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# Feshbach resonance described by the boson fermion coupling

## I Introduction

Superconductivity is a quantum state which appears at sufficiently low temperatures $`TT_c`$ in various systems like e.g. metals (Hg, Pb), alloys (Nb3Sn), copper oxides (La-Sr-Cu-O, Y-Ba-Cu-0), exotic compounds (MgB2, UGe2, ZrZn2), the liquid 3He, etc. Depending on a material, $`T_c`$ can range from 10-3 to more than hundred K and various underlying mechanisms could be responsible for superconductivity (like the phonon or magnetically mediated attraction between electrons, the BE condensation of tightly bound electron pairs, etc). One should add to this list a recently obtained superfluidity in the binary mixtures of the trapped alkali atoms such as: rubidium Rb , potassium K  and lithium Li . Transition temperatures $`T_c100`$ nK became there experimentally accessible due to the “resonance superfluidity”. Atoms of different hyperfine configuration are scattered from each other with a strength depending on the external magnetic field $`B`$ in a following way $`a=a_0\left[1\mathrm{\Delta }B/(BB_{res})\right]`$. Near the resonance $`BB_{res}`$ atoms experience a considerably amplified attractive interaction which gives rise to $`T_c`$’s comparable with the Fermi temperature $`T_F`$.

From the theoretical point of view such controlled way of adjusting the effective interactions between atoms is very appealing. It opens new possibilities to explore for instance such fundamental problems like a crossover from the weak coupling BCS superconductivity to the BE superfluidity of tightly bound atom pairs. On a microscopic level, the resonant type interactions are however rather delicate to treat (for example near the resonance the usual perturbation theory can not be applied). So far, the most reasonable way of describing such interactions was proposed by Timmermans Timmermans  in terms of the boson fermion (BF) model. This idea was recently intensively investigated by the JILA group Kokkelmans  and independently by Griffin and Ohashi Ohashi .

Alkali atoms of different hyperfine configurations are represented within the BF model via fermion fields which are characterized by a two labeled index, e.g. $`\sigma =,`$. These fermions are assumed to interact with a boson field - bosons can be thought of as some bound molecules made of two atoms. According to the theory Timmermans  the resonant type interaction arises when a total energy of two colliding fermions matches the energy of boson state, the so called Feshbach resonance Feshbach .

Using the BF model in the above mentioned context it was shown that transition temperature $`T_c`$ can become extremely high, of the order 0.2 $`T_F`$ for a uniform gas and about 0.5 $`T_F`$ in an isotropic harmonic trap Kokkelmans ; Ohashi . Since the effective pairing potential modulates from weak to strong values the crossover study, along the lines of Nozières and Schmitt-Rink NSR  was carried out Kokkelmans ; Ohashi  clarifying such important issues like the collective modes, etc.

It is worth to recall that the BF model has been known in the solid state physics for almost 20 years Ranninger-85 . It suits very well for studying superconductivity in systems with the arbitrary effective coupling strength. Originally, the model was introduced Ranninger-85  for description of the electron-phonon system in a regime between the adiabatic and antiadiabatic limits. Later on, also the other possible relations were pointed out, e.g. to: the periodic Anderson model Robaszkiewicz-87 , the extended Hubbard model Friedberg-94 , the 2D Hubbard model in its strong interaction limit Auerbach-02 , and the $`tJ`$ model Kochetov-02 . There is a rich literature discussing properties of the superconducting and normal phases described by this model. Many of such properties were experimentally observed in the high temperature superconductors (HTSC) so the BF model is considered as a candidate for their description.

Since it becomes very popular also for description of the trapped alkali atoms, we want to check in this short report if a resonant type scattering is really possible to be generated within the BF model. We shall prove that indeed, the boson fermion interaction may give rise to the effective resonant type scattering between fermions. This result is obtained by us via: 1) the standard canonical transformation and 2) using a continuous canonical transformation capable to trace the feedback effects Domanski-01 . Our study thus justifies applicability of the BF model for a description of the Feshbach type interactions Timmermans ; Kokkelmans ; Ohashi .

## II The model

For simplicity we consider here a model of free fermions coupled to the molecular boson field as described by the following Hamiltonian Ranninger-85

$`H^{BF}`$ $`=`$ $`{\displaystyle \underset{𝐤,\sigma }{}}\left(\epsilon _𝐤\mu \right)c_{𝐤\sigma }^{}c_{𝐤\sigma }+{\displaystyle \underset{𝐪}{}}\left(E_𝐪2\mu \right)b_𝐪^{}b_𝐪`$ (1)
$`+`$ $`v{\displaystyle \underset{𝐤,𝐪}{}}\left(b_𝐪^{}c_{𝐤+𝐪}c_𝐤+\text{h.c.}\right).`$
neglecting the fermion fermion interactions which eventually would be responsible for the background scattering Timmermans ; Kokkelmans ; Ohashi . We use the second quantization operators $`c_{𝐤\sigma }^{}`$, $`c_{𝐤\sigma }`$ for the fermion state of energy $`\epsilon _𝐤`$ which can exist in two possible hyperfine configurations symbolically denoted by $`\sigma =,`$ and $`b_𝐪^{}`$, $`b_𝐪`$ for the molecular boson state of energy $`E_𝐪`$. Fermion and boson subsystems are coupled through the isotropic interaction $`v`$ (in the context of HTSC, it should be anisotropic Micnas-01 ). Since a pair of fermions can “dissociate” into the boson state it implies that bosons are carrying the double fermions’ charge. In order to satisfy the charge conservation we introduce the common chemical potential $`\mu `$ and work in the grand canonical ensemble.

It is worthwhile to comment that within the BF model the mechanism of superconductivity is unconventional Ranninger-85 ; Robaszkiewicz-87 ; Friedberg-89 ; Ranninger-95 . Due to interaction $`v`$ bosons acquire a well established effective mass $`m_B^10`$, even if at the outset they are immobile ($`E_𝐪=\mathrm{\Delta }_B`$). At a critical temperature $`T_{BE}^B`$ bosons undergo the BE condensation and simultaneously this triggers a superconducting ordering of the fermion subsystem $`T_{sc}^F=T_{BE}^BT_c`$ Kostyrko-96 ; Domanski-01 .

Let us point out some of the unusual properties predicted theoretically on a basis of this BF scenario which are relevant for the HTSC materials but could possibly manifest somehow also in the mixtures of the trapped alkali atoms. As far as superconducting phase is concerned: ($`i`$) critical temperatures $`T_c`$ is known to become extremely high because the effective pairing potential \[on a level of the mean field theory estimated to be $`|V(T)|=\frac{v^2}{\mathrm{\Delta }_B2\mu }\mathrm{tanh}\left(\frac{\mathrm{\Delta }_B2\mu }{2k_BT}\right)`$ Robaszkiewicz-87 \] is very large in the, so called, mixed regime of coexisting fermion and boson particles Ranninger-85 ; Robaszkiewicz-87  which occurs when $`\mu \mathrm{\Delta }_B/2`$); ($`ii`$) in the mixed regime, high values of $`T_c`$ are accompanied by the non-BCS ratio $`\mathrm{\Delta }_{sc}(0)/k_BT_c>4`$ Robaszkiewicz-87 ; Ranninger-95 ; ($`iii`$) the upper critical field $`H_{c2}(T)`$ has a characteristic upward curvature $`d^2H_{c2}(T_c)/dT^2>0`$ Hc2\_03 . In the normal phase above $`T_c`$ it was shown that: ($`i`$) $`dc`$ resistivity is linear with respect to $`T`$ up to very high temperatures Eliashberg-87 , ($`ii`$) depending on a doping level and on temperature there is a change of sign of the Hall constant Geshkenbein-97 , ($`iii`$) in a temperature regime $`T^{}>T>T_c`$ the pseudogap (partial depletion of the fermion density of states) builds up near the Fermi energy perturbative ; DMFT ; Domanski-01 , ($`iv`$) the single particle spectrum reveals a clear particle-hole asymmetry Auerbach-02 ; Geshkenbein-97 ; Domanski-03 .

## III The single step transformation

For studying effective physics of the BF model it is convenient first to apply the standard canonical transformation. We treat the boson fermion interaction as a perturbation $`H_{pert}=v_{𝐤,𝐪}\left(b_𝐪^{}c_{𝐤+𝐪}c_𝐤+\text{h.c.}\right)`$ and try to eliminate it from (1) via the unitary transformation $`e^S`$. Choosing

$`S`$ $`=`$ $`{\displaystyle \underset{𝐤,𝐪}{}}\left({\displaystyle \frac{vb_𝐪^{}c_{𝐤+𝐪}c_𝐤}{E_𝐪\epsilon _𝐤\epsilon _{𝐤+𝐪}}}\text{h.c.}\right),`$ (2)
such that $`H_{pert}+[S,H_0]=0`$, we obtain the transformed Hamiltonian $`\stackrel{~}{H}e^SHe^S`$ as

$`\stackrel{~}{H}`$ $`=`$ $`{\displaystyle \underset{𝐤,\sigma }{}}\left(\stackrel{~}{\epsilon }_𝐤\mu \right)c_{𝐤\sigma }^{}c_{𝐤\sigma }+{\displaystyle \underset{𝐪}{}}\left(\stackrel{~}{E}_𝐪2\mu \right)b_𝐪^{}b_𝐪`$ (3)
$`+`$ $`{\displaystyle \underset{𝐤,𝐩,𝐪}{}}U_{𝐤,𝐩,𝐪}c_𝐤^{}c_𝐩^{}c_𝐪c_{𝐤+𝐩𝐪}+o(v^3),`$
where $`o(v^3)`$ stands for other terms of the order $`v^3`$. The renormalized quantities $`\stackrel{~}{\epsilon }_𝐤`$, $`\stackrel{~}{E}_𝐤`$ and $`U_{𝐤,𝐩,𝐪}`$ present in (3) are given by

$`\stackrel{~}{\epsilon }_𝐤`$ $`=`$ $`\epsilon _𝐤+v^2{\displaystyle \underset{𝐪}{}}{\displaystyle \frac{f_{BE}(E_𝐪)}{\epsilon _𝐤+\epsilon _{𝐤+𝐪}E_𝐪}}`$ (4)
$`\stackrel{~}{E}_𝐪`$ $`=`$ $`E_𝐪v^2{\displaystyle \underset{𝐤}{}}{\displaystyle \frac{1f_{FD}(\epsilon _𝐤)f_{FD}(\epsilon _{𝐤+𝐪})}{\epsilon _𝐤+\epsilon _{𝐤+𝐪}E_𝐪}}`$ (5)
$`U_{𝐤,𝐩,𝐪}`$ $`=`$ $`\left[{\displaystyle \frac{v^2/2}{\epsilon _𝐤+\epsilon _𝐩E_{𝐤+𝐩}}}+{\displaystyle \frac{v^2/2}{\epsilon _𝐪+\epsilon _{𝐤+𝐩𝐪}E_{𝐤+𝐩}}}\right]`$ (6)
with $`f_{BE}`$, $`f_{FD}`$ denoting the Bose-Einstein and Fermi-Dirac distributions respectively. In the $`𝐪=𝐩`$ channel thus induced interaction between fermions of different $`\sigma `$ simplifies to

$`{\displaystyle \frac{v^2}{\epsilon _𝐤+\epsilon _𝐩E_{𝐤+𝐩}}}c_𝐤^{}c_𝐤c_𝐩^{}c_𝐩`$ (7)
which explicitly exhibits a divergence. We notice that a scattering potential has a resonant type character when total energy of two colliding fermions is equal to the energy of boson field (Feshbach resonance Feshbach ).

One may argue that validity of canonical transformation is limited only to such states which are far from the resonance because otherwise the operator (2) is ill defined. Our conclusion about the resonant scattering strength (7) may then seem questionable. However, in the next section we shall prove that such resonance is not an artifact, it indeed exists although somewhat smeared.

## IV Continuous canonical transformation

Instead of a single step transformation we will now disentangle the fermion from boson subsystems applying a sequence of infinitesimal transformations. The main idea behind is to proceed with a continuous canonical transformation $`S(l)`$ (where $`l`$ denotes some formal flow parameter which can vary between 0 and any other value) until a given structure of the Hamiltonian $`H(l)=e^{S(l)}He^{S(l)}`$ is obtained. A virtue of this method is that one can freely manipulate with $`S(l)`$ in order to get a constrained structure of $`H(l)`$.

In this work we follow the algorithm outlined by Wegner Wegner-94  for constructing the generating operator $`\eta (l)dS(l)/dl`$ of the continuous transformation. An arbitrary Hamiltonian $`H(l)=H_0(l)+H_{pert}(l)`$ can be reduced to a semidiagonal structure by choosing $`\eta (l)=[H_0(l),H_{pert}(l)]`$ which assures that $`lim_l\mathrm{}H_{pert}(l)=0`$. During the transformation $`H_0(l)`$ part does evolve too, its $`l`$-dependent parameters have to be deduced from the general flow equation $`dH(l)/dl=[\eta (l),H(l)]`$ Wegner-94 . In practice, this flow equation can never be identically satisfied because the higher and higher order interactions (not present in $`H_0`$) are generated from the commutator. Flow equation is often approximated by truncating the higher order interactions in a spirit of the perturbation theory, however the nonperturbative methods are in principle possible too Kehrein-99 .

In the previous work Domanski-01  we have already formulated the continuous canonical transformation for the BF model. The corresponding flow equations (16-21) of Ref. Domanski-01  were derived within a perturbational estimation up to order $`v^3`$. In this short report we want to study in some more detail the resonant-type interactions induced between fermions in the effective Hamiltonian $`\stackrel{~}{H}=H(l\mathrm{})`$.

In a course of transformation the interactions between fermions evolve from zero, at $`l=0`$, to some effective value $`\stackrel{~}{U}_{𝐤,𝐩,𝐪}`$ at $`l=\mathrm{}`$ when boson and fermion subsystems are finally decoupled from each other. Flow of the potential is governed by the equation Domanski-01

$`{\displaystyle \frac{dU_{𝐤,𝐩,𝐪}(l)}{dl}}=\left[\alpha _{𝐤,𝐩}(l)+\alpha _{𝐪,𝐤+𝐩𝐪}(l)\right]v_{𝐤,𝐩}(l)v_{𝐪,𝐤+𝐩𝐪}(l)`$
(8)
where $`\alpha _{𝐤,𝐩}(l)=\epsilon _𝐤(l)+\epsilon _𝐩(l)E_{𝐤+𝐩}(l)`$ and the introduced momentum dependence of the boson-fermion coupling $`v_{𝐤,𝐩}(l)b_𝐪^{}c_{𝐤+𝐪}c_𝐤`$ arises from $`dH/dl`$. Equation (8) is convoluted with the following ones Domanski-01

$`{\displaystyle \frac{dv_{𝐤,𝐩}(l)}{dl}}`$ $`=`$ $`\alpha _{𝐤,𝐩}^2(l)v_{𝐤,𝐩}(l),`$ (9)
$`{\displaystyle \frac{d\epsilon _𝐤(l)}{dl}}`$ $`=`$ $`2{\displaystyle \underset{𝐩}{}}\alpha _{𝐤,𝐩}(l)v_{𝐤,𝐩}^2(l)f_{BE}(E_{𝐤+𝐩}(l)),`$ (10)
$`{\displaystyle \frac{dE_𝐪(l)}{dl}}`$ $`=`$ $`2{\displaystyle \underset{𝐤}{}}\alpha _{𝐪𝐤,𝐤}(l)v_{𝐪𝐤,𝐤}^2(l)`$ (11)
$`\times \left[12f_{FD}(\epsilon _{𝐤𝐪}(l))\right].`$
These four $`l`$-dependent quantities $`v_{𝐤,𝐩}(l)`$, $`\epsilon _𝐤(l)`$, $`E_𝐪(l)`$, $`U_{𝐤,𝐩,𝐪}(l)`$ should be determined simultaneously. Mathematically it is a tremendous task, nevertheless we shall estimate $`\stackrel{~}{U}`$ either in an approximate way or numerically and, in one special case, exactly.

### IV.1 Exact solution at $`T<T_c`$

Some exact statements can be done for the superconducting/superfluid phase of the BF model. For temperatures $`T`$ smaller than a critical $`T_c`$ there exists a finite fraction of condensed bosons $`n_0^B=b_𝐪^{}b_𝐪_{𝐪=\mathrm{𝟎}}`$ and chemical potential is then located at the lowest boson energy $`\mu (T)=E_\mathrm{𝟎}/2`$. The flow equation (10) $`d\epsilon _𝐤(l)/dl4\xi _𝐤(l)n_0^Bv_{𝐤,𝐤}^2(l)`$ combined with (9) $`dv_{𝐤,𝐤}(l)/dl=4\xi _𝐤^2(l)v_{𝐤,𝐤}(l)`$ lead to the following invariance $`\xi _𝐤(l)^2+v_{𝐤,𝐤}^2(l)=const`$, where $`\xi _𝐤\epsilon _𝐤(l)\mu `$. In consequence, for the $`l\mathrm{}`$ limit, we obtain the effective Bogolubov type spectrum $`|\xi _𝐤(\mathrm{})|=\sqrt{\xi _𝐤^2+n_0^Bv^2}`$ \[see Eqn. (52) of the Ref. Domanski-01 \].

Using the flow equation (8) we find that, in the $`𝐩=𝐪=𝐤`$ channel, potential $`U_{𝐤,𝐩,𝐪}(l)`$ is given by

$`{\displaystyle \frac{dU_{𝐤,𝐤,𝐤}(l)}{dl}}=4\xi _𝐤(l)v_{𝐤,𝐤}^2(l)={\displaystyle \frac{1}{2\xi _𝐤(l)}}{\displaystyle \frac{dv_{𝐤,𝐤}^2(l)}{dl}}`$ (12)
due to $`dv_{𝐤,𝐤}^2(l)/dl=8\xi _𝐤^2(l)v_{𝐤,𝐤}^2(l)`$. After integration by parts we get from (12)

$`\xi _𝐤(l)U_{𝐤,𝐤,𝐤}(l)|_0^{\mathrm{}}{\displaystyle _0^{\mathrm{}}}{\displaystyle \frac{d\xi _𝐤(l)}{dl}}U_{𝐤,𝐤,𝐤}(l)={\displaystyle \frac{v^2}{2}}`$ (13)
because $`v_{𝐤,𝐤}(\mathrm{})=0`$. Since according to (10) we have $`d\xi _𝐤/dlv^2`$ and from our previous estimation Domanski-01  also $`U_{𝐤,𝐩,𝐪}v^2`$ we finally conclude

$`U_{𝐤,𝐤,𝐤}(\mathrm{})={\displaystyle \frac{v^2+o(v^4)}{2\text{sign}\left(\xi _𝐤\right)\sqrt{\xi _𝐤^2+n_0^Bv^2}}}.`$ (14)
This equation shows that two colliding electrons with total energy $`\epsilon _𝐤+\epsilon _𝐤=E_{𝐪=\mathrm{𝟎}}`$ have a resonant-like scattering strength (remember that in this case $`E_\mathrm{𝟎}=2\mu `$ and due to symmetry $`\epsilon _𝐤=\epsilon _𝐤`$). Amplitude of the resonance is now finite and is controlled by the superconducting gap $`\mathrm{\Delta }_{sc}(T)=v\sqrt{n_0^B(T)}`$.

### IV.2 Approximate solution for $`TT_c`$

Effective interaction between fermions can be calculated approximately, for instance iteratively. In the first step we can neglect $`l`$-dependence of $`\alpha _{𝐤,𝐩}(l)`$ in the flow equations (8) and (9) because fermion $`\epsilon _𝐤(l)\epsilon _𝐤`$ and boson energies $`E_𝐪(l)E_𝐪`$ are rather weakly renormalized during the transformation Domanski-01 .

With an approximation $`\alpha _{𝐤,𝐩}(l)\alpha _{𝐤,𝐩}(l=0)`$ we can easily obtain $`v_{𝐤,𝐩}(l)=v\text{exp}[\left(\epsilon _𝐤+\epsilon _𝐩E_{𝐤+𝐩}\right)^2l]`$. When further substituted to equation (8) we get the following asymptotic value $`U_{𝐤,𝐩,𝐪}(l\mathrm{})`$

$`{\displaystyle \frac{v^2\left(\epsilon _𝐤+\epsilon _𝐩+\epsilon _𝐪+\epsilon _{𝐤+𝐩𝐪}2E_{𝐤+𝐩}\right)}{\left(\epsilon _𝐤+\epsilon _𝐩E_{𝐤+𝐩}\right)^2+\left(\epsilon _𝐪+\epsilon _{𝐤+𝐩𝐪}E_{𝐤+𝐩}\right)^2}}`$ (15)
which is less divergent than (6). However, in the $`𝐪=𝐩`$ channel it again reduces to the resonant type potential given in (7). Divergence at $`\epsilon _𝐤+\epsilon _𝐩=E_{𝐤+𝐩}`$ occurs here because the flow equations (8\- 11) were not investigated fully selfconsistently.

In order to check, whether a selfconsistent treatment does not lead to any divergence we solved equations (8-11) numerically by the Runge Kutta method. At the starting point $`l=0`$, we used the parabolic dispersions $`\epsilon _𝐤=(\mathrm{}𝐤)^2/2m_e`$, $`E_𝐪=\mathrm{\Delta }_B+(\mathrm{}𝐪)^2/2m_b`$ and introduced the ultraviolet cutoff $`\mathrm{\Lambda }\mu (T)`$.

We obtained the effective potential $`U_{𝐤,𝐩,𝐪}(l\mathrm{})`$ for several temperatures $`T`$ using a fixed total charge concentration $`_{𝐤\sigma }c_{𝐤\sigma }^{}c_{𝐤\sigma }+2_𝐪b_𝐪^{}b_𝐪=const`$. Temperature had rather a negligible influence on a magnitude of the fermion fermion interaction for $`T>T_c`$. Using a given $`\mathrm{\Delta }_B`$ value we adjusted the total charge concentration so, that number of bosons $`N_B=_𝐪f_{BE}(E_𝐪)`$ and fermions $`N_F=_𝐤f_{FD}(\epsilon _𝐤)`$ were comparable. Chemical potential was located very close to the bottom of boson states $`\mu (T)\mathrm{\Delta }_B/2`$. Figure 1 illustrates the behavior of $`U_{𝐤,𝐩,𝐩}(\mathrm{})`$. Again, we notice an appearance of the resonant type interaction for $`\epsilon _𝐤+\epsilon _𝐩=\mathrm{\Delta }_B`$ but, in distinction from (7), amplitude of the resonance is finite.

## V Conclusions

In summary, we analyzed the resonant type interactions between fermions (experimentally achievable for example in the binary mixtures of 85Rb Rb , 40K K  or 6Li atoms Li  in a presence of the magnetic field) using the microscopic boson fermion (BF) model. Within the BF scenario, fermions are coupled to the boson field (the long lived molecules composed of two atoms). This coupling is responsible for the many body effects and, in particular at $`T_c`$ it drives a system to the superconducting/superfluid ordering Ranninger-85 . When approaching the critical temperature from above, several precursor features can be observed which show that the pairing and the long range pair coherence may occur in this model at different temperatures $`T^{}`$ and $`T_cT^{}`$, respectively.

We determined the effective fermion fermion interaction induced by elimination of the boson fermion coupling via the canonical transformation. Boson and fermion subsystems were disentangled (i) by the single step transformation, and (ii) through a continuous sequence of transformations taking account of the feedback effects Domanski-01 . In both methods we obtained the effective resonant type interactions between fermions. At temperatures $`T>T_c`$ the resonance appeared to be more sharp (although of finite amplitude), while for $`T<T_c`$ its amplitude reduced to a magnitude of the superconducting gap.

The resonant scattering seems to be a robust feature of the mixed boson-fermion system. It has an impact on several physical properties, for instance, it is responsible for the particle-hole asymmetric spectrum Domanski-03 . Other aspect which is important in a context of the soft matter physics is that the microscopic BF model can serve as a convenient tool for description of the resonant type interactions $`a=a_0\left[1\mathrm{\Delta }B/(BB_{res})\right]`$ Timmermans ; Kokkelmans ; Ohashi . Many body effects can there be studied in a secure way (though still far from trivial) without a necessity to deal with any divergences.

Author kindly acknowledges valuable discussions with Profs J. Ranninger, F. Wegner and K.I. Wysokiński.


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# Time-resolved spectra of polar-polarizable chromophores in solution

## I Introduction

Time-resolved spectroscopy is a powerful tool to investigate solvent dynamics simon ; fleming , one of the central issues in modern chemical physics, and a key to understand the rate of chemical reactions in solution rossky ; heitele . Detailed information on solvent dynamics can in fact be obtained from time-resolved spectra of properly chosen probe molecules in solution. Good solvation probes have strongly solvatochromic and intense absorption (and/or emission) bands in the visible region reichardt , as not to interfere with transitions in the ultraviolet region. Polyconjugated chromophores with good electron-donor (D) and acceptor (A) groups (also called push-pull chromophores) work fine in this respect: intense and low-lying transitions are guaranteed by polyconjugation, and the large charge displacement from D to A (or viceversa) driven by the transition is responsible for a large variation of the dipole moment upon excitation, that makes the frequency of the transition largely dependent on the polarity of the surrounding medium.

In the simplest model for solvation, the solvent is described as a dielectric continuum medium hosting solute molecules into Onsager-type cavities liptay . The electric dipole moment of the (polar) solute polarizes the solvent so that the solute itself experiences an electric field, the reaction field, proportional to the solute dipole moment via a proportionality constant that depends on the macroscopic properties of the solvent, and on the shape and size of the Onsager cavity. Two contributions to the reaction field can be distinguished dibella ; chandler . The electronic clouds of solvent molecules surrounding the solute deformate in response to the solute dipole moment. The resulting electronic polarization is very fast with respect to the relevant degrees of freedom of the solute. As a consequence, the dynamics of the electronic polarization is irrelevant to our discussion chemphys . The second contribution to the reaction field originates from the reorientation of the (polar) solvent molecules around the solute. This contribution, that of course vanishes in non-polar solvents, is slower than the solute degrees of freedom liptay ; dibella . It is responsible for the large solvatochromic behavior of push-pull chromophores reichardt  and dominates the temporal evolution of observed spectra in time-resolved experiments simon .

In a typical time-resolved experiment the system is shot by a pulse, or a series of pulses, that induces a transition between the ground and the excited state (or viceversa). During this process the solvent molecules have not time to reorient in response to the sudden change of the solute dipole moment, and an out of equilibrium (orientational) polarization is generated. Provided the state generated by impulsive excitation lives long enough, the orientational contribution to the reaction field ($`F_{or}`$) slowly evolves from its initial value (i.e. that equilibrated with the solute dipole moment before excitation), towards the equilibrium value for the state reached upon excitation. Within linear perturbation theory, the energy of the states involved in the transition is linearly affected by the reaction field, and the frequency of the relevant transition acquires a linear dependence on the reaction field: $`\mathrm{}\omega (F_{or})=\mathrm{}\omega (F_{or}=0)F_{or}(\mu _E\mu _G)`$, where $`\mu _{G(E)}`$ is the electric dipole moment of the ground (excited) state liptay . Then, the experimentally accessible temporal evolution of the transition frequency, $`\omega (t)`$, gives direct information on the temporal evolution of the orientational solvent polarization.

The continuum dielectric model reduces the highly irregular and complex motion of the solvent molecules to the motion of a single effective solvation coordinate, the reaction field loring . The dynamical behavior of this special coordinate is subject to large frictional random forces, that guarantee for an energy dissipation mechanism heitele . In the hypothesis of large friction (overdamped motion) the resulting dynamics is very simple. The solvation correlation function (also called the spectral correlation function),

$$C(t)=\frac{\omega (t)\omega (\mathrm{})}{\omega (0)\omega (\mathrm{})}$$
(1)
has in this hypothesis a simple exponential form, and the corresponding relaxation time, $`\tau _S`$, coincides with the longitudinal relaxation time, $`\tau _L`$, of the pure solvent simon . Deviations from this simple behavior are expected in the case of low-friction or when the translational motion of solvent molecules dominates over orientational motion simon ; zwan .

Extensive experimental work has been devoted by several groups to collect time-resolved spectra of polar chromophores in solution lds750b ; maroncelli2 ; rosenthal ; jarzeba ; maroncelli1 ; dcm2 ; dcm1 ; dcm ; lds750 ; c153 ; ernsting ; blanchard . The interpretation of experimental data proved more difficult than described in the simple picture summarized above. First of all a finite contribution to the Stokes shift ($`\omega (0)\omega (\mathrm{})`$) is given by the vibrational degrees of freedom of the solute molecule, as demonstrated most clearly by the observation of finite Stokes shifts for chromophores dissolved in non-polar solvents. Internal vibrational coordinates are in fact slower than electronic degrees of freedom, and hence contribute to the Stokes shift. However, thanks to the different timescales of vibrational and solvation motions, their contributions to the temporal evolution of spectra can be at least approximately separated maroncelli1 . The basic idea is that, after impulsive excitation, vibrational degrees of freedom relax almost instantaneously with respect to solvation time-scales, so that vibrational relaxation is essentially done before solvent relaxation starts. Accordingly, the zero-time frequency, $`\omega (0)`$, to be inserted into Eq. (1), is not the true zero-time frequency, i.e. that relevant to the unrelaxed (vertical) system, but represents the frequency measured at an effective zero-time for the solvation motion, i.e. the hypothetical time when vibrational coordinates are fully relaxed, but the solvent is still frozen in its vertical configuration. This effective $`t=0`$ time, first introduced by Maroncelli and coworkers in the analysis of time-resolved fluorescence spectra fee , has no experimental counterpart, and $`\omega (0)`$ cannot be measured directly. Maroncelli proposed a clever approach to extract $`\omega (0)`$ from experimental steady-state spectra collected in polar and apolar solvents fee . The procedure unavoidably introduces uncertainties in the estimated $`\omega (0)`$ that add to the uncertainties in the frequencies estimated from the broad and asymmetric fluorescence bands maroncelli2 . Precise estimates of $`C(t)`$ are therefore difficult. On a more fundamental vein, the simplest solvation model outlined above, and, a fortiori, the approach suggested by Maroncelli, both rely on the hypothesis of instantaneous vibrational relaxation and on the hypothesis of an ideal solvation probe: i.e. of a molecule whose spectral properties are largely affected by the surrounding medium, but whose presence does not affect the solvent dynamics. The assumption of a complete separation of vibrational and solvation time-scales is expected to work well unless one is interested in the very early times of solvation (the first few tens of femtoseconds). Deviations can be predicted for molecules with very slow (conformational) degrees of freedom, particularly if solvents with very fast relaxation dynamics are considered. The assumption of the solvent response being unaffected by the perturbing solute is only valid in the linear regime for the solute-solvent perturbation. But linear approaches are inadequate to treat solvation of push-pull chromophores. Just in view of the strong absorption in the visible region, in fact, push-pull chromophores have large polarizabilities (and hyperpolarizabilities): the reaction field then not only affects the solute energy, but also its dipole moment. The dipole moment in turn affects the reaction field in a feed-back mechanism that is responsible for large non-linearity.

In recent years we have developed a simple yet powerful method to describe steady-state electronic and vibrational spectra of polar chromophores in solution cpl ; sm1 ; jpc1 ; baba . The solute is described in terms of two electronic states linearly coupled to internal vibrations (Holstein coupling) and to the reaction field chemphys . This model allows for non-perturbative solutions and naturally describes several features of experimental spectra that were not understood in standard linear approaches. The reliability of the model is proved by extensive comparison with steady-state electronic and vibrational spectra collected for several chromophores in different solvents baba ; jpc2 ; sm2 . In this paper we extend the model to describe time-resolved spectra. In particular we show that accurate time-resolved spectra of polar-polarizable chromophores can be calculated adopting the same set of parameters used for steady-state spectra without the need to introduce additional adjustable parameters. Working in the hypothesis of a complete separation of solvation and vibrational dynamics, the model accounts for deviations of $`C(t)`$ from the simple exponential form, and rationalizes the observation of time-dependent band-shapes and the appearance of temporary isosbestic points (TIPs). These characteristic features of time-resolved spectra of polar-polarizable chromophores dcm ; lds750 ; c153 ; ernsting ; blanchard , are a direct consequence of the solute (hyper)polarizability, and cannot be rationalized within the standard linear picture for solvation outlined above. As a matter of fact these features have often been taken as evidences of the failure of the continuum solvation model maroncelli2 ; rosenthal ; jarzeba  or for the failure of the two-state description of the chromophore blanchard . We demonstrate instead that they can appear as natural consequences of the molecular polarizability and can be described within the simplest model for solvation, provided the fundamental interactions of electronic degrees of freedom with molecular vibrations and with the solvent reaction field are treated beyond linear perturbative approaches.

## II The model

We consider two electronic states linearly coupled to molecular vibrations and to solvent degrees of freedom, according to the following Hamiltonian chemphys :

$``$ $`=`$ $`2z_0\widehat{\rho }t{\displaystyle \underset{\sigma }{}}\left(a_{D,\sigma }^{}a_{A,\sigma }+a_{A,\sigma }^{}a_{D,\sigma }\right)`$ (2)
$`+`$ $`{\displaystyle \underset{i}{}}\left[{\displaystyle \frac{1}{2}}(P_i^2+\omega _i^2Q_i^2)\sqrt{2ϵ_i}\omega _iQ_i\widehat{\rho }\right]`$
where the first two terms describe the electronic problem, with $`\widehat{\rho }=_\sigma a_{A,\sigma }^{}a_{A,\sigma }`$ counting electrons on A site, and $`a_{A,\sigma }^{}`$, $`a_{D,\sigma }^{}`$ creating an electron with spin $`\sigma `$ on D and A site, respectively. $`Q_i`$ and $`P_i`$, with $`i>0`$, are the coordinates and conjugated momenta describing the coupled vibrations of the chromophore, and $`Q_0`$ is the effective solvation coordinate. All coordinates are harmonic, with frequency $`\omega _i`$; the relevant relaxation energy is $`ϵ_i`$. In the following we explicitly account for a single coupled vibration, $`Q_1`$. This simplifies equations and limits the number of adjustable parameters in the model, with no major loss of accuracy in the calculation of electronic spectra baba . The extension to the multimode case is possible, and interesting effects of the mixing among different vibrational coordinates are indeed expected in vibrational spectra jpc1 ; sm2 .

In the adiabatic approximation, the Hamiltonian in Eq. (2) can be diagonalized at fixed $`Q_i`$’s on the basis of $`|DA`$ and $`|D^+A^{}`$ states chemphys ; cpl98 . The resulting ground and excited states are fully defined in terms of a single $`Q_i`$-dependent parameter, $`\rho =G|\widehat{\rho }|G`$, as follows:

$`|G`$ $`=`$ $`\sqrt{1\rho }|DA+\sqrt{\rho }|D^+A^{}`$
$`|E`$ $`=`$ $`\sqrt{\rho }|DA+\sqrt{1\rho }|D^+A^{}`$ (3)
The corresponding energies define the multidimensional ground and excited state potential energy surfaces (PES), as shown in Fig. 1a. The calculated PES are interesting in several respects. All coordinates inserted into the Hamiltonian are harmonic, and no term appears into Eq. (2) explicitly accounting for the mixing of different coordinates. The PES in Fig. 1 are instead clearly anharmonic and indicate a large mixing between the two involved coordinates. The softening of the ground state PES, and the hardening of the excited state PES are also recognized. All these effects are due to the coupling of the $`Q_i`$’s to the electronic system jpc1 . In particular we underline that the coupling between vibrational and solvation coordinates stems out naturally from their common coupling to the electronic system.

The PES in Fig. 1 represent the potential for the motion of slow coordinates, $`Q_i`$’s. Internal vibrations with typical frequencies in the mid-infrared region, are true quantum-mechanical objects. The relevant anharmonic problem defined by the PES in Fig. 1 has been solved numerically, and large effects of the anharmonicity of internal vibrational modes have been demonstrated in static hyperpolarizabilities cplfreo ; jcp . On the contrary, vertical processes, like, e.g., absorption and emission are hardly affected by anharmonicity cplfreo ; tpa ; under . In particular, vertical processes are quite accurately described by replacing the two anharmonic PES by the two parabolas that best fit the ground and excited state PES in the relevant region of the $`Q`$ space (best harmonic approximation cplfreo ; jcp ; tpa ). Of course the role of anharmonicity can be recognized in the variation of the effective harmonic parameters fitting absorption and emission processes in this local-harmonic approximation.

Within the local harmonic approximation, electronic spectra and their variation in the $`Q`$-space are fully defined in terms of $`\rho `$. The vertical transition frequency and the transition dipole moment are cpl ; jpc1 :

$`\mathrm{}\omega _{CT}`$ $`=`$ $`{\displaystyle \frac{\sqrt{2}t}{\sqrt{\rho (1\rho )}}}`$
$`\mu _{CT}`$ $`=`$ $`\mu _0\sqrt{\rho (1\rho )}`$ (4)
where $`\mu _0`$ is the dipole moment of $`|D^+A^{}`$. The Huang-Rhys (HR) factor for the coupled vibrational coordinate ($`Q_1`$) is cpl ; jpc1 :

$$\lambda _1=\frac{ϵ_1}{\mathrm{}\omega _1}(12\rho )^2$$
(5)
Based on Eqs. (4) and (5), absorption and emission spectra at any specified position in the $`Q`$ space are calculated as baba :

$$𝒮(\omega )\omega ^M|\mu _{CT}|^2\underset{n}{}\frac{\lambda _1^2}{\sqrt{n!}}I(\omega \omega _n)$$
(6)
where $`\omega _n`$ is the frequency of the $`n`$-th vibronic line, and $`I(\omega )`$ is the intrinsic line-shape function that we choose as a Gaussian with standard deviation $`\sigma `$. $`M=1,3`$ for absorption and emission, respectively.

The solvation coordinate describes the slow orientational motion of polar solvent molecules around the polar solute. The relevant coordinate, $`Q_0`$, can then be treated as a classical coordinate, and, at finite temperature, it is responsible for inhomogeneous broadening. Since the solvation motion is coupled to electronic degrees of freedom, and, through them, to internal vibrations, inhomogeneous broadening has in these systems quite peculiar features. Due to thermal disorder in fact, the solution can be thought of as a collection of chromophores each one surrounded by a slightly different $`Q_0`$ configuration. Both electronic and vibrational motions are very fast if compared to solvation, so that each solute molecule readjusts instantaneously its polarity and its geometry in response to the local $`Q_0`$ configuration jpc1 . Thermal disorder in $`Q_0`$ is then responsible for disorder in electronic and vibrational properties, that shows up in electronic and vibrational spectra, and, most apparently, in the anomalous dispersion of resonant Raman frequencies with the excitation line jpc1 ; jpc2 . With reference to Fig. 1, the thermally equilibrated state in either the ground or excited state PES is defined in terms of a Boltzmann distribution of states lying along the dashed lines drawn across the isopotential lines in Fig. 1b and 1c to mark the local minimum path with respect to the vibrational coordinate. The steady-state absorption and emission spectra are then sums of the contributions in Eq. (6) calculated for each point along the minimum path in the ground state and excited state PES, respectively, and weighted by the relevant Boltzmann distribution jpc1 ; baba .

This simple model has been applied successfully to describe electronic and vibrational spectra of several chromophores, reproducing many features of experimental spectra that were not understood before baba ; jpc2 ; sm2 . Just as an example, Fig. 2A and 2B shows the absorption and emission spectra calculated in the proposed approach to fit experimental spectra of DCM dissolved in several solvents. These spectra accurately reproduce experimental data baba , and deserve some comment. The red-shift of absorption and emission bands with increasing solvent polarity (positive or normal solvatochromism) is typical of chromophores with a neutral ground state ($`\rho <0.5`$) reichardt . For these chromophores the solute polarity increases upon excitation, and the excited state is stabilized by a polar surrounding medium. The evolution of the band-shape with the solvent polarity is a more subtle phenomenon that can be understood only if the polarizability of the solute is accounted for jpc1 ; baba . In fact, the polarity of the (polarizable) solute increases with the polarity of the surrounding medium. For neutral chromophores then $`\rho `$ increases towards 0.5, and HR factors decrease: even if inhomogeneous broadening increases with the solvent polarity, absorption and emission bands apparently narrows, since the underlying vibronic profile narrows ($`\lambda _1`$ decreases, see Eq. (5)). For zwitterionic chromophores ($`\rho >0.5`$), instead, the ionicity increases towards 1, and HR factors increase with the solvent polarity: in this case the effects of solvent polarity on inhomogeneous broadening and HR factors sum up to widen absorption and emission bands. This behavior is experimentally verified in dyes with inverse solvatochromism lds750 ; metzger ; hr , and is reproduced in Fig. 2C and 2D for a hypothetical dye with the same molecular parameters as DCM, but a different $`z_0`$, as to have a zwitterionic ground state.

Another direct consequence of the molecular polarizability is recognized in the non-specularity of steady-state absorption and emission bands cpl ; baba . The behavior is similar for neutral and zwitterionic chromophores, with narrower emission than absorption bands. In all chromophores, in fact, the mixing between the two basis states increases in the relaxed excited state, so that, in both cases steady-state emission spectra correspond to states with $`\rho `$ nearer to 0.5 than states relevant to absorption spectra. According to Eq. (5), HR factors for emission are always smaller than for absorption then justifying quite naturally the observed narrowing of emission bands.

## III Relaxation dynamics

The success of the two-state model in reproducing steady-state absorption and emission spectra invites modeling time-resolved experiments, as related to the dynamics of non-equilibrium states created by impulsive excitation in either the ground or excited state PES. We are not interested in the fast relaxation of vibrational coordinates (typically accomplished within few tens of femtoseconds after excitation) maroncelli1 ; ernsting , rather we model the slower solvation dynamics in the hundreds of femtoseconds to picosecond temporal window. The problem is therefore greatly simplified if we work in the hypothesis of a complete separation of vibrational and solvation dynamics. First of all, just after a (sequence of) pulse(s) has created an out of equilibrium state in one of the PES, an instantaneous relaxation of vibrational coordinates takes place before solvation relaxation starts maroncelli1 . Moreover, during the subsequent relaxation of solvation degrees of freedom, internal coordinates immediately readjust with respect to the instantaneous configuration of the solvent. Due to the non-linearity of the coupled problem, the electronic wavefunction readjusts following $`Q_0`$ and, as a consequence, the equilibrium geometry of the chromophore varies with $`Q_0`$. Since electronic and vibrational degrees of freedom are much faster than solvation, they are always in equilibrium with the instantaneous configuration of the solvent, and the relaxation of the effective solvation coordinate does not proceeds along a horizontal line (fixed $`Q_1`$) in Fig. 1b or 1c, but follows the dashed lines drawn across the isopotential lines to mark the minimum energy path in each surface.

In a time-resolved fluorescence experiment, an impulsive excitation drives the system from the thermally equilibrated ground state (centered on point G in Fig. 1b) to the vertical excited state (point G’ in Fig. 1c). After excitation, the instantaneous relaxation of vibrational degrees of freedom drives the system to point F, i.e. to the local minimum in the excited state PES, at the $`Q_0`$ relevant to the equilibrium ground state configuration. During the G$``$G’$``$F path, the $`Q_0`$ configuration is unaffected. Once the system has reached point F, solvent relaxation starts. Since vibrational degrees of freedom follow adiabatically the solvent relaxation, the relaxation path towards the minimum of the excited state PES (F$``$E) follows the minimum energy path, i.e. the dashed line drawn across points F and E in Fig. 1c. So, in spite of being driven by orientational degrees of freedom of the solvent, the dynamics of the system occurs along an effective coordinate that describes a concerted motion of solvation degrees of freedom and internal vibrations. Once again, the coupling between the two kinds of motion originates from their common coupling to the electronic system, and is a direct consequence of the molecular polarizability.

Time-resolved fluorescence spectra can be calculated following the same procedure described in the previous section for steady-state spectra, provided the temporal evolution of the $`Q_0`$ probability distribution is known. To such an aim we rely on a Fokker-Planck description of the dynamics of the joint probability distribution in the space of the solvation coordinate and momentum caldeira ; mukamel , $`W(Q_0,P_0)`$, as described by the following equation of motion:

$$\frac{W}{t}=\dot{Q_0}\frac{W}{Q_0}\dot{P_0}\frac{W}{P_0}+\gamma \left\{W+P_0\frac{W}{P_0}+kT\frac{^2W}{P_0^2}\right\}$$
(7)
where $`\gamma `$ is the phenomenological friction coefficient for the motion along the relevant relaxation path. Starting from point F, where the distribution is rigidly translated from the equilibrium ground state distribution, the Fokker-Planck equation can be easily integrated along the F-E path in Fig. 1c. The calculation can be simplified by recognizing the overdamped nature of the solvation coordinate ($`\gamma \omega _0`$). In the overdamped regime, the momentum rapidly attains the equilibrium, so that it needs not to be considered as an independent dynamic variable mukamel . The only relevant dynamics involves the $`Q_0`$-distribution, $`w(Q_0)`$, as described by Smoluchowski equation:

$$\frac{w}{t}=\frac{1}{\gamma }\left[w\frac{^2V}{Q_0^2}+\frac{V}{Q_0}\frac{w}{Q_0}+kT\frac{^2w}{Q_0^2}\right]$$
(8)
where $`V(Q_0)`$ is the (classical) potential for the $`Q_0`$ motion. We verified that for $`\gamma >2\omega _0`$ the Smoluchowski equation leads to the same results as the Fokker-Planck equation. Apart from a simplification in the integration procedure, working in the overdamped limit has the advantage of reducing the number of free parameters required to model solvation dynamics. In fact, as it is well known mukamel  and as we have explicitly verified, in that limit all dynamic properties depend on $`\gamma `$ and $`\omega _0`$ only through the ratio $`\tau =\gamma /\omega _0^2`$. $`\tau `$ represents an effective solvation time, and can be fixed as the longitudinal relaxation time ($`\tau _L`$) of the pure solvent simon .

Fig. 3 shows time-resolved spectra calculated for DCM dissolved in two different solvents (CH<sub>3</sub>CN and CHCl<sub>3</sub>). All molecular parameters, and the solvent relaxation energies as well, are kept fixed at the values previously obtained from the fit of steady-state spectra baba  (cf Fig. 2, left panels). According to literature data, we fix $`\tau =0.3`$ and 2.8 ps for CH<sub>3</sub>CN and CHCl<sub>3</sub>, respectively maroncelli1 . The spectra in Fig. 3 compare nicely with experimental spectra dcm2 ; dcm1 , and accurately reproduce the progressive red-shift of the band, as well as its narrowing. In order to better understand the origin of the evolution of band-shapes during solvation, Fig. 4 shows time-resolved spectra calculated for the same parameters as Fig. 3A, but without accounting for inhomogeneous broadening, i.e. by collapsing the $`w(Q_0)`$ distribution into a $`\delta `$-function. The comparison between inhomogeneously broadened spectra in Fig. 3A and homogeneous spectra in Fig. 4 demonstrates that the evolution of the band-shape accompanying the solvent relaxation is essentially due to the evolution of the vibronic structure (i.e. of HR factors), and reflects quite naturally the evolution of the molecular geometry along the relaxation path. The $`w(Q_0)`$ distribution, obtained from the solution of the Smoluchowski equation, also evolves with time, but it affects calculated spectra in a more subtle way. In fact $`w(Q_0)`$ is responsible for inhomogeneous spectral broadening, whose temporal evolution is hardly recognized in the fairly broad emission spectra of polar chromophores in polar solvents.

Similar features, including the progressive red-shift of the emission band and its narrowing, are recognized in time-resolved emission spectra of many other dyes, including neutral dyes like coumarin 153 maroncelli1 , and zwitterionic dyes like LDS-750 lds750b . In fact, in spite of the opposite solvatochromism, neutral and zwitterionic dyes are predicted to have similar behavior with respect to time-resolved emission, as demonstrated by the time-resolved spectra calculated in Fig. 5 for the same zwitterionic dye whose steady-state absorption and emission spectra are reported in Fig. 2, right panels. Both the red-shift and the narrowing of time-resolved emission bands are due to the increase of the mixing between the two basis states during the relaxation of the system along the effective solvation coordinate, as discussed in the previous section with reference to steady-state spectra.

Other time-resolved experiments can be described within the proposed approach. Transient hole-burning experiments have been designed to follow the relaxation along the ground state PES. Specifically, we make reference to the experiment described in Ref. ernsting, . In this experiment, a solution of coumarin 102 (C102) dissolved in CH<sub>3</sub>CN is impulsively excited to transfer population from the minimum of the ground state PES (point G in Fig. 1b) to the vertical excited state (point G’ in Fig. 1c). After a delay time long enough as to allow for the complete relaxation of the system in the excited PES (from G’ to E in Fig. 1c), a second dump pulse is applied to vertically transfer the equilibrated population in the excited state PES into the ground state PES (from E to E’ in Fig. 1b). We are not interested in modeling the initial relaxation of vibrational coordinates occurring during the first few tens of fs ernsting , but, much as it was done for time-resolved fluorescence, we want to model the slower spectral evolution due to the solvent relaxation. We then assume an instantaneous (within the relevant solvation timescale) relaxation along the vibrational coordinate, towards point R in the ground state PES (Fig. 1b) lying on the local minimum path with respect to $`Q_1`$. The calculation of transient absorption spectra then goes via the solution of the Smoluchowski equation for $`w(Q_0)`$ from time zero (where the equilibrium $`w(Q_0)`$ relevant to the excited state PES is rigidly translated to point R in the ground state PES) towards the ground state equilibrium in G.

Figure 6 shows transient differential absorption spectra calculated for C102 in CH<sub>3</sub>CN. Molecular parameters for C102, as well as the solvent relaxation energy relevant to C102 in CH<sub>3</sub>CN, are obtained from the fit of steady-state absorption and emission spectra prepa . The additional parameter entering the Smoluchowski equation, $`\tau `$, is again fixed to 0.3 ps. In order to compare directly with experimental results, the upper and lower panel in Fig. 6 report the spectra calculated in two different temporal windows. The comparison with experimental spectra in Fig. 5 of Ref. ernsting,  is very good: in particular we reproduce not only the blue-shift of the band, but also the appearance of a TIP, and its temporal evolution. The origin of TIPs is easily recognized in the variation of the band-shape of the transient absorption that accompanies its progressive blue-shift. Whereas the rigid translation to the blue of the transient absorption band is quite easily understood based on the simplest linear model for solvation, the temporal evolution of the band-shape is a direct consequence of the molecular polarizability. In fact, as long as the system relaxes along the R-G path in Fig. 1b, the molecule readjusts its polarity (from $`\rho 0.23`$ to 0.16, in the specific case of C102 in CH<sub>3</sub>CN), and HR factors relevant to the absorption process change with time. TIPs are puzzling features of time-resolved spectra that cannot be explained easily within the standard picture for solvation, but are a natural consequence of the polarizability of the solute molecule.

TIPs appear quite commonly in pump-probe experiments dcm ; lds750 ; c153 ; blanchard . In these experiments, after the application of a pump pulse that drives the system to the excited state PES, the variation of the optical density of the solution is monitored by a probe-beam as a function of the delay time after the pulse. The experiment is easier than the hole-burning experiment, but the interpretation of resulting spectra is more complex. In fact at least three processes can contribute to the observed signal at each frequency. Both the bleaching of the absorption from the ground state (due to the reduced ground state population) and stimulated emission decrease the optical density, leading to a negative signal, whereas the absorption from the excited state increase the optical density, originating a positive signal. A reasonable separation of the different contributions is only possible if the three processes occur in well separated spectral regions. For polar chromophores in polar solvents, the large Stokes-shifts guarantee in general a reasonable discrimination between signals originating from the bleaching of the ground state absorption and from stimulated emission. If the positive signal from excited state absorption does not interfere too much, the pump-probe experiment gives information on the evolution of the emission band during the relaxation of the system along the F-E path in the excited state PES (Fig. 1c), so that, in favorable cases, the pump-probe experiment gives similar information as time-resolved fluorescence. According to the previous discussion, we then predict a progressive red-shift and narrowing of the emission band, in quite good agreement with available experimental data for several chromophores, with either a neutral dcm ; c153 ; blanchard  or a zwitterionic ground state lds750 . We underline once more that the red-shift of the stimulated emission band is easily rationalized in the standard solvation model. On the opposite, the narrowing of the band, being related to the variation of the molecular polarity with the solvent relaxation, can only be understood in models where the molecular polarizability is properly accounted for. The concomitant red-shift and narrowing of the emission band are responsible for the appearance of TIPs in observed spectra.

## IV Discussion

Push-pull chromophores are interesting molecules in several respects: they find application as solvation probes fleming ; reichardt , as laser-dyes, and as chromophores for non-linear optics kanis . They are also good two-photon absorbers albota  and work as molecular rectifiers metzger2 . From a theoretical point of view, the possibility to describe the electronic structure of these molecules in terms of an effective two-state model makes these systems fascinating model systems to understand electron-transfer in solution and specifically to investigate the physics of solvation in electron-transfer processes heitele ; barbara ; walker ; myers . In a series of recent papers chemphys ; cpl ; jpc1 ; baba , we have extended the standard two-state model for push-pull chromophores oudar ; goddard ; barzoukas  to account for solvation and molecular vibration. The model allows for a non-perturbative treatment of the relevant couplings and fully accounts for the solute (hyper)polarizability, yielding to a successful picture for steady-state spectra of push-pull chromophores in solution baba ; jpc2 ; sm2 . Here we extend the model to time-resolved spectra and demonstrate the important role of the solute hyperpolarizability in several characteristic and non-trivial spectroscopic features.

Consider a simple system with no electron-vibration coupling. Due to the molecular (hyper)polarizability, the reaction field affects the solute properties and, in turn, is affected by the presence of the solute. As a consequence of this feedback interaction, the ground and excited state PES for the $`Q_0`$ motion are deformed under . The linear polarizability ($`\alpha _{G/E}`$) is responsible for a renormalization of the relevant harmonic frequencies jpc1 :

$$\mathrm{\Omega }_{G/E}=\omega _0\sqrt{12ϵ_0\alpha _{G/E}/\mu _0^2}$$
(9)
while higher order polarizabilities originate anharmonic corrections cplfreo ; jcp  that can be fairly large for chromophores with large NLO responses. The role of the molecular first polarizability, $`\alpha `$, on solvation dynamics is easily understood and has already been discussed by several authors cichos ; kim ; glasbeek ; matyushov . If the hyperpolarizability is neglected, the PES are harmonic and the solvation relaxation function, $`C(t)`$, has a simple exponential form. The relaxation time, $`\tau _{G/E}=\gamma /\mathrm{\Omega }_{G/E}^2`$, is however renormalized with respect to the relaxation time of the pure solvent, $`\tau =\gamma /\omega _0^2`$, and depends on specific properties of the solute. A qualitatively different behavior is expected if hyperpolarizabilities are accounted for, leading to anharmonic PES. In this case, a non-exponential $`C(t)`$ is expected, whose detailed behavior depends the details of the relevant PES. The role of the solute hyperpolarizabilities on solvation dynamics has not been recognized so far and the observed deviations of $`C(t)`$ from the simple exponential behavior have always been ascribed to the failure of the continuum model for the solvent or to the underdamped nature of the solvation coordinate maroncelli2 ; rosenthal ; jarzeba . Instead a non-exponential behavior can show up within the simplest model for solvation, as a consequence of the solute hyperpolarizability.

The molecular (hyper)polarizability has even more important effects in the presence of coupled internal vibrations. In fact the common coupling of vibrational and solvation degrees of freedom to the electronic system induces a mixing between the two kinds of coordinates, even if no direct coupling between the modes is included in the hamiltonian. The physical origin of the mixing lies in the molecular (hyper)polarizability: the polarizable molecule in fact readjusts its polarity to any variation of solvation or of vibrational coordinates, but this variation of polarity affects in turn all coordinates, leading to an interdependence of all motions. As discussed in the previous section, even in the simplifying hypothesis of a complete separation of the timescales of vibrational and solvation motion, the relaxation of the solvent coordinate always implies, for a polarizable solute, a concomitant relaxation along the vibrational coordinates. Therefore time-resolved experiments performed on polarizable chromophores measure a complex motion where the molecular geometry readjusts following the solvent relaxation. Deviations of the observed relaxation time from the relaxation time of the pure solvent, as well as deviations from the simple exponential behavior for $`C(t)`$, are obviously predicted in this model. Just as an example, Fig. 7A compares the spectral correlation function calculated for hole-burning experiment on C102 described in the previous section. Deviations of the exact result from the simple exponential behavior, as well as an overall slowing down of the solvation dynamics with respect to the pure solvent, can be appreciated from the figure, even if, due to the large experimental uncertainties in $`C(t)`$, they are possibly too small to be safely identified in experimental data. Larger effects are predicted for more polarizable solute molecules, as shown in Figure 7B for phenol blue, an interesting solvatochromic probe whose large hyperpolarizability is known since date marder . Quite irrespective of their magnitude, these effects are important since they demonstrate that the presence of a polarizable solute affects solvation dynamics: the relaxation time obtained from the spectral relaxation function is not a property of the pure solvent, but also depends on the solute molecule. Good solvation probes should be largely solvatochromic and *hardly polarizable* as well.

The two-state model unavoidably assigns the excited state a linear polarizability equal in magnitude and opposite in sign to the ground state polarizability, then pointing to a solvation time in the excited state smaller than the longitudinal relaxation time of the pure solvent. As discussed in Ref. matyushov2,  the negative polarizability of the excited state is probably an artifact of the two-state model, that neglects the mixing of the low-lying excited state with higher excited states whose (positive) contribution to $`\alpha _E`$ usually over-compensate the negative contribution from the mixing with the ground state. Estimates of excited state polarizabilities are available for just a few chromophores and all confirm positive $`\alpha _E`$ values peteneau ; matyushov3 . However, the possibility of observing a negative $`\alpha `$ for the excited state of highly polarizable chromophores cannot be excluded a priori. In any case, it is possible to modify the proposed approach to account for the role of (a few) higher excited states. However, this would introduce new adjustable parameters in the model, whose definition is arbitrary in the absence of accurate experimental information on the polarizability of the excited state, or on the relaxation dynamics in the excited state.

The analysis of $`C(t)`$ is hindered by large experimental uncertainties, and the effects of the solute (hyper)polarizability are more easily recognized in the temporal evolution of band-shapes. As recently suggested by Matyushov matyushov , if one accounts for the solute linear polarizability, the different curvatures in the ground and excited state PES lead to different equilibrium $`w(Q_0)`$ distributions in the two states. Then a temporal evolution of $`w(Q_0)`$ is easily predicted in time-resolved experiments, resulting in an evolution of the inhomogeneous broadening profiles in observed spectra. The solute hyperpolarizability makes the phenomenon more complex: anharmonic PES, as originated by non-linear polarizabilities cplfreo ; jcp , in fact lead to non-Gaussian distribution profiles. However, it is important to recognize that, as discussed in the previous section, band-shapes are actually governed by vibronic profiles, inhomogeneous broadening being only responsible for their smearing out. The observed evolution of band-shapes is indeed originated by the coupling between solvation and vibrational degrees of freedom, as induced by the molecular (hyper)polarizability. The role of vibronic profiles in defining observed band-shapes was recognized in Ref. marcus, , but the temporal evolution of HR factors was introduced ad hoc. We demonstrate instead that it is a natural consequence of the solute (hyper)polarizability.

The evolution of band-shapes that accompanies the red- (blue-) shifts of time-resolved fluorescence (absorption) bands can be responsible for a crossing of observed spectra. The resulting TIPs are not true isosbestic points, as their location smoothly varies with time. In any case, the appearance of TIPs has puzzled experimentalists and theorists since date dcm ; lds750 ; ernsting ; blanchard . Recently, a paper appeared aimed to demonstrate the failure of the two-state picture for push-pull chromophores, based on the appearance of TIPs in pump-probe spectra blanchard . In this paper, TIPs are ascribed to a barrier-activated reaction occurring in the excited state towards a transient emissive product. Whereas further theoretical and experimental work is needed to settle this point, we underline that the molecules investigated in Ref. blanchard,  are among the best chromophores for NLO, and are therefore largely (hyper)polarizable. The observed large deviations of relaxation times from the longitudinal relaxation times of the pure solvents, point quite nicely to deviations from the standard linear perturbative picture of the solute-solvent interaction and perfectly fit within our two-state model for polar-polarizable chromophores, and suggest an alternative explanation of TIPs.

## V Conclusions

Time-resolved spectra of polar-polarizable chromophores in solution are described based on a continuum solvation model. A two-state picture is adopted for the solute, and linear coupling to internal vibrations is also accounted for. The model, originally developed to account for NLO responses chemphys ; cpl98  and steady-state spectra cpl ; jpc1  of push-pull chromophores in solution, is extended here to describe time-resolved spectra. The comparison with experimental data confirms that the proposed model quite successfully grasps the essential physics of polar-polarizable chromophores in solution. The model presents some obvious drawbacks. The two-state picture must be extended to account for higher-energy states if detailed information is required on excited state properties. Moreover, the Holstein model for electron-vibration coupling only accounts for linear terms: quadratic coupling is expected to be important in cases when a very different geometry (and hence very different bond orders) can be attributed to the two basis states. Again the extension of the model in this direction is easy, but requires detailed spectroscopic information to fix all the model parameters. Finally, the continuum model for solvation has serious limitations, particularly in cases were large site-specific interactions (like, e.g., H-bonds) are expected. The hypothesis of complete separation of vibrational and solvation time-scales can fail for molecules with particularly slow internal degrees of freedom and/or for solvents with a very fast dynamics. In spite of these limitations, and quite irrespective of its applicability to some specific systems, the proposed model opens the way to obtain exact, non-perturbative solutions of the solvation problem also in the presence of electron-vibration coupling. The spectral consequences of the molecular (hyper)polarizability, that is unavoidably neglected in the standard linear perturbative approach to solvation, are important and non-trivial, and show up quite consistently in steady-state and time-resolved spectra of push-pull chromophores. In particular here we have demonstrated that deviations from the exponential decay of the spectral relaxation function, that are usually taken as proof of the failure of the continuum model for solvation, appear quite naturally within the simplest picture, provided the molecular (hyper)polarizability is accounted for. Similarly, the temporal evolution of band-shapes, as well as the appearance of TIPs, usually ascribed to the failure of the two-state model, are another consequence of non-linearity. More complex models can of course be developed, and will lead to a better or more detailed description of spectral properties of push-pull chromophores in solution. Based on an Occam-razor approach, we believe however that the available body of experimental data does not require any more complex physics than described here.


text:
# 1 Introduction

## 1 Introduction

In cosmic ray physics, the following problems are not solved yet; anomalous detection of extremely high energy cosmic rays  above the GZK cutoff ($`5\times 10^{19}`$ eV) , and TeV-$`\gamma `$ rays  from Mrk 501 and Mrk 421. It was suggested that the absence of the GZK cutoff is closely related to violation of the Lorentz invariance . If the Lorentz invariance is violated or deformed, there is the possibility to explain that there is not the GZK cutoff at $`E=5\times 10^{19}`$ eV . Therefore we have to consider a mechanism for the violation or deformation of the symmetry.

One of the characteristic features with respect to quantum gravity is the Plack length. If we would like to deal with this as an observer independent scale, the special relativity becomes a deformed one which has two scales; a velocity $`c`$ and a mass $`\kappa `$. This is called the doubly special relativity  which is explicitly realized by the $`\kappa `$-Poincare algebra .

The $`\kappa `$-Poincare algebra is defined by replacing the Poincare algebra with a quantum group (Hopf algebra) with a parameter $`\kappa `$ . In the limit $`\kappa \mathrm{}`$, the Hopf algebra is reduced to the ordinary Lie algebra. Majid and Ruegg  have pointed out that the $`\kappa `$-deformed algebra is the symmetry in the $`\kappa `$-Minkowski spacetime in which time and spatial coordinates are non-commutative.

Some authors have discussed particle’s velocity formulae  in the $`\kappa `$-Minkowski spacetime. In the arguments, it was assumed that a velocity is defined by $`v=\frac{E}{p}`$ which is true in the commutative Minkowski spacetime. In , by applying the formula to a massless particle, it was predicted that the speed of light is dependent on its energy $`E`$ and the parameter $`\kappa `$. In , by changing the rule of differentiation with respect to momenta, it was mentioned that the speed of light is undeformed. However validity of using the formula $`v=\frac{E}{p}`$ in the $`\kappa `$-Minkowski spacetime has not been discussed sufficiently yet.

It is known that there exists some bases of the $`\kappa `$-Poincare algebra , which are related with each other by redefinition of the translation operators . In other words, the $`\kappa `$-deformation of the Poincare algebra is not unique. Since the dispersion relation is given as the Casimir operator of the algebra, the particle’s velocity depends which bases we use, if the formula $`v=\frac{E}{p}`$ is used. In this paper we would like to consider a velocity by avoiding using the formula, and would like to compare results.

The present paper is organized as follows. In the next section, we review the $`\kappa `$-Minkowski spacetime and the $`\kappa `$-Poincare algebra. Some velocity formulae are given explicitly by using the bicrossproduct basis. In the section 3, we will see that the action of a free particle does not depend on $`\kappa `$, and $`c`$ is interpreted as the expectation value of photon’s velocity. There is the deviation of the photon’s velocity from the value $`c`$, because of the spacetime non-commutativity. The section 4 is devoted to the summary and the remarks.

## 2 Review of $`\kappa `$-Minkowski spacetime

In this section, we briefly review the $`\kappa `$-deformed Poincare algebra, and present discussions about velocities of particles in the $`\kappa `$-Minkowski spacetime.

Drinfeld  and Jimbo  have proposed a prescription how to define a quantum enveloping algebra, which is q-deformation of an universal enveloping algebra of a simple Lie algebra, in terms of a Hopf algebra. Since the Poincare algebra is not a simple Lie algebra, it is not straightforward to apply the Drinfeld-Jimbo prescription to the Poincare algebra. It is well known that the Poincare algebra can be obtained by contraction of the $`3+2`$ dimensional AdS algebra $`o(3,2)`$ which is a simple Lie algebra. In the limit $`R\mathrm{}`$ which is the AdS radius, the AdS algebra is reduced to the Poincare algebra. The contraction  $`R\mathrm{}`$ with $`iR\mathrm{log}q\kappa ^1`$ of the q-deformed AdS algebra gives a $`\kappa `$-deformed Poincare algebra . Here $`\kappa `$ is a real constant, and $`q`$ is an imaginary parameter222It is possible to use a real parameter  instead of the imaginary $`q`$. In this case, contraction is $`R\mathrm{log}q\kappa ^1`$.  with $`|q|=1`$. The $`\kappa `$-deformation of the Poincare algebra is not unique , however which are related by redefinition of translation generators . For example, the $`\kappa `$-Poincare algebra in the bicrossproduct basis  is given by

$`[p_\mu ,p_\nu ]=0,[p_0,M_i]=0,[p_i,M_j]=iϵ_{ijk}p_k`$ (2.1)
$`[M_i,M_j]=iϵ_{ijk}M_k,[M_i,N_j]=iϵ_{ijk}N_k,[N_i,N_j]=iϵ_{ijk}M_k`$ (2.2)
$`[N_i,p_0]=ip_0,[N_i,p_j]=i\delta _{ij}\left({\displaystyle \frac{\kappa }{2}}(1e^{2\frac{p_0}{\kappa }})+{\displaystyle \frac{1}{2\kappa }}𝐩^2\right){\displaystyle \frac{i}{\kappa }}p_ip_j`$ (2.3)
with translation $`p_\mu `$, rotation $`M_i`$ and boost $`N_i`$ generators. The $`o(3)`$ subalgebra is undeformed. The coproducts are given by

$`\mathrm{\Delta }(M_i)`$ $`=`$ $`M_i1+1M_i`$ (2.4)
$`\mathrm{\Delta }(N_i)`$ $`=`$ $`N_i1+\mathrm{exp}\left({\displaystyle \frac{p_0}{\kappa }}\right)N_i+{\displaystyle \frac{1}{\kappa }}ϵ_{ijk}p_jM_k`$ (2.5)
$`\mathrm{\Delta }(p_i)`$ $`=`$ $`p_i1+\mathrm{exp}\left({\displaystyle \frac{p_0}{\kappa }}\right)p_i`$ (2.6)
$`\mathrm{\Delta }(p_0)`$ $`=`$ $`p_01+1p_0.`$ (2.7)
When the coproducts are given, counits and antipodes are obtained uniquely. But we do not write the detailed form since we do not use them in the present paper. In the limit $`\kappa \mathrm{}`$, the Hopf algebra are reduced to the Poincare algebra. The mass shell condition is obtained as the Casimir operator;

$`m^2=\left(2\kappa \mathrm{sinh}\left({\displaystyle \frac{p_0}{2\kappa }}\right)\right)^2𝐩^2e^{\frac{p_0}{\kappa }}.`$ (2.8)
The mass $`m`$ is not a physical one. A relation with a physical mass is suggested in . We find that the expression gives the upper bound of the momentum; $`p_ip^i\kappa ^2`$.

It was noticed that quantum groups can be realized as symmetries in non-commutative spaces333As a review article, see . . The $`\kappa `$-Poincare algebra is the symmetry in the $`\kappa `$-Minkowski spacetime  which is non-commutative;

$`[X^i,X^0]={\displaystyle \frac{1}{\kappa }}X^i,[X^i,X^j]=0.`$ (2.9)
Although there are some bases of the algebra , all of them correspond to the commutator .

In the commutative Minkowski spacetime, a particle’s velocity is written as

$`v_i={\displaystyle \frac{E}{p^i}}`$ (2.10)
with $`E=\sqrt{p^2+m^2}`$. Many authors have assumed that this relation is true also in the $`\kappa `$-Minkowski spacetime . For a massless particle, by solving (2.8) and using the formula (2.10) we have

$`v^2=c^2\mathrm{exp}\left({\displaystyle \frac{2E}{\kappa }}\right).`$
So the velocity of a massless particle is deformed from the constant c, and has energy dependence. Because of the effect, the $`\kappa `$ has the constraint $`|\kappa |^1<10^{33}`$m from the astronomical observation of $`\gamma `$ rays . On the other hand, in , it was mentioned that the rule for the differentiation with the momentum is changed since the momentum sum rule is $`\kappa `$-deformed. From the coproduct (2.6), we notice that the sum of momenta $`p_1`$ and $`p_2`$ of two particles is deformed as

$`p_1+\mathrm{exp}\left({\displaystyle \frac{E_1}{\kappa }}\right)p_2`$
which is non-Abelian. By applying this to the velocity formula, we have two kinds of velocities;

$`V_l^i=\mathrm{exp}\left({\displaystyle \frac{E}{\kappa }}\right)V^i,V_r^i=\left(1+{\displaystyle \frac{1}{\kappa }}pV\right)^1V^i.`$
We find that these two velocities satisfies $`(V_l^i)^2=(V_r^i)^2=c^2`$ for massless particles.

A common property with respect to them is that the velocities are determined uniquely when their energies are given. In other words, the particle velocities have no uncertainty. However, there have to be exist such an uncertainty, because time and spatial coordinates of particles cannot be observed simultaneously by the non-commutativity (2.9). We would like to investigate the point in the next section.

## 3 Uncertainty of velocity

Here we would like to see how velocities of point particles are deformed in the $`\kappa `$-Minkowski spacetime by using a method by which we can avoid arguments which depend on the bases of the $`\kappa `$-Poincare algebra. In order to do this, we consider a particle in coordinate space $`X^\mu `$ instead of the momentum space.

When a space is a non-commutative one, there is the possibility that a symmetry on the space becomes a quantum group . The quantum group makes a commutator of coordinates covariant. In this formalism, a parameter of the non-commutativity is an invariant scale. By virtue of this, the doubly special relativity can be realized as a quantum group . We apply this to the $`\kappa `$-Minkowski spacetime (2.9).

All of known bases of the $`\kappa `$-Poincare algebra correspond to the commutator (2.9) . So we can perform an analysis which is independent on a choice of the basis if we start from the commutator (2.9). The Poincare quantum group transformation of the coordinates is defined by

$`X^\mu =\mathrm{\Lambda }_\nu ^\mu X^\nu +a^\mu `$
with

$`\eta _{\mu \nu }\mathrm{\Lambda }_\rho ^\mu \mathrm{\Lambda }_\sigma ^\nu =\eta _{\rho \sigma }.`$ (3.1)
Here $`\eta ^{\mu \nu }=(,+,+,+)`$ is the flat metric tensor. We demand that the transformed coordinates $`X^\mu `$ also satisfy the commutator (2.9). The Poincare quantum group does not determined only by the covariance of the commutator. Furthermore we demand that differentiation with respect to $`X^\mu `$ is not deformed;

$`dX^\mu dX^\nu =dX^\nu dX^\mu .`$
In order for the condition (3.1) to be compatible with the Poincare quantum group, (3.1) have to be commutative with all of the elements of the quantum group. By using the conditions, the Poincare quantum group  is determined uniquely;

$`[\mathrm{\Lambda }_\rho ^\mu ,\mathrm{\Lambda }_\sigma ^\nu ]`$ $`=`$ $`0,[a^\mu ,a^\nu ]={\displaystyle \frac{1}{\kappa }}(\delta _i^\mu \delta _0^\nu \delta _i^\nu \delta _0^\mu )a^i`$ (3.2)
$`[a^\mu ,\mathrm{\Lambda }_k^\nu ]`$ $`=`$ $`{\displaystyle \frac{1}{\kappa }}[(\mathrm{\Lambda }_{0}^\nu \delta _0^\nu )\mathrm{\Lambda }_\rho ^\mu +(\mathrm{\Lambda }_\rho ^0\delta _\rho ^0)\eta ^{\mu \nu }].`$ (3.3)
which is the dual Hopf algebra  of (2.1)-(2.3).

Next we would like to see kinematics of a particle in the $`\kappa `$-Minkowski spacetime. The action of a free particle which is invariant under the Poincare quantum group (3.2) and (3.3) have the usual form;

$`S={\displaystyle \frac{1}{2}}{\displaystyle 𝑑\tau [\frac{1}{e}(\dot{X}^\mu )^2em^2]}`$ (3.4)
with $`\dot{X}^\mu =\frac{dX^\mu }{d\tau }`$. On the other hand, when we consider the $`\kappa `$-deformed Poincare algebra (2.1)-(2.3) as a bicrossproduct Hopf algebra , the invariant metric is

$`(X_0)^2(X^i)^2+{\displaystyle \frac{3}{\kappa }}X_0`$
which is different from ours. It is not clear why they are different. The canonical Hamiltonian is also $`\kappa `$-independent

$`H={\displaystyle \frac{1}{2e}}[P_\mu P^\mu m^2].`$
The action of the free particle does not depend on the non-commutativity parameter $`\kappa `$ in the $`\kappa `$-Minkowski spacetime. It is known that, in the non-commutative spacetime with $`[X^\mu ,X^\nu ]=i\theta ^{\mu \nu }`$, $`\theta ^{\mu \nu }`$-dependent parts of free field theories’ action vanish. This is the characteristic point in common. Although the action is $`\kappa `$-independent, the non-commutativity effects a change of physical quantities. In the rest of the present section, we see this explicitly.

Let’s consider a velocity of a particle which is described by the action (3.4). Because of the spacetime non-commutativity, we cannot observe strict values of $`X^i`$ and $`X^0`$ simultaneously, and there exists an ambiguity of the particle’s velocity. At first, we see the expectation value of the velocity. It is natural to make the expectation values of the coordinates $`x^\mu :=X^\mu `$ be a solution of the equations of motion which are derived from the action (3.4) with $`X^\mu x^\mu `$. The expectation value of the particle velocity is

$`v^i`$ $`=`$ $`{\displaystyle \frac{dx^i}{dt}}={\displaystyle \frac{\dot{x}^i}{\dot{t}}}.`$
By using the equation of motion, we have $`v^2=c^2`$ for massless particles. The expectation value of the velocity satisfies the ordinary velocity formula. The invariant scale $`c`$ can be interpreted as the expectation value of a velocity of a massless particle.

Next we would like to see a deviation from the expectation value. The expectation value of a deviation from the expectation value $`x^\mu `$ satisfy the inequality

$`(\mathrm{\Delta }X^i)^2(\mathrm{\Delta }T)^2{\displaystyle \frac{1}{4c^2\kappa ^2}}|X^i|^2`$ (3.5)
with $`\mathrm{\Delta }X^\mu :=X^\mu x^\mu `$. Here the index $`i`$ is not summed. The inequality means that time and spatial coordinates of a particle cannot be detected precisely at once except for at the origin in a coordinate system. When $`|X^i|`$ is large, so is the uncertainty. This depends which coordinate systems we use.

Let’s consider a case in which a free particle starts from the origin $`X^\mu =0`$ of the spacetime. At a later time, the particle is at $`X^\mu :=x^\mu `$ with $`x^00`$. Since the $`o(3)`$ subalgebra of the Poincare algebra is not $`\kappa `$-deformed, without loss of generality, we can choose a coordinate system with

$`L:=x^10,x^2=x^3=0.`$ (3.6)
In this case $`X^i`$ in the right hand side of (3.5) is an expectation value of a propagation length of the particle during the time $`x^0`$. Hence when the length $`L`$ is very large so is the spacetime uncertainty.

Here we would like to see a deviation from the expectation value $`v:=V`$. We denote $`\delta X^i=\sqrt{(\mathrm{\Delta }X^i)^2}`$ and $`\delta T=\sqrt{(\mathrm{\Delta }T)^2}`$. Although the inequality (3.5) does not forbid both of $`\delta X^i`$ and $`\delta T`$ to be large, by analogy with quantum mechanics, we assume that they are small with the equality (3.5) satisfied. Under the condition with the configuration (3.6), we find that the uncertainties along the directions $`x^2`$ and $`x^3`$ vanish; $`\delta X^2=\delta X^3=0`$, and $`\delta T`$ and $`\delta X^1`$ have non-zero values. The spacetime uncertainty brings about the following velocity’s uncertainty;

$`\delta V^2=2{\displaystyle \frac{L^2}{t^3}}\delta T\pm 2{\displaystyle \frac{L}{t^2}}\delta X^14{\displaystyle \frac{L}{t^3}}\delta X^1\delta T\pm {\displaystyle \frac{3L^2}{t^4}}(\delta T)^2+{\displaystyle \frac{1}{t^2}}(\delta X^1)^2`$ (3.7)
up to second order in $`\delta X^i`$ and $`\delta T`$. We assume that $`\delta X^i`$ and $`\delta T`$ are so small that the first two terms in (3.7) are the dominant part. If we choose a configuration in which the first order terms are canceled with each other, this gives the minimum value of $`\delta V^2`$ approximately. So the minimum value of $`\delta V^2`$ is

$`\delta V^2|_{\mathrm{min}}{\displaystyle \frac{3v^3}{|\kappa L|c}}.`$ (3.8)
Here we have used $`v:=\frac{L}{t}`$.

## 4 Summary and remarks

In this paper, we have investigated free particle’s motion in the $`\kappa `$-Minkowski spacetime in which the Poincare group becomes the quantum group. The particle’s action is not $`\kappa `$-deformed, since the invariant metric of the $`\kappa `$-Minkowski spacetime does not have $`\kappa `$-dependence in our formalism. When we define particle’s velocity, there exists uncertainty of the velocity because the spacetime coordinates are non-commutative operators with the commutator (2.9). The point is different from the discussions in momentum spaces . We saw that the particle’s velocity can depend on $`\kappa `$, even if the action is $`\kappa `$-independent.

In ordinary relativistic classical theories, massless particles propagate only with the velocity $`c`$ which is defined by $`c=299792458m/s`$. However in the $`\kappa `$-Minkowski spacetime, the massless particle’s velocity have the uncertainty

$`\delta V^2|_{\mathrm{min}}{\displaystyle \frac{3c^2}{|\kappa L|}}`$
which does not depend on the energy of the particle but on the propagation length $`L`$ of the particle. When $`L`$ is small, so is the spacetime uncertainty (3.5). However for a small $`L`$, the velocity’s uncertainty is large. The constant $`c`$ can be interpreted as the expectation value of the photon’s velocity.

In order to compatible with the observed value of $`c`$, we have the bound $`|L\kappa |>10^{20}`$. The typical length of light paths in experiments of velocity of light is of order $`10^2`$-1$`0^3`$m . So $`\kappa `$ is $`|\kappa |>10^{17}`$m which is weaker restriction than the one which is derived by using the formula (2.10).

In a non-relativistic limit $`\frac{v}{c}0`$, the uncertainty (3.8) of the velocity can be negligible. The result is compatible with the fact that the only Lorentz boost part of the Poincare algebra is $`\kappa `$-deformed.

Acknowledgment

The author would like to thank the Yukawa institute for hospitality, where a part of the research was done.


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# Absolute Lineshifts – a new diagnostic for stellar hydrodynamics

## 1. Progress in understanding stellar atmospheres

Improved understanding of physical processes in stellar atmospheres comes from the interplay between theory and observations. The validity of, e.g., hydrodynamic simulations of stellar photospheres can be tested by whether they succeed in reproducing observed shapes and asymmetries of photospheric spectral lines. On one hand, the success of such models (at least for solar-type stars) is encouraging in suggesting that many physical processes probably are beginning to get understood. However, on the other hand, different models with dissimilar parameter combinations sometimes are able to produce similar results, showing the need for further observational constraints. New diagnostic tools are needed to, e.g., segregate 2-dimensional models from 3-dimensional ones, to identify effects of non-LTE, or of 3-dimensional radiative transfer in line formation.

One has to remember that progress in astronomy (and natural science in general) depends upon the falsification of theoretical concepts and hypotheses. If the ambition is to improve a model, the aim is not to have it fit the observations, but rather to identify situations where the model and observations are in disagreement (in the case of agreement, there is really nothing more that can be learned). A route for progress in stellar-atmospheres research is then to identify new diagnostic tools that both can be accurately observed and be precisely predicted by models. A confrontation between these observational and theoretical measures may then segregate among competing concepts and guide models toward greater realism and sophistication.

This paper discusses one such new diagnostic tool: ’Absolute’ wavelength shifts of photospheric spectral lines. This denotes the wavelength displacement of spectral lines away from the positions they naively would be expected to have, had the lines been affected by only the Doppler shift caused by the relative star-Earth motion. In the past, such absolute lineshifts could be studied only for the Sun (since the relative Sun-Earth motion, and the ensuing Doppler shift is known from planetary-system dynamics, and does not rely on measurements in the solar spectrum). For other stars, this is now becoming possible thanks to three separate developments: (a) Accuracies reached in space astrometry has made it possible to accurately determine stellar radial motion from second-order effects in astrometry only, without using any spectroscopy; (b) The availability of high-resolution spectrometers with accurate wavelength calibration (such as designed for exoplanet searches), and (c) Accurate laboratory wavelengths for several atomic species. Already the two latter points (b) and (c) permit studies of differential shifts between different classes of lines in one and the same star even if, in the absence of astrometric radial velocities, the shifts can not be placed on an absolute scale.

Asymmetries and wavelength shifts of photospheric absorption lines originate from correlated velocity and brightness patterns (stellar granulation): rising (blueshifted) elements are hot (bright), and convective blueshifts normally result from a larger contribution of such blueshifted photons than of redshifted ones from the sinking and cooler (darker) gas. The exact amount of shift differs among lines with different conditions of formation. For example, high-excitation lines may form predominantly in the hottest (also the most rapidly rising, and most blueshifted) elements, and thus show a more pronounced blueshift. By contrast, lines formed in high-lying layers of convective overshoot may experience an inverted correlation, instead resulting in a convective redshift. For overviews of processes causing such shifts, see Dravins (1999), Asplund et al. (2000), Allende Prieto et al. (2002), and references therein. One observational advantage of lineshifts (as opposed to line asymmetries or precise line profile shapes) is that they may be simpler to measure also at modest spectral resolutions, when the bisectors describing line asymmetries may already be strongly perturbed (Dravins & Nordlund 1990b; Hamilton & Lester 1999).

## 2. Radial velocities without spectroscopy!

Traditionally, stellar radial velocities have been determined by spectroscopy, utilizing the Doppler effect. The advent of high-accuracy (milli-arcsecond) astrometric measurements now permits radial velocities to be obtained also by purely geometric methods. Such astrometric radial velocities, giving the motion of the stellar center-of-mass, are independent of phenomena affecting stellar spectra, such as stellar pulsation, convection, rotation, winds, isotopic composition, pressure, and gravitational potential. Among the several astrometric techniques (Dravins et al. 1999b), one method reaches sub-km s-1 accuracies already with existing data. This ’moving-cluster method’ is based on the circumstance that stars in suitable open clusters move through space with a common \[average\] velocity vector. The radial-velocity component makes the cluster appear to contract or expand due to its changing distance. This relative rate of apparent contraction (observed through stellar proper motions) equals the relative rate of change in distance, which can be converted to a linear velocity (in km s-1) if the distance is known from trigonometric parallaxes. Once the space velocity is known, the radial velocity for any member star follows by projecting the cluster’s velocity vector onto the line of sight. The method can be regarded as an inversion of the classical moving-cluster problem, where the distance is derived from proper motions and (spectroscopic) radial velocities: here, by instead first knowing the distances, the radial velocities follow: Figure 1.

## 3. Lineshifts intrinsic to stellar atmospheres

On Hipparcos, an observing program was carried out for stars in moving clusters, yielding astrometric radial-velocity solutions for more than 1,000 stars (Madsen et al. 2002), including about one hundred stars in the Hyades and Ursa Major groups. The error budgets are somewhat complex, but typical accuracies reach around 0.5 km s-1.

Differences between astrometrically determined radial velocities (giving true motions of the stellar centers of mass) and the apparent spectroscopic velocities of different features reveal lineshifts intrinsic to stellar atmospheres, such as convective and gravitational lineshifts. Figure 2 for Hyades stars indicates that F-type spectra have enhanced convective blueshifts relative to cooler ones (as expected from hydrodynamic simulations; Dravins & Nordlund 1990ab; Allende Prieto et al. 2002), a tantalizing trend that seems to continue to even hotter stars (where corresponding hydrodynamic models are not yet developed).

## 4. Gravitational redshifts

Another phenomenon affecting the difference between spectroscopic and astrometric radial velocities is the gravitational redshift, $`V_{\mathrm{grav}}=GM/Rc`$, involving the constant of gravitation, the speed of light, and the stellar mass and radius. Using accepted solar values, we obtain 636 m s-1 for light escaping from the solar photosphere to infinity, and 633 m s-1 for light intercepted at the Earth. A spectral line formed at chromospheric heights (30 Mm, say), will have this shift decreased by some 20 m s-1, and a coronal line by perhaps 100 m s-1. For other stars, the shift scales as ($`M/M_{}`$)($`R_{}/R`$).

It is believed that this shift can be reasonably well predicted from stellar structure models (for well-studied single main-sequence stars to an accuracy of perhaps 50 m s-1), and it is not expected to change significantly between different photospheric lines. Therefore, it should be much less of an unknown variable than the convective lineshifts.

Figure 3 shows expected gravitational redshifts predicted from standard models. The shift does not vary much on the main sequence between A5 V and K0 V ($``$ 650 m s-1), but reaches twice that value for more massive early-B stars with $`M`$ 10$`M_{}`$. However, the convective lineshift, $`V_{\mathrm{conv}}`$, is expected to be about $``$1000 m s-1 for F5 V, $``$400 m s-1 for the Sun, and $``$200 m s-1 for K0 V (Dravins 1999, and references therein). The difference $`V_{\mathrm{spec}}V_{\mathrm{astrom}}`$ can thus be expected to lie in the range between $``$400 and +400 m s-1, when moving along the main sequence from F5 V to K0 V ($`BV`$ between 0.4 and 0.9).

## 5. 3-D models of convective shifts in different stars

Synthetic line profiles from three-dimensional hydrodynamical models do well reproduce photospheric line shapes and shifts in solar-type stars. Figure 4 serves to (a) illustrate the magnitude of the effect, and (b) to show that the intensity profile alone (at least on first sight) does not reveal any striking signature of the complex convective velocity fields shaping it.

Figure 5 shows normalized bisectors of synthetic spectral lines in different solar-type stars, obtained from 3-D hydrodynamic models. It shows how the asymmetry of such lines may be quite similar, although their wavelength shifts differ by a full factor of 5! Clearly, lineshifts are sensitive signatures of dissimilar convection patterns in different stars. In particular, the more vigorous convection in subgiants produces a stronger convective blueshift than in dwarfs, despite quite similar line profile shapes (Dravins & Nordlund 1990a).

## 6. Non-LTE diagnostics

Lineshifts offer a non-LTE diagnostic for synthetic line profiles, since such effects may show up more clearly in shifts than in either profiles or asymmetries. Although line shapes may well be similar in LTE, line shifts can be different. For lines in the visual from neutral metals in solar-type stars, non-LTE calculations normally reveal a smaller convective blueshift because the fastest upflows occur in the hottest granular elements. These emit strong ultraviolet flux, ionizing the gas above, thus decreasing the most blueshifted line absorption contributions from neutral species. Close to the stellar limb, the bisector effects become more significant, an effect of a ’corrugated’ stellar surface (Figure 6).

## 7.  Solar lineshift patterns

For the Sun, absolute lineshift studies have been possible since long ago. Of course, models for the solar atmosphere are developed to a much higher sophistication than those for other stars, implying that more detailed model predictions can be made and tested. Observational limits are set by systematic errors in wavelength scales which, even in the best solar spectrum atlases, correspond to about 100 m s-1 or worse; comparable to the noise in the best sets of laboratory wavelengths for low-excitation lines from neutral metals. The most sensitive tests of various models might be with high-excitation lines, lines from ionized species, or from molecules. Unfortunately, such lines also appear to be those most sensitive to systematic errors in the determination of laboratory wavelengths. Nevertheless, improved laboratory measurements make an increasing number of lines available for study. Figure 7 shows the pattern of convective lineshifts for Fe II lines at solar disk center, using recent laboratory data.

Figure 8 is a sample of theoretically predicted convective lineshifts for specific Fe II lines, a subset of the observed ones in Figure 7. These line-bottom shifts of 21 Fe II lines at solar disk center were computed from two-dimensional hydrodynamic models. Squares show results from one particular model, and circles from another one, differing in horizontal extent and depth. Although the predicted pattern is qualitatively similar to the observed one in Figure 7, the granulation structure produced by 2-D models is not sufficiently vigorous to fully reproduce the amplitude of observed lineshifts, for which 3-D models thus are required. (The purpose of this figure is not to argue for any specific degree of agreement between theory and observation, but to demonstrate how different hydrodynamic models may be segregated though the different lineshift patterns predicted.)

The increasing availability of accurate laboratory wavelengths now permits studies for more species than the classically used iron only, including Ca I, Co I, Cr I, Ti I, and Ti II. This both increases the available sample of lines, and probes different conditions of line formation. As an example, Figure 9 shows the solar lineshift pattern for lines from neutral nickel.

## 8.  A new diagnostic for stellar atmospheres

A combination of observational and experimental advances now permit absolute lineshifts to be introduced as a diagnostic tool for stellar atmospheres, beyond the previously established ones of line-strength, -width, -shape, and -asymmetry.

On the theoretical side, lineshift patterns cannot yet be predicted across the whole HR-diagram. Not only do these require a credible modeling of the atmospheric hydrodynamics, but the lineshifts may vary greatly among different classes of spectral lines. This complex dependence actually is an advantage: Since the exact line displacements depend on so many parameters, stellar atmospheric properties can be constrained by many different wavelength measures for various lines in the same star, or between different stars.

The longer-term outlook appears quite promising since the accuracies for astrometric radial velocities will improve with planned future space astrometry missions (e.g., the ESA project GAIA). For stars in nearby clusters, the improvement will perhaps not be very dramatic (the accuracy then being limited by cluster kinematics), but more distant clusters will become accessible, offering samples of more unusual (but astrophysically important) spectral types.

For a further discussion, see links from http://www.astro.lu.se/~dainis/

### Acknowledgments.

This work is supported by The Swedish Research Council, the Swedish National Space Board, and The Royal Physiographic Society in Lund.

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