42) becomes

$$S_T=T\mathrm{exp}\left[d^4xf(x_0x_0^{(0)})\overline{\psi }(\stackrel{}{x},x_0)\left(i\stackrel{}{\alpha }\stackrel{}{}\right)\psi (\stackrel{}{x},x_0)\right].$$
(50)
Finally, it suffices to sum over an infinite set of time origins to restore time translations. As for this set, we would be forced to solve the dynamics of replica interactions, which is beyond the scope of this paper. As in the instanton case we assume a simpler picture of a dilute gas (in time) of replicas. So let us consider a diluted chain of $`N`$ time origins $`\{f(x_0x_0^{(n)})\}_N`$, here called f-chain:

$$F(x_0)=\underset{n=1}{\overset{N}{}}f(x_0x_0^{(n)})\underset{n=1}{\overset{N}{}}f_n(x_0),$$
(51)
$$f_n(\omega )=\left[\frac{\mathrm{\Delta }\phi (p_{}(\omega ))}{2p_{}(\omega )}\theta (2\mathrm{\Delta }+\omega )+\frac{\mathrm{\Delta }\phi (p_{}(\omega ))}{2p_{}(\omega )}\theta (2\mathrm{\Delta }\omega )\right]e^{i\omega x_0^{(n)}}.$$
(52)
Notice that for well separated functions $`f_n(x_0)`$ in the sum (51) all interference terms are suppressed:

$$f_n(\omega )f_m(\omega )\delta _{nm},$$
(53)
for the separation $`|x_0^{(n)}x_0^{(m)}|1/\lambda `$. This is the case for a diluted chain. As a result, we have the sum of $`N`$ equivalent contributions coming from $`N`$ independent isolated f-vertices. For $`N`$ going to infinity, with the fixed mean separation between two neighbours $`\tau `$, one naturally arrives at the notion of the density $`n=N/T=1/\tau `$. It is sufficient to consider an equally spaced one-dimensional f-chain with $`x_0^{(n)}=n\tau `$. Within this dilute approximation it is straightforward to recover the overall energy conservation law (time translational invariance). Indeed, if a diagram does not contain external legs, like the fish-like diagram in Fig. 3b, then the overall phase factor coming from the definition (49) disappears automatically due to the properties of the f-vertex (see Eq. (52)):

$$f_n(\omega )f_n(\omega )=f_n(\omega )f_n^{}(\omega )=|f_n(\omega )|^2.$$

On the contrary, in the case of $`N_{\mathrm{ext}}`$ external legs attached to the diagram we have a phase factor for the $`m`$th f-vertex in the chain, the exponent $`\mathrm{exp}[ix_0^{(m)}_{i=1}^{N_{\mathrm{ext}}}E_i^{\mathrm{ext}}]`$, where $`E_i^{\mathrm{ext}}`$ is the energy delivered by the $`i`$th external leg of the diagram of $`N_{\mathrm{ext}}`$. As a result, if the total energy is not conserved, $`_{i=1}^{N_{\mathrm{ext}}}E_i^{\mathrm{ext}}0`$, then each f-vertex brings in a contribution to the total sum with a random phase factor, so that the total amplitude vanishes. Formally, this can be demonstrated as follows:

$$\underset{m=1}{\overset{N}{}}\mathrm{exp}\left(ix_0^{(m)}\underset{i=1}{\overset{N_{\mathrm{ext}}}{}}E_i^{\mathrm{ext}}\right)\underset{m=1}{\overset{N}{}}\mathrm{exp}\left(im\tau \underset{i=1}{\overset{N_{\mathrm{ext}}}{}}E_i^{\mathrm{ext}}\right)\underset{N\mathrm{}}{}\frac{1}{\tau }\delta \left(\underset{i=1}{\overset{N_{\mathrm{ext}}}{}}E_i^{\mathrm{ext}}\right).$$
(54)
The physical reason for such a relation is the fact that, for an infinitely long f-chain, one recovers the translational invariance in time and therefore the total energy conservation law is also restored.

Then time translation invariance can be coded into two extra Feynman rules, in addition to the previous two rules:

* the full diagram is to be supplied by an overall energy conservation $`\delta `$-function, so that for the diagram with K f-vertices only K-1 independent integrals over pumped energies remain;
* the full amplitude is to be multiplied by the time density of the replica excitations, $`n=N/T`$, which accounts for the fact that during the full time of the hadronic process $`T`$ the replica has been excited $`N`$ times.

### VI.2 Fermionic propagator in the presence of replica

The quark propagator in the presence of the replica is given by the formula:

$$S^{}(x)=0|T\psi (x)\overline{\psi }(0)S_T|0_c,$$
(55)
where $`S_T`$ is the operator creating the f-chain and, as discussed before, only connected diagrams are to be considered. Expanding the propagator (55) in powers of f-vertex insertions with a truncation at the quadratic term, one finds:

$$S^{}(x)0|T\psi (x)\overline{\psi }(0)|0+d^4yF(y_0)0|T\psi (x)\overline{\psi }(0)\left[\overline{\psi }\left(i\stackrel{}{\alpha }\stackrel{}{}\right)\psi \right]_y|0$$

$$+d^4yd^4zF(y_0)F(z_0)0|T\psi (x)\overline{\psi }(0)\left[\overline{\psi }\left(i\stackrel{}{\alpha }\stackrel{}{}\right)\psi \right]_y\left[\overline{\psi }\left(i\stackrel{}{\alpha }\stackrel{}{}\right)\psi \right]_z|0+\mathrm{},$$
(56)
with $`F(t)`$ being the f-chain profile function. In momentum space, using the Feynman rules for the replica derived above, one arrives at

$$S^{}(p_0,\stackrel{}{p})=S(p_0,\stackrel{}{p})+nf(0)S(p_0,\stackrel{}{p})(\stackrel{}{\alpha }\stackrel{}{p})S(p_0,\stackrel{}{p})$$

$$+n\frac{d\omega }{2\pi }f(\omega )f(\omega )S(p_0,\stackrel{}{p})(\stackrel{}{\alpha }\stackrel{}{p})S(p_0+\omega ,\stackrel{}{p})(\stackrel{}{\alpha }\stackrel{}{p})S(p_0,\stackrel{}{p})+\mathrm{}.$$
(57)
We neglect all terms containing $`f(0)`$, since, in our model, $`f(0)`$ turns out to be very small $`(f(0)1/\sqrt{\sigma _0})`$ albeit not exactly zero. It corresponds to large quark momenta, $`pp_{}(\omega =0)300MeV`$, and it is clear that for this range of quark momenta we should have only one phase — governed by perturbative QCD with quarks and gluons — and, therefore, $`\mathrm{\Delta }\phi `$ should be identically zero rather than being very small. Having no gluons, being a mean-field theory, in the gluonic sector, the class of Nambu-Jona-Lasinio models we use in this paper cannot address the physics in this region, being already remarkable that chiral symmetry requirements alone should force an almost identical asymptotic behaviour, in momenta, for the quark dispersive relations in different chiral phases.

Having this in mind, we finally arrive at simplified Feynman rules in the presence of replicas. They are:

* each f-vertex is supplied by the product $`(\stackrel{}{\alpha }\stackrel{}{p})`$, where $`\stackrel{}{p}`$ is the three-dimensional momentum floating into the f-vertex along the fermionic line;
* the two f-vertices are connected by an effective f-propagator of the form

$$G(p)=nf(p_0)f(p_0)(2\pi )^3\delta ^{(3)}(\stackrel{}{p})$$
(58)
with $`n`$ being the time density of f-vertices in the chain;
* global conservation of the energy and the three-momentum is ensured in the usual way.

Notice that we chose to move the distribution function $`f(\omega )`$ from the vertex to the propagator in order to have its form close to those adopted in the solid-state physics.

Using the new Feynman rules, one can rewrite formula (57) for the propagator as a Dyson series,

$$S^{}(p)=S(p)+S(p)\mathrm{\Sigma }(p)S(p)+\mathrm{},$$
(59)
$$\mathrm{\Sigma }(p)=\frac{d^4q}{(2\pi )^4}G(pq)(\stackrel{}{\alpha }\stackrel{}{q})iS(q)(\stackrel{}{\alpha }\stackrel{}{p}),$$
(60)
where $`S(p)`$ is given by Eq. (11). Straightforward calculations yield:

$$\mathrm{\Sigma }(p)=\frac{n}{2}|\stackrel{}{p}|^2\left[\gamma _0\mathrm{\Lambda }_+(\stackrel{}{p})|f(p_0+E_p)|^2\gamma _0\mathrm{\Lambda }_{}(\stackrel{}{p})|f(p_0E_p)|^2\right],$$
(61)
and Eq. (59) can be approximately rewritten as

$$S^{}(p)\frac{\mathrm{\Lambda }_+(\stackrel{}{p})\gamma _0}{p_0E_p\frac{n}{2}|\stackrel{}{p}f(p_0+E_p)|^2+i0}+\frac{\mathrm{\Lambda }_{}(\stackrel{}{p})\gamma _0}{p_0+E_p+\frac{n}{2}|\stackrel{}{p}f(p_0+E_p)|^2i0}.$$
(62)
Using the fact that the first term in Eq. (62) is peaked at $`p_0E_p`$ and the second term is peaked at $`p_0E_p`$, we can neglect the effect of the dressing on the projectors and approximately substitute $`f(p_0\pm E_p)`$ by $`f(2E_p)`$ in both denominators, which yields:

$$S^{}(p)\frac{\mathrm{\Lambda }_+(\stackrel{}{p})\gamma _0}{p_0(E_p+\delta E_p)+i0}+\frac{\mathrm{\Lambda }_{}(\stackrel{}{p})\gamma _0}{p_0+(E_p+\delta E_p)i0}S(p)+\frac{S(p)}{E_p}\delta E_p+\mathrm{},$$
(63)
where

$$\delta E_p=\frac{n}{8}(\mathrm{\Delta }\phi )^2.$$
(64)
In other words, the effect of the replica on the fermionic propagator amounts to a shift of the poles of the latter from $`\pm E_p`$, as in Eq. (11), to $`\pm [E_p+\frac{n}{8}(\mathrm{\Delta }\phi )^2]`$.

Relations (59) and (60) together can be presented in the form of the Dyson-Schwinger equation for the new fermionic propagator in the presence of the replica:

$$S^1(p)S^1(p)=i\frac{d^4q}{(2\pi )^4}G(pq)(\stackrel{}{\alpha }\stackrel{}{q})S^{}(q)(\stackrel{}{\alpha }\stackrel{}{p}),$$
(65)
which we solve up to the terms of order $`(\mathrm{\Delta }\phi )^2`$. We do not dress the vertex in Eq. (65), since this leads to higher corrections in powers of $`\mathrm{\Delta }\phi `$. Thus we conclude that, at the given level of accuracy, quarks propagate in the presence of the replica, as if a new type of inter-quark interaction defined by the quark current-current interaction kernel (58) had been introduced. This effective interaction is present only in the BCS vacuum with spontaneously broken chiral symmetry and amounts to the change of the quark dispersive law, as given in Eq. (64).

## VII Discussion and Conclusions

References BNR  and oni , when taken together, show that vacuum replication should constitute the rule rather than the exception for, at least, NJL-type models. Recent developments on this class of models pp  show them to be able to describe, in a physically transparent way, low energy $`\pi \pi `$ scattering. This arises because Ward identities force the cancellation (for $`m_\pi =0`$) of all $`\pi \pi `$ T-matrix contributions which are independent of the pion momenta. This observation (the Adler zero) implies a two-pion overlap kernel proportional to $`p^2`$. This general observation, when taken together with the fact that pions have a size (a cutoff in momentum space), must then lead to overlap kernels numerically behaving as $`p^2e^{\beta p^2}`$ with $`\beta ^1`$ playing the role of this cut-off. Other overlap kernels, with higher rank tensors in the relative $`\pi \pi `$ momenta, may also exist. This requirement is model independent. It then happens that this type of kernels is known, starting with the work of Van Beveren et al. doubling , to hold, if strong enough, a light sigma. This is probably the common cause underneath the various independent calculations where a light sigma was found.

Similarly, we would also like to argue vacuum replication to be a general feature of low energy effective theories for hadron physics. This hope is reinforced by the map which is known to exist between extended NJL models and $`ChPT`$ Lagrangians cahill . However it remains to be seen whether this map is also able to inject the existing vacuum replication of NJL into $`ChPT`$. In any case it is clear that the Weinberg limit for the pion-pion scattering We  is left untouched by the existence of such a vacuum replica. Indeed, the difference $`\mathrm{\Delta }\phi =\phi _0\phi _1`$ playing a crucial role for the theory of the vacuum replica vanishes as $`|\stackrel{}{p}|`$ at small momenta $`\stackrel{}{p}`$. The amplitudes of physical processes with the excitation of the replica are, roughly speaking, proportional to $`(\mathrm{\Delta }\phi )^2`$ or higher, so that they vanish at least as $`\stackrel{}{p}^2`$ when $`\stackrel{}{p}0`$, as compared to the amplitudes of the same processes without excitation of the replica. On the other hand, for finite momenta, the excitation of the vacuum replica does provide corrections to the standard formulae, which are interesting and instructive to extract and to study both theoretically and experimentally.

The Feynman rule of Eq. (58) together with Eq. (65) constitute the central results of this work. They show that the existence of a replica is tantamount to the existence of a new quark-quark force going like (at BCS level) $`G(p)=nf(p_0)f(p_0)(2\pi )^3\delta ^{(3)}(\stackrel{}{p})`$ and a quark energy renormalization, $`E_pE_p+\frac{n}{8}(\mathrm{\Delta }\phi )^2`$. This new interaction will add to sigma-exchange quark-quark forces in the intermediate energy range. Thus, we predict a new scalar particle-like object which exists in the theory together with the “standard” doubling  $`\sigma `$-meson. In contrast to the latter, the vacuum-induced $`\sigma `$ has not a fixed mass, but rather a distribution given by the function $`f(\omega )`$. The structure of this new particle in terms of the fermionic fields is rather peculiar and has nothing to do with the naive scalar structure $`\overline{\psi }\psi `$. Finally this new quark-quark force can be used to evaluate the decay of the replica into pairs of pions (and/or photons), as the lightest particles. This will be the subject of a future work.

###### Acknowledgements.

The authors are grateful to P. Bicudo and Yu. S. Kalashnikova for many fruitful discussions and for reading the manuscript and critical comments. A. Nefediev would like to thank the staff of the Centro de Física das Interacções Fundamentais (CFIF-IST) for cordial hospitality during his stay in Lisbon and to acknowledge the financial support of RFFI grants 00-02-17836, 00-15-96786, 01-02-06273 and INTAS grants OPEN 2000-110 and YSF 2002-49.


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# Theoretical study of finite temperature spectroscopy in van der Waals clusters. II Time-dependent absorption spectra

## I Introduction

Clusters of van der Waals atoms or molecules are known to exhibit significant finite size effectsjortner  in their thermodynamic behavior. In particular, their structure and low-temperature stable phase can strongly depend on size. By doping such clusters with a chromophoric atom, spectroscopic techniques are able to characterize the structure of the whole complex. Very often, the chromophore only acts as a small perturbation on the geometry of the host van der Waals cluster, and spectroscopy can then be used as a probe of structure and structural changes in the cluster. These ideas, which date back to experimental studies in the eighties,hahn ; even  have received some theoretical support in the recent years.curotto ; moseler  In the previous paper in this series,paperI  the influence of temperature and cluster size on the photoabsorption spectrum in CaArn clusters was investigated. In some cases, such as CaAr13 or CaAr37, features in the absorption spectrum were seen to originate from the competition between specific isomers. These results were obtained using the quantum superposition method,jcpquantum  which yields ergodic data by construction from a database of local minima on the potential energy surface (PES).

However, the equilibrium properties computed from the superposition approach obviously provide no information about the way in which equilibrium was established, or how long equilibration would take from a given starting distribution. As was shown by Miller and coworkers,ar38miller  relaxation can be rather slow when the competing minima are separated by large (free) energy barriers. In cases such as Ar38, conventional molecular dynamics simulations are presently unable to reach equilibrium and thus cannot provide estimates of the rate constants. However, the master equation dynamics approach, introduced in cluster physics by Kunz and Berry,kunz  has been successfully applied to this system,doyemw99a  although a subsequent discrete path sampling study located somewhat faster pathways.dps  In particular, it has been used to calculate activation energies in the interconversion of (NaCl)$`{}_{}{}^{}{}_{35}{}^{}`$ nanocrystalsdoyew99  that could be compared to those extracted from ion mobility measurements.hudgins

It is important to characterize the dynamics of the CaArn clusters investigated previously at thermodynamical equilibrium, because the time required for reaching equilibrium may not always be accessible in experiments. In addition, the most powerful way to investigate phase changes through spectroscopy on single clusters may require ion trapping.maier ; KruckebergSMP00  In principle, this technique can be used to examine the system over very long time scales, which makes it a possible tool for studying dynamics, including relaxation toward thermal equilibrium, possibly via kinetic traps.

This article is a natural extension to our previous work, and provides an investigation of the relaxation dynamics in some selected CaArn clusters, as evidenced by their photoabsorption spectra. In the next section, we briefly recall the basic ingredients of the master equation approach, and we incorporate quantum corrections to the equilibrium probabilities and rate constants. These corrections are necessary for consistency with the previous article.paperI  Before actually studying dynamical processes, we construct and discuss disconnectivity graphsbecker ; walesacp  in Sec. III. Such graphs are very helpful in elucidating the role of the underlying PES on the kinetics. Disconnectivity graphs are presented and discussed for the clusters CaAr6, CaAr10, CaAr13, and CaAr37, which were investigated in reference paperI, . Using the Gaussian theory of absorption inspired by Wadi and Pollak,paperI ; wp  we calculate the photoabsorption intensity of these clusters as a function of both time and excitation energy. The results are given and analysed in Sec. IV, before we summarize and conclude in Sec. V.

## II Master equation dynamics

In the master equation approach,master ; kunz95  the interbasin dynamics on the energy landscape is described by the time evolution of a vector, $`𝐏(t)`$, whose components are the probabilities of the system residing in each of the basins at time $`t`$. The differential equations governing this evolution are

$$\frac{dP_i}{dt}=\underset{ji}{}\left[k_{ij}P_j(t)k_{ji}P_i(t)\right],$$
(1)
where $`k_{ij}`$ is the rate constant for transitions leading from minimum $`j`$ to minimum $`i`$. A transition matrix $`𝐖`$ is defined with componentsmaster ; kunz95 ; walesacp

$$W_{ij}=k_{ij}\delta _{ij}\underset{m}{}k_{mi},$$
(2)
and Eq. (1) is solved analytically after symmetrization and diagonalization of the matrix $`𝐖`$.kunz95 ; walesacp  The rate constant $`k_{ij}`$ is the sum over all transition states separating minima $`i`$ and $`j`$:

$$k_{ij}=\underset{\alpha }{}k_j^\alpha ,$$
(3)
where $`k_j^\alpha `$ is given by the usual Rice-Ramsperger-Kassel-Marcus theory. RiceR27 ; RiceR28 ; Kassel28 ; Marcus52 ; WiederM62 ; Marcus65 . In the canonical ensemble we have

$$k_j^\alpha (T)=\frac{k_BT}{2\pi \mathrm{}}\frac{Z_j^\alpha (T)}{Z_j(T)},$$
(4)
where $`k_B`$ and $`h`$ are Boltzmann’s and Planck’s constants, respectively. $`Z_j^\alpha `$ and $`Z_j`$ are the partition functions corresponding to the transition state $`\alpha `$ between $`i`$ and $`j`$, and to the minimum $`j`$, respectively. Here we use the harmonic approximation to model both $`Z_j^\alpha `$ and $`Z_j`$, but we incorporate quantum corrections by employing the expressions for quantum oscillators:

$`Z_j(T)`$ $`=`$ $`{\displaystyle \frac{h_j}{(2\pi )^\nu N!}}e^{\beta E_j}{\displaystyle \underset{k=1}{\overset{\nu }{}}}{\displaystyle \frac{\mathrm{exp}(\beta \mathrm{}\omega _{jk}/2)}{1\mathrm{exp}(\beta \mathrm{}\omega _{jk})}};`$ (5)
$`Z_j^\alpha (T)`$ $`=`$ $`{\displaystyle \frac{h_j^\alpha }{(2\pi )^{\nu 1}N!}}e^{\beta E_j^\alpha }{\displaystyle \underset{k=1}{\overset{\nu 1}{}}}{\displaystyle \frac{\mathrm{exp}(\beta \mathrm{}\omega _{jk}^\alpha /2)}{1\mathrm{exp}(\beta \mathrm{}\omega _{jk}^\alpha )}}.`$ (6)
In these expressions, $`h_j`$ (resp. $`h_j^\alpha `$) denotes the order of the point group of minimum $`j`$ (resp. transition state $`\alpha `$ between minima $`i`$ and $`j`$). $`E_j`$ and $`E_j^\alpha `$ are the energy of these stationary points, and $`\{\omega _{jk}\}`$ and $`\{\omega _{jk}^\alpha \}`$ are their respective normal mode frequencies. $`\nu =3N6`$ is the number of independent degrees of freedom of the cluster, and $`\beta =1/k_BT`$. In the limit $`\mathrm{}0`$, the rate constant tends to its usual classical value

$$k_j^\alpha (\mathrm{}0)=\frac{h_j^\alpha }{h_j}\frac{(\overline{\omega }_j)^\nu }{(\overline{\omega }_j^\alpha )^{\nu 1}}e^{\beta (E_j^\alpha E_j)},$$
(7)
where $`\overline{\omega }_j`$ and $`\overline{\omega }_j^\alpha `$ are the geometric mean normal mode frequencies of the minimum and transition state, respectively. In the low temperature limit $`\beta \mathrm{}`$, the rate is proportional to $`T\mathrm{exp}[(E_j^{\alpha 0}E_j^0)/k_BT]`$, where $`E_j^{\alpha 0}`$ and $`E_j^0`$ are the energies of the two stationary points including the zero-point energy contributions. While $`E_j^\alpha E_j`$ is always positive, it may well be that $`E_j^{\alpha 0}<E_j^0`$, leading to a divergent rate. In this case the two minima cannot be treated independently because of strong quantum delocalization effects. However, this situation should not arise at high or moderate temperatures where $`k_BT`$ is large compared to the zero-point energy, and this is the regime of interest in the present work.

Application of the master equation approach requires one to build a connected set of minima and the interwell transition states.walesacp  To do this we used eigenvector-followingef  in conjunction with several methods to sample the local minima.walesacp  For small clusters containing less than 11 atoms, systematic searches were started from the global minimum, and continued until no new minima were found after searching for transition states along every eigenvector of each minimum in the set. For these systems the connected set of minima should be nearly complete. For CaAr13, we expect the number of distinct local minima to be significantly larger than in Ar14, which itself possesses more than $`10^4`$, excluding permutation-inversion isomers. We decided to perform only one cycle of systematic eigenvector-following transition state searches from each mode of every minimum in the database collected for the study at thermodynamic equilibrium.paperI

The situation becomes quite critical for CaAr37. As was shown in our previous study,paperI  several minima with different structures coexist at low energy, and we were not able to build a connected set containing all these minima using one systematic eigenvector-following cycle from the database obtained with parallel tempering Monte Carlo. For this larger cluster, we selected a small set of the low energy minima of interest, and we attempted to find discrete pathways (series of minima-transition states-minima) connecting them. To do this we followed the method described in reference dps, , where a connected path is built up using successive double-ended pathway searches. The nudged-elastic-band approach MillsJ94 ; JonnsonMJ98 ; HenkelmanUJ00 ; HenkelmanJ00 ; HenkelmanJ01 ; MaragakisABRK02  was used to generate initial guesses for transition states, which were then used as the starting points for hybrid eigenvector-following transition state searches munrow99 ; kumedamw01 . These initial paths generally have rather high barriers, and so the discrete path sampling approach was then employed to provide a more realistic account of the rates.dps  These calculations also produce connected databases of minima and transition states that should provide a more appropriate picture of the dynamics, either in visualisations using disconnectivity graphs, or from master equation calculations. All the geometry optimisations and pathway calculations were performed with the OPTIM software package,optim ; walesacp  for which we implemented the pairwise potential describing the ground state potential energy surface of CaArn clusters.epjd

## III Energy landscapes

A convenient way of visualizing complex energy landscape is to construct a disconnectivity graph. Such graphs were introduced by Becker and Karplusbecker  in their study of a tetrapeptide. They have since been used in a much wider context.walesacp  Disconnectivity graphs show how the minima of the PES are connected to each other and, more importantly, what is the height of the barriers between these minima. Further details about the construction of disconnectivity graphs can be found in reference walesacp, .

In the present work we have included zero-point energy corrections for the energies of the minima and transition states. Burnham et al. have previously found that zero-point effects change the appearance of disconnectivity graphs for the water hexamer significantly.BurnhamXMAM02  As noted in the previous section, the zero-point terms sometimes lead to the merging of two (and possibly more) minima. However, such events were not observed in CaAr6, for which we located twelve distinct minima and twenty transition states. The disconnectivity graph for this cluster is shown in Fig. 1 along with the two lowest energy isomers. According to the terminology introduced in reference walesnat, , this graph has a typical ‘palm tree’ character: the global minimum lies at the bottom of a single funnel, and the absence of large energy barriers is expected to permit relatively fast relaxation toward equilibrium.

A similar picture was found for the larger cluster, CaAr10, as shown in Fig. 2. In this case we located 391 distinct minima connected via 1831 transition states. At the bottom of the funnel, the three lowest-energy minima lie close together. They are all based on the incomplete icosahedra, with different substitional sites for the calcium atom. As Fig. 2 shows, the two lowest minima are extremely close in energy, and the energy barrier that separates them is very small (less than $`10^3`$ eV). Hence these two isomers can barely be considered distinct.

The disconnectivity graph of CaAr13 is shown in Fig. 3. The ‘palm tree’ character of this graph also suggests that relatively fast relaxation should be possible to the global minimum. However, the bottom of the funnel is slightly rugged due to the presence of additional isomers with respect to what would be expected for Ar14. The four extra structures found by changing the substitutional site of the calcium atom create a secondary side funnel. They are close in energy to the global minimum, and are displayed in Fig. 3 next to a more detailed view of the corresponding part of the graph. The ordering between these isomers is straightforwardly explained by the weaker Ca–Ar bond compared to Ar2. The lowest-energy barrier between the global minimum and the next four isomers lies about $`2.19\times 10^3`$ eV/atom above isomer 1, which is equivalent to a temperature of about 25 K. Below this temperature we expect the relaxation to the global minimum to become significantly slower due to trapping in the secondary funnel.

Finally we consider the larger CaAr37 cluster. Starting from the ten lowest minima in the database obtained by systematic quenching along a parallel tempering Monte Carlo trajectory,paperI  we were able to establish twenty connected discrete pathways using the method described in reference dps, . New low-energy minima were discovered, two of them lower than some in the initial set. Four additional pathways were then constructed in the same way. As mentioned above, these initial pathways found may be far from optimal in terms of rates. The typical initial path contained 30–40 minima and the disconnectivity graph constructed just from the initial pathway searches contained 731 distinct minima and 820 transition states. It is shown in Fig. 4, together with a selection of low-energy structures chosen from the initial sample. Clearly this graph does not show the single funnel aspect of the previous clusters, and resembles more the ‘banyan tree’ form.walesnat

In fact, the energy landscape of CaAr37 is more complicated than that of Ar38, which only has two main funnels associated with truncated octahedral or icosahedral structures, respectively. It is closer to the actual multiple funnel shape of the disconnectivity graph in the ionic cluster (NaCl)$`{}_{}{}^{}{}_{35}{}^{}`$.doyew99b  This increased complexity is due to the larger number of isomers and possible binding sites for calcium, and to the existence of a particularly stable decahedral isomer. The stabilization of the anti-Mackay icosahedral structures (isomer 4) due to zero-point effects is another complicating factor.jcpquantum

The CaAr37 cluster exhibits several similarities with Ar38, such as the nonicosahedral global minimum and the multiple-funnel energy landscape. In thermal equilibrium, the low-temperature behavior is essentially governed by the decahedral and Mackay-type icosahedral minima.paperI  The truncated octahedral isomer is not expected to play a major role in the relaxation dynamics, except if it contributes significantly to the initial conditions.

From Fig. 4 we see that the decahedral and Mackay icosahedra isomers belong to the same superbasin at relatively low energies. Hence we expect to find significantly faster relaxation than in Ar38, where the truncated octahedron and the icosahedra are much farther apart in configuration space, and separated by a relatively high barrier. However, to obtain insight into the relative stabilities of the isomers at the temperature where relaxation is simulated, it may be helpful to include entropic effects in the disconnectivity graphs.KrivovK02 ; EvansW03  To achieve this goal we simply computed the free energies of the minima and transition states instead of potential energy minima, replacing $`E_j`$ ($`E_j^\alpha `$) by $`F_j=k_BT\mathrm{ln}Z_j`$ ($`F_j^\alpha =k_BT\mathrm{ln}Z_j^\alpha `$), where the partition functions were obtained in the harmonic approximation, and taken from Eqn. (5,6).

The free-energy disconnectivity graph of CaAr37 at $`T=20`$ K is represented in Fig. 5. As can be clearly seen on this figure, the most stable minimum at this temperature is the anti-Mackay icosahedron isomer (4), and the free energy barrier to the decahedral and Mackay-icosahedral minima seems rather large. This change in the most stable funnel with respect to the $`T=0`$ disconnectivity graph should hinder relaxation, and we therefore anticipate particularly slow dynamics.

## IV Relaxation to equilibrium: Time-dependent absorption spectra

We now turn to the relaxation properties of CaArn clusters resulting from the solution of the master equation. Two types of relaxation have been considered, either starting from $`T=0`$ (only the quantum global minimum is occupied) and moving to higher $`T`$, or starting from a finite temperature equilibrium distribution and changing to lower $`T`$. The equilibrium distributions were calculated within the quantum harmonic superposition approach applied to the same database of minima that was used to construct the disconnectivity graphs, without reweighting. For CaAr37, this procedure yields a heat capacity peak corresponding to melting located at about 25 K, slightly higher than the one obtained in the more thorough previous study.paperI  For the other clusters the harmonic approximation wthout reweighting performs rather well.

Here we focus on the photoabsorption spectrum as a possible probe of cluster structure in a dynamical context. The absorption intensity of the $`4s^24s^14p^1`$ excitation for calcium was calculated using the Gaussian theory adapted and extended from the work of Wadi and Pollak.paperI ; wp  The excited state potential energy surfaces were modelled by a diatomics-in-molecules (DIM) Hamiltonian, which was fully described in Ref. epjd, .

We first show in Fig. 6 the time evolution of the absorption spectrum of CaAr6, starting at $`t=0`$ from the zero temperature distribution, and relaxing at $`T=25`$ K, slightly above the melting point.paperI  The spectrum remains essentially doubly-peaked, and at very small times $`t<5`$ ps the red peak can be separated into two distinct lines characteristic of the ground state isomer. The blue wing of this peak soon becomes a shoulder. These results correspond to fast relaxation, which barely has a spectroscopic signature. Such simple dynamics is perfectly consistent with the energy landscape of this cluster, as seen from its disconnectivity graph. In the upper panel of Fig. 6, the characteristic time constants, $`\tau _i`$, of the rate matrix $`𝐖`$ are represented on a horizontal axis, for both the quantum and classical regimes. They are calculated from the nonzero eigenvalues, $`\lambda _i`$, of $`𝐖`$ as $`\tau _i=1/\lambda _i`$. At 25 K, the largest time constant is a few tens of picoseconds, which is roughly in agreement with the observed decay of the spectroscopic signal, although the experimental relaxationis faster, by about one order of magnitude, than the slowest time constant $`\tau _{\mathrm{max}}`$. Such quantitative discrepancies are typical of the errors that simple rate theories based upon harmonic densities of states are expected to introduce. Quantum effects are small in this system and the relaxation kinetics for CaAr10 were found to be very similar, so detailed discussion is omitted.

Relaxation from a zero temperature distribution has also been investigated in CaAr13 for a temperature jump to $`T=40`$ K, which lies close to the melting point of this cluster.paperI  At this temperature, the occupation probability of the secondary funnel is quite large. The time-dependent spectrum in Fig. 7 indeed exhibits a transition from the ground state, identified by two absorption peaks, to vibrationally excited isomers and the three-peak pattern characteristic of calcium located in the icosahedral shell.paperI  Monitoring the time-dependent signal shows that relaxation typically occurs on a 50 ps time scale, which is again one order of magnitude faster than $`\tau _{\mathrm{max}}`$ in this system, as seen in the upper part of Fig. 7.

At $`T=20`$ K, the global minimum of CaAr13 is predicted to have an equilibrium occupation probability larger than 90%,paperI  hence the next metastable isomers play only a minor role in the thermodynamic properties. Relaxation from a high temperature distribution (50 K) has also been simulated using the master equation approach. The time-dependent absorption spectrum is plotted in Fig. 8 along with the distribution of characteristic decay times from the rate matrix. The variations observed in the spectrum are in clear contrast with the previous results. During the first 100 ps, the cluster relaxes from a broad distribution of isomers towards the main funnel that corresponds to the capped icosahedron. As indicated by the two-peak absorption spectrum, the secondary funnel has a larger occupation probability about 5 ns after the dynamics has started. The cluster then finally relaxes to its equilibrium distribution following single exponential kinetics, characterized by a rather large time constant of about $`10^5`$ ps. This value is still one order of magnitude faster than the calculated $`\tau _{\mathrm{max}}10^6`$ ps, represented in the upper part of Fig. 8. The two-step relaxation process observed here can be easily interpreted thanks to the disconnectivity graph in Fig. 3. The secondary funnel constitutes a kinetic trap, resulting in a significant slowing down of the dynamics. While the cluster easily finds its way into this secondary funnel, escape to the global minimum is much slower due to the rather large energy barrier. In agreement with previous work, this multiple-funnel landscape exhibits a separation of timescales in its dynamics.walesnat ; walesacp

We finally discuss the case of CaAr37, for which we solved the master equation at $`T=20`$ K, starting from the $`T=0`$ initial distribution. The magnitude of the characteristic decay times, as computed from the eigenvalues of the rate matrix, are remarkably large, reaching values close to one second. The calculated absorption spectrum is shown in Fig. 9 as a function of time. The choice of a logarithmic scale emphasizes the different time scales present in this system. The multiple funnels of the energy landscape are in competition below 20 K, and the cluster undergoes multiple transitions before reaching equilibrium. As we deduced from the free energy disconnectivity graph in Fig. 5, relaxation from 0 to 20 K in this system requires the cluster to escape from its initial decahedral/icosahedral funnel. At least four significant changes in behaviour are detected through absorption spectroscopy, after $`10^2`$, $`10^6`$, $`10^{10}`$, and $`10^{12}`$ ps, respectively. The transient regime thus appears particularly slow, in a similar way to the dynamics observed in Ar38.ar38miller  The spectra in Fig. 9 show that some intermediate minima, which are too high in energy to be significantly occupied at equilibrium, may still contribute to the spectrum as transient species with a long lifetime.

For CaAr37 the set of connected minima was initially constructed in a rather artificial manner by means of direct pathway searches. As mentioned in the previous section, these initial paths are usually rather long and correspond to high barriers. Therefore the interconversion rates predicted using this database are probably unrealistic and much too low. The discrete path sampling techniquedps  was therefore used to optimize the pathway between the two lowest decahedral and Mackay icosahedral minima. We found pathways containing fewer than seven minima (including the two end points) with a rate constant about eight orders of magnitude larger than that of the initial 45-step pathway. This improvement is even more impressive than the one found for Ar38.dps  However, in CaAr37 the distance between the two minima in question is rather shorter, because they belong to the same funnel.

We did not attempt to optimize the 23 other initial pathways using the discrete path sampling method, since the effect of refining the interconversion pathways is not expected to affect the complex variation with time of the absorption intensity.

## V Conclusions

The complexity of the energy landscapes of CaArn clusters is reflected not only on their equilibrium properties, but also in their relaxation kinetics. By employing the master equation approach, quantum corrected harmonic partition functions and the Gaussian theory of absorption,wp  we have investigated the time-dependence of the photoabsorption intensity. The clusters were chosen to provide a selection of various finite-size effects. Our main result is that spectroscopy may be able to probe the isomerization of a given cluster in real time, and provide estimates of the interconversion rates themselves. We have found evidence that CaArn clusters can display simple kinetics (as in CaAr6 or CaAr10), two-state kinetics and trapping in auxiliary funnels (aAr13), or more intricate kinetics and multiple transient regimes (CaAr37), all with a distinct spectroscopic signature. experiments?

A number of approximations have been used to achieve these results, including the harmonic superposition approximation using incomplete samples of minima for the larger clusters. The master equation approach also contains some assumptions, such as local equilibrium inside each basin and Markovian dynamics. Finally, the Gaussian theory of absorption also contains some approximations. Because of these restrictions, our investigation may be semi-quantitative with respect to actual CaArn clusters, even before we allow for the approximate nature of the Hamiltonians used to model the ground- and excited-state potential energy surfaces.epjd  Nevertheless, the present study provides the next step beyond the analysis of equilibrium properties discussed in our previous paper.paperI  We believe that it further supports the need for future experiments on size-selected, trapped clusters studied via spectroscopic techniques.


text:
# 1 Introduction

## 1 Introduction

The study of the Ly-$`\alpha `$ forest has been revolutionized in recent years by the high resolution measurements using Keck HIRES spectrograph and by the development of theoretical understanding using hydrodynamical simulations and analytical models. The picture that has emerged from these studies is one where the neutral gas responsible for the absorption is in a relatively low density, smooth enviroment, which implies a simple connection between the gas and the underlying dark matter. The neutral fraction of the gas is determined by the interplay between the recombination rate (which depends on the temperature of the gas) and ionization caused by ultraviolet photons, the so called UV background. Photoionization heating and expansion cooling cause the gas density and temperature to be tightly related, except where mild shocks heat up the gas. This leads to a tight relation between the absorption flux and the gas density. Finally, the gas density is closely related to the dark matter density on large scales, while on small scales the effects of thermal broadening and Jeans smoothing have to be included. In the simplest picture described here all of the physics ingedients are known and can be modelled. In practice, the nonlinear physics requires the use of hydrodynamic simulations with sufficient dynamic range which are only now becoming available.

In the past couple of years cosmological observations such as redshift-luminosity relation from supernovae and position of the acoustic peaks in cosmic microwave background (CMB) combined with local matter density estimates have revealed the presence of another component in the universe, the so called dark energy. This component has negative pressure and the recent constraints indicate that $`w=p/\rho 1`$. However, at the moment direct constraints are still allowing for a significant range in $`w`$, specially if it is allowed to vary in time. Many models have been proposed where $`w`$ either increases or decreases with redshift (some of these are discussed in these proceedings). Theoretical studies have been performed on how to extract this evolution using low redshift probes. While statistical power for some of these planned or proposed experiments, such as SNAP using supernovae, LSST using weak lensing or optical, X-ray and Sunyaev-Zeldovich telescopes counting clusters, is truly impressive, the control of systematics is less well understood. For this reason it is important to have as many independent tests as possible.

One possibility that has not been discussed much so far is using Ly-$`\alpha `$ forest as a probe of dark energy. Since direct observations of quasars from the ground restrict one to the optical wavelengths ($`\lambda >3600\AA `$) one can only observe Ly-$`\alpha `$ forest for $`z>2`$. If $`w=1`$ independent of the redshift then if dark energy to dark matter density ratio $`\mathrm{\Omega }_{\mathrm{de}}/\mathrm{\Omega }_m=2`$ today the ratio will be below 0.1 at $`z>2`$. In this case the growth factor will scale almost linearly with the scale factor just as in an Einstein-de Sitter universe and one cannot detect the presence of dark energy. On the other hand, if $`w>1`$ either today or at a somewhat higher redshift then the decline of the dark energy fraction relative to dark matter is slowed down and dark energy can be dynamically important even at $`z>2`$. In this case there will be deviations in the growth factor from the expected scaling that can be detected using the forest observations.

So far the only tests of the dark energy proposed have been using either the growth factor or the redshift luminosity distance. If one wishes to extract $`w(z)`$ then both of these involve a double integral over this quantity and degeneracies arise. A more direct and still in principle observable way is to measure the Hubble parameter $`H(z)`$, which is related to $`w(z)`$ through a single integral. One way to measure it is to have a characteristic feature which is fixed in comoving coordinates and observed in redshift space. The relation between redshift space and comoving space is the Hubble parameter itself and so observing the feature as a function of redshift provides $`H(z)`$ directly. The problem of course is that there are no characteristic features imprinted in large scale structure, since the distribution of structure in the universe is stochastic in nature. One must therefore look for a characteristic scale in correlations between structures. In principle such features could be provided by baryonic oscillations imprinted in the matter power spectrum, but in practice this is a weak effect limited to very large scales and so cannot be made very precise. One is thus left with the variations in the correlation function slope as a function of scale. It is well known that the power spectrum slope varies from $`n1`$ on large scales to $`n3`$ on small scales independent of redshift in CDM models. Hence the scale at which the slope takes a specific value can be viewed as a standard ruler and can be traced with redshift. If this slope is measured in redshift space, as is the case for either galaxy clustering along the line of sight or Ly-$`\alpha `$ forest correlations, then one is measuring directly $`H(z)`$. To be able to do this one has to detect the curvature in the slope over the dynamic range of observations. This is challenging, since the dynamic range is narrow and the error on the slope will be large. We will show below that such a detection should be possible with the current sample, but is not expected to improve the constraints on $`w(z)`$ significantly.

## 2 Error estimation

The basic approach to the error estimation is a standard one. Arranging the statistics one is estimating (in our case power spectrum and bispectrum) into a vector $`𝐱`$ and the parameters one is interested in into vector $`𝐲`$ the Fisher matrix is given by

$$F_{kl}=\left(\frac{\mathrm{d}𝐱}{\mathrm{d}y_k}\right)^T𝖢^1\left(\frac{\mathrm{d}𝐱}{\mathrm{d}y_l}\right),$$
(1)
where $`C_{ij}=(x_ix_i)(x_jx_j)`$.

One must thus compute both the covariance matrix and the derivatives with respect to the parameters on the statistic than one is using. We have found that combining the bispectrum and the power spectrum information significantly improves the determination of the amplitude of fluctuations. The reason for this is a degeneracy between the mean flux absorption and the linear amplitude. Changing the mean flux changes the power spectrum of the flux significantly, as does the variation in the linear amplitude. The mean flux absorption is a free parameter, since it is governed by the amount of UV background that controls the fraction of neutral gas in ionizing equilibrium. While it can be determined directly using independent methods such as continuum fitting or principal component analysis of spectra, the precision of these methods is not sufficient to break the degeneracies entirely. However, at the 3-point function level gravity predicts a very specific pattern of correlations, which cannot be mimicked by the mean flux variation. A full analysis reveals that this can improve the precision of amplitude determination by a factor of 3.

To compute the covariance matrix of power spectrum and bispectrum we use hydro-PM simulations to simulate the forest, apply the analysis on many realizations of the simulations and compute the mean and covariance matrix of the statistics. We use power spectrum and bispectrum information for $`10^3s/km<k<2\times 10^2s/km`$, which is the range of interest for the SDSS data. We then vary by small amount the parameters of interest one at a time, rerun the simulation with the same initial conditions to minimize the sampling variance and recompute the mean. This allows us to compute the derivatives $`dx_i/dy_j`$ of the statistic $`x_i`$ with respect to the parameter $`y_j`$. The parameters we vary are the amplitude of fluctuations as a function of redshift (we use 9 bins between $`2.2<z<3.8`$), mean flux as a function of redshift, slope and curvature of the primoridal spectrum and temperature density relation parametrized as a power law with amplitude and slope as the parameters, both of which can vary with redshift.

The assumed redshift distribution of the sample mimics the SDSS distribution in the current data. We have scaled the length of the forest to match the overall number of quasars to 3000, which is significantly less than the final sample of around 10,000 QSOs. Our results are thus conservative and will be improved significantly in the future, assuming that systematic errors can be kept under control. We assume the spectra have signal to noise of 5 and resolution of 70km/s, which is typical of the SDSS spectra. Neither signal to noise nor resolution are particularly critical in this application, since one is mostly interested in large scale correlations where other parameters such as the temperature of the gas or the density temperature relation do not play a major role.

## 3 Dark energy constraints

To study the dark energy parameters we project the Fisher matrix to fewer parameters, parametrizing the growth factor evolution in terms of $`\mathrm{\Omega }_{\mathrm{de}}`$ and $`w(z)`$. For the redshift evolution we limit ourselves to constant and linear evolution models, $`w_q=w_0+w_1(a1)`$. The density in dark energy and equation of state are degenerate if one only uses information from Ly-$`\alpha `$ forest. This is not surprising, since the redshift range probed is too small to determine two parameters from the growth factor evolution (as mentioned above, we find that $`H(z)`$ information does not provide any additional constraints). In the following we fix $`\mathrm{\Omega }_{\mathrm{de}}`$ and present errors on equation of state only. The motivation for this is that other tests, most notably CMB combined with large scale structure tests (e.g. cluster counts, galaxy clustering, weak lensing), will be able to determine $`\mathrm{\Omega }_{\mathrm{de}}`$ at $`z=0`$ very accurately. If these tests also provide independent constraints on $`w_0`$ then for the time dependent $`w`$ one can use our results to constrain $`w_1`$.

Since the sensitivity to the dark energy depends strongly on the amount of dark energy at $`z>2`$ it is clear that the errors will depend strongly on the assumed values of $`\mathrm{\Omega }_{\mathrm{de}}`$ and $`w(z)`$. For the models studied here their values are given in table 1. The table also shows the errors on $`w_0`$ assuming fixed $`\mathrm{\Omega }_{\mathrm{de}}`$ (and $`w_1`$ in time dependent models) and errors on $`w_1`$ assuming fixed $`\mathrm{\Omega }_{\mathrm{de}}`$ and $`w_0`$. The errors are marginalized over all the other parameters. One can see that the limits improve if $`w_0`$ is more positive or if $`w_1`$ is significantly negative, since the dark energy is then more important at higher redshift. Of particular interest are the limits on time dependent $`w`$. For example, in models 7 and 8 we assume today $`w_0=0.8`$, which increases to $`w=0.4`$ and $`w=0.2`$ at z=2.6, respectively. In such models the error on $`w_1`$ is 0.2, which makes them distinguishable at 1.5$`\sigma `$ with the current sample and 3$`\sigma `$ with the full sample, assuming that both $`\mathrm{\Omega }_{\mathrm{de}}`$ and $`w_0`$ can be accurately determined with the other methods. These errors improve further if we live in a universe with lower matter density than $`\mathrm{\Omega }_m=0.33`$ assumed here.

While there is no simple single parameter combination that describes the sensitivity to dark energy it is clear that the precision is correlated with $`\mathrm{\Omega }_{\mathrm{de}}`$ at $`z=2.6`$. Our results show that if $`\mathrm{\Omega }_{\mathrm{de}}(z=2.6)>0.2`$ then the deviations in the growth factor are sufficiently large to be detected in Ly-$`\alpha `$ forest spectra using the current SDSS sample. With the full SDSS sample this limit can be improved further and models with $`\mathrm{\Omega }_{\mathrm{de}}(z=2.6)>0.1`$ should be detectable. While this is still not sufficiently accurate to measure dark energy directly for cosmological constant model ($`w=1`$) $`\mathrm{\Omega }_m0.3`$, it will provide important constraints on the more general models of dark energy such as the tracker models, where equation of state naturally increases in value at higher redshifts.