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# 3D Simulations of Relativistic Precessing Jets Probing the Structure of Superluminal Sources

## 1 Introduction

Numerical hydrodynamic simulations were initially used to study radiosources from their largest scales (Burns, Norman, & Clarke, 1991) to the collimation and formation of their associated jets (Koide et al., 2002). Due to the relativistic nature of these sources, relativistic hydrodynamic simulations have become necessary to study the superluminal sources present in the nuclei of active galaxies and in the microquasars of our galaxy. Improving on previous idealized analytical calculations (Marscher & Gear, 1985), these numerical methods are capable of studying the time–dependent non–linear relativistic fluid dynamics, like for instance the formation and propagation of shocks (Martí, Müller, & Ibáñez, 1994; Duncan & Hughes, 1994; Koide, Nishikawa, & Mutel, 1996; Falle & Komissarov, 1996; Aloy et al., 1999a). The computation of the non-thermal emission from such hydrodynamic models provides the means for a direct comparison between observations and theory, and is hence a significant step forward towards an understanding of the emission and structural variability of relativistic jets (Gómez et al., 1995, 1997; Komissarov & Falle, 1997; Mioduszewski, Hughes, & Duncan, 1997; Aloy et al., 1999b, 2000; Agudo et al., 2001).

Motivated by recent observations (e.g., Gómez et al., 2000; Tingay, Preston, & Jauncey, 2001; Wehrle et al., 2001) revealing complex jet structure and dynamics suggestive of being the result of multi–dimensional non–linear jet instabilities, we present a three–dimensional relativistic hydrodynamic and emission simulation of a precessing jet.

## 2 Hydrodynamic model

Our hydrodynamic code GENESIS (Aloy et al., 1999a) is based on high resolution shock capturing techniques, best suited to describe ultra-relativistic flows with strong discontinuities. The code employs the method of lines to achieve third order accuracy both in space (using a Parabolic Piecewise Monotonic -PPM- inter-cell reconstruction) and time (by means of a third order Total Variation Diminishing -TVD- Runge-Kutta scheme). Guided by observational data we simulate a jet composed of an ultra-relativistic plasma (adiabatic index 4/3, and specific energy $`50c^2`$, $`c`$ being the speed of light) in pressure equilibrium with an ambient atmosphere in which the jet propagates. The plasma is injected with a bulk Lorentz factor of 6, and is $`10^3`$ times lighter than the environment. We enforce a twofold precession of the jet by imposing helical perturbations on the injection velocity with amplitudes $`\zeta _1`$ ($`\zeta _2`$) = 0.035 (0.005), and periodicities $`\tau _1`$ ($`\tau _2`$) = 400$`R_b/c`$ (25$`R_b/c`$), where $`R_b`$ is the beam radius (the definitions of $`\zeta _{1,2}`$ and $`\tau _{1,2}`$ are the same as in Aloy et al. (1999b)). The first, long wavelength precession ($`\lambda _1=400R_b`$) causes a slight bending of the jet (within the computational domain of longitudinal size 90$`R_b`$), while the second precession, with a much shorter wavelength ($`\lambda _2=25R_b`$) and smaller amplitude than the first one, gives rise to a small helical modulation of the beam. Both structural characteristics are observed in many astrophysical sources (e.g., 3C 120; Gómez et al., 2000).

According to the recent observations of Marscher et al. (2002) radio components are generated by the injection into the jet of material coming from the inner accretion disk. Motivated by these observations, we perturb the jet by injecting a blob of relativistic particles through the jet inlet during 0.8$`R_b/c`$ in the frame attached to the source (LAB-frame). The blob, initially a cylindrical region of thickness 0.8$`R_b`$ and width 1.0$`R_b`$, is four times denser than the jet plasma, but has the same velocity and internal energy per particle. As the injected perturbation travels downstream it spreads asymmetrically along the beam and splits into two regions (Fig. 2) that have distinct observational signatures (§ 3). The fact that injected jet perturbations experience substantial evolution is general, i.e., is not specific to the perturbation that we have chosen. Indeed, a similar hydrodynamic evolution should be

expected for any perturbation that either does not match the shock jump conditions at its boundaries or propagates along a non-uniform beam. An idealized 1D model of the perturbation allows us to explain the basic features of its evolution. The original state disappears after $`15R_b/c`$ and displays a noticeable split after 30$`R_b/c`$ and beyond in the LAB-frame (Fig. 2). In the 3D simulation the evolution of the perturbation is also affected by its interaction with the external medium and changing beam conditions downstream. The front region (A) of the original blob shows the largest Lorentz factor ($`9`$) and relatively small energy density, while the back region (B) possesses the largest energy density but the smallest Lorentz factor ($`4.5`$).

Initially the perturbation is ballistic as a consequence of its high relativistic density ($`9.7`$ times that of the external medium) and moves in a straight trajectory until

it impacts on the bent walls of the beam, between times 20 and 40$`R_b/c`$. This causes an increase of the internal energy density and a reduction of the Lorentz factor in the region of maximum shear (Fig. 3b, 3c). The heating is a consequence of the compression of the perturbation, which is enhanced by the presence of a standing shock in the beam (Fig. 3a). The interaction also leads to the formation of a conical shaped bow shock that continues along with the perturbation expanding at $`0.2c`$, which is seen in Fig. 3a as a strong increase of the energy density emerging from the component and forming a small angle with the beam. In the bottom part of the component the bow shock is weaker. The effect of the collision against the edge of the beam is relatively small because of the very small impact angle of $`5^{}`$. A 2D analytic modeling of the impact shows the generation of a rarefaction instead of a shock for impact angles smaller than $`35^{}`$. \[This is a genuine relativistic effect (Pons, Martí, & Müller, 2000; Rezolla & Zanotti, 2002).\] After $`55R_b/c`$ the perturbation is no longer ballistic and no longer covers the whole beam’s width.

## 3 Emission

We compute the synchrotron emission from the hydrodynamic model assuming that the magnetic energy density is proportional to the particle energy density and that this proportionality remains constant throughout the whole computational domain (as in Gómez et al., 1995). We also assume that magnetic field is dynamically negligible and we account for the appropriate relativistic effects (including light travel time delays as in Gómez et al., 1997), aimed to obtain synthetic radio maps (Fig. 3) that can be compared with observations of superluminal sources. To relate emission features in the observer’s frame (O-frame;

Fig. 3) with their hydrodynamic counterparts, we provide a space-time diagram (Fig. 3).

Figure 3 shows the appearance of a large region of increased emission, associated with the imposed perturbation, passing by several standing knots (S1, S2, S3) caused by jet recollimation shocks. The large extension of this new emitting region is caused by the light travel time delays between the front and back of the perturbation, which stretch it by a factor $`(1\beta \mathrm{cos}\theta )^1`$ ($`\beta `$ and $`\theta `$ being the velocity –in units of $`c`$– of propagation and the viewing angle, respectively). As a consequence, the structure of the perturbation is magnified leading to brightness distribution variations within the component in the O-frame. This may have significant implications when interpreting the observations of superluminal sources. First of all, the quite common practice of identifying brightness peaks in radio maps with components may be misleading, as the component selected in this way may only be one of many brightness features caused by a single perturbation and may not be related to any physical structure on its own. Moreover, a component may result from different regions of the perturbation having different hydrodynamic properties (Fig. 3). For instance, identifying the brightness peak in the newly ejected emitting region in Fig. 3 as component M leads to variations in its apparent motion from 1.4 to 4.2$`c`$. The LAB-frame pattern Lorentz factors of the perturbation inferred from these values are 2 to 4.3, which cannot be associated to any flow or pattern speeds in the jet. On one hand, they are not related to the motion of any fluid element as the bulk Lorentz factors (Fig. 2) in the perturbation dynamically vary from the initial value of 6 (uniform within the perturbation) to values ranging from 4 (region B) to 9 (region A). On the other hand, the

pattern motions in the perturbation that correspond to the shocks confining regions A and B have Lorentz factors of 7 and 4, respectively, which differ significantly from the estimated values. The proper motion of M is almost constant during the last four epochs and equals 1.7$`c`$, corresponding to a LAB-frame pattern Lorentz factor of 2.2, which is only slightly smaller than the Lorentz factor of the back shock of region B during these epochs ($`2.7`$; Fig. 3).

The internal brightness distribution of the superluminal component M also changes due to the interaction of the perturbation with the ambient medium and the jet. The azimuthal position of the region of maximum interaction (corresponding to the maximum energy density in region B) varies with time because the perturbation moves (during its ballistic epoch) along a straight trajectory while the beam is helical. The resulting interaction, together with the squeezing of the perturbation when it passes through standing knots in the jet, leads to transverse motions of the component’s emission peak. A similar behavior has been observed in the jet of 3C 120 (Gómez et al., 2001), supporting the idea of a precessing jet in this source and of interactions between components and the external medium.

While region B generates the most significant features in the radio maps, no observable knot is produced by region A because Lorentz factors are higher in this region and the radiation is thus beamed into a cone smaller than the viewing angle. A larger viewing angle would beam region A and the resulting component would present a faster superluminal motion. Hence, the jet viewing angle may introduce a selection effect determining which parts of the perturbation appear as superluminal components (with different apparent speeds) in observed radio maps.

In contrast to M, the component H1 suddenly appears at some distance further downstream in the jet (Fig. 3). This pop-up component (PUC) results from the non-linear evolution of the secondary helical motion of the beam, and hence does not correspond to any bulk fluid motion. Its apparent speed is 1.4$`c`$, which agrees with its LAB-frame pattern Lorentz factor of 2.0 (Fig. 3). PUCs occur when a relativistic perturbation (observable or not) causes enhanced beamed emission which suddenly becomes observable. In our model the enhanced emission is produced by shock heated matter at the edge of region A of the perturbation, and the beaming is produced by the relativistic flow speeds in that region. The pop-up effect arises when the emitting region moving along the helical beam turns towards the observer, and the edge of the beamed radiation suddenly crosses the line of sight. PUCs appear to have been observed in actual sources (0420–014; Zhou et al., 2000) and provide a good example of a coupling between phase (helical) and bulk (the fluid in region A) motions leading to the formation of new components.

## 4 Conclusions

Our simulation shows that the non-linear hydrodynamic evolution of perturbations can determine the observed radio emission properties of superluminal sources, and that the interpretation of observed radio maps is error-prone when naively associating single shocks to superluminal components. Indeed, if the radio components of actual sources are correctly represented by those studied in our model, most observable features should not be related to fluid bulk motions, but instead to a complex combination of bulk and phase motions, viewing angle selection effects, and non-linear interactions between perturbations and the underlying jet and/or ambient medium. Further simulations spanning a wide range of the relevant parameters are underway.

M. A. A. acknowledges the EU-Commission for a fellowship (MCFI-2000-00504). This research was supported in part by the Spanish Dirección General de Ense anza Superior grant AYA-2001-3490 and through an agreement between the Max-Planck-Gesellschaft and the Consejo Superior de Investigaciones Científicas.


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# Multianode Photo Multiplier Tubes as Photo Detectors for Ring Imaging Cherenkov Detectors

## 1 Introduction

We have evaluated the 64-channel Multianode Photo Multiplier (MaPMT) as a candidate photo detector for the LHCb Ring Imaging Cherenkov (RICH) counters. The MaPMT contains a 8x8 array of 64 dynode chains enclosed in a single vacuum envelope. The window is made of UV glass instead of borosilicate which extends the transparency down to 200 nm. According to the manufacturer, the bi-alkali photo cathode has a quantum efficiency of 22% at a wavelength of 380 nm. The pitch between anode pixels is 2.3 mm. When accounting for the inactive 0.2 mm gaps between pixels, the MaPMT has an active area coverage of only 38%. The full angular coverage with 85% active area can be restored by mounting a fused silica lens with one flat and one spherical surface with a radius of curvature of 25 mm in front of the tube. The lens has a demagnification factor of about two-third and focuses the incoming photons onto the sensitive area of the MaPMT.

## 2 Test Beam Results

The sensitivity of the MaPMT to Cherenkov photons has been tested with particle beams of 120 GeV/c pions at the SPS accelerator at CERN. A detailed account of these tests is described in reference . Here we present the main results. A 3x3 cluster of closely packed MaPMTs has been mounted onto a prototype of the RICH 1 detector for the LHCb experiment. The radiator gas was CF4 at a pressure of 700 mbar and the photo cathode was set at -1000 V. To demonstrate that the MaPMTs will work at the LHC the data were recorded with the APVm chip running at 40 MHz.

In Figure 1 we show the results for two runs of 6000 events each, one with and one without the lenses mounted in front of the MaPMTs. In both cases, a ring of Cherenkov photons is clearly visible. The ratio of yields with and without lenses is 1.55 as is expected from a simulation. With the lenses the full Cherenkov ring is captured which demonstrates that MaPMTs can be closely packed to restore full geometrical acceptance. We observe $`6.96\pm 0.33`$ photo electrons per event, in very good agreement with the simulation. The corresponding figure of merit for a RICH detector is $`N_0=110\pm 7\mathrm{cm}^1`$.

In Figure 2 we show the pulse height spectrum for a single pixel. The data were corrected as follows. A common-mode baseline has been subtracted and signals due to cross-talk stemming from the read-out electronics have been removed. We clearly distinguish between the pedestal peak and the signal containing mainly one photo electron. Overlaid is a fit where $`\lambda `$ is the mean number of photo electrons.

## 3 LED Scans, Signal Shape, Low Gains

We have also studied the performance of MaPMTs in the laboratory. As a light source we used a blue LED coupled to a mono-mode fibre which could be moved with respect to the MaPMT by semi-automated optical stages. Two read-out systems were employed. One is the 40 MHz read-out with the APVm chip also used for the beam tests, and another one is based on CAMAC amplifiers and ADCs.

In addition to the nine tubes studied with test beams we obtained two more MaPMTs which, according to the manufacturer, have an increased quantum efficiency of maximum 25 - 27% at 360 nm. The focusing of these new tubes has been improved. Firstly, the acceptance at the outside edges of the active area of the MaPMT has been increased, and another focusing wire has been added. Secondly, the distance between the focusing grid and the entry slits to the dynode chain has been reduced. We have studied these new MaPMTs with a LED light scan. The data have been taken by moving the light source in steps of 0.1 mm along the front face of the MaPMT, with the photocathode at -900 V.

The pulse height spectra have been fit with a Gaussian curve as single photo electron signal shape. Shown in Figure 3 are the average single photon pulse height, $`s`$, and $`\lambda `$, the mean number of measured photo electrons as a function of the relative position along the tube. The gain is proportional to $`s`$ and the collection efficiency is closely related to $`\lambda `$. We observe that the edge pixels have a larger acceptance for the new MaPMT (solid histograms) with respect to the standard focusing tube (dashed histograms). Due to the improved focusing, both the gain and the collection efficiency are more homogeneous.

Most front-end chips developed for the LHC have been optimised for signals from Silicon sensors or micro-strip gas chambers with a charge of 26000 - 40000 $`e`$. At a voltage of 800 V between anode and photocathode the gain of the MaPMT is around 300000 which is about 10 times higher. To make use of one of these front-end chips for the the MaPMT a gain adaptation is needed. The preferred solution is to modify a preamplifier to a lower gain. A second possibility is to make use of an attenuator network. This has been used for the APVm read-out by means of an AC coupler. However this approach suffers from cross talk problems. A third way that we have investigated is the feasibility to run the MaPMTs at a lower gain.

To reduce the gain of the MaPMT we have changed the values of the resistors between the photo cathode, the first, second and the third dynode, respectively. The basic idea is to keep the gain at the first dynode while lowering the overall gain. The values for the default, a medium and a low gain option are given in Table 1.

The signal width is mainly due to the Poisson distribution for multiplication at the first dynode and can be estimated as $`g_1=s^2/\sigma ^2`$ where $`\sigma `$ is the Gaussian width of the single photon signal. Using the CAMAC read-out we have measured the overall gain of the MaPMT for a center and a border pixel as a function of the high voltage for the three different resistor chains.

In Figure 4 top) we plot $`s`$ as a function of the applied high voltage for the three different resistor chains. At a given voltage the gain of the MaPMT reduces by a factor of four for the low gain option. In the bottom plot we plot $`g_1=s^2/\sigma ^2`$ as a function of $`s`$. As expected we observe that $`g_1`$ increases with $`s`$. However there are no differences between the different resistor chains. We have repeated these measurements with the APVm read-out and the results agree.

We have studied the loss of signal below the threshold cut of $`5\sigma _{ped}`$ where $`\sigma _{ped}`$ is the Gaussian width of the pedestal peak. We have employed different fit methods. Besides a Gaussian signal shape we have implemented a fit which uses a Poisson distribution for the first two photo electrons . This method also allows for photons which pass through the photo cathode to be converted into photo electrons at the first dynode.

A Gaussian or a Poisson fit to the pulse height spectra are inadequate to describe the region of small signals close to the pedestal. In Figure 5 we show a pulse height spectra recorded with the CAMAC read-out and the photo cathode at -900 V. The superimposed fit (dotted line) allows for photo electrons to be produced at the first dynode. This fit still does not follow the data points correctly for small signals. There is a broad additional contribution of small pulse heights, but no evidence for a second peak in the data. Including a contribution due to production of photo electrons at the first dynode improves the description of the data. However, the fit improves the overall description of the data and, for the spectrum shown above, yields a gain at the first dynode of $`K_1=6.1`$ which is in agreement with expectations whereas the Gaussian and Poisson fit give $`K_1g_1=3.2`$ and $`K_1=4.1`$, respectively. The parameter $`\lambda `$ is independent of the fit method. Due to gain variations for pixels within a tube the loss of signal below the threshold varies from pixel to pixel. Using the Poisson fit including the “1st dynode” effect gives the most reliable results. The average signal loss of the 64 pixels of an MaPMT is 13%. We have also measured that the signal loss below threshold scales with $`s`$. Consequently, running at lower gains increases this loss.

## 4 Beetle Chip Studies

The APVm read-out is not compatible with the LHCb architecture. A possible candidate to read out the MaPMT is the Beetle chip. It can be run in analogue and binary mode. The binary mode has several advantages, as it ties in better with the Pixel HPD development for LHCb, described in reference , which also has a binary read-out, and for which a design of the Off-Detector Electronics (ODE) is underway. In addition there would be substantial cost savings.

A program has been undertaken to develop a Beetle adaptation to the MaPMT. By adding a charge and a voltage attenuator at the input of the preamplifier we have lowered the gain of the Beetle chip. Test structures have been produced and studied for this design. For the charge attenuator, measurements with a test charge agree very well with the simulation. The dynamic range of the preamplifier is 10 photo electrons. This preamplifier has been mounted onto a MaPMT and a pulse height spectrum from an LED light source has been measured. The signal from mostly single photo electrons is nicely separated from the pedestal. In this approach the load capacitance affects the gain which would require to keep the input capacitances of all channels within a few pF.

## 5 Magnetic Field Studies

A consequence of the optimisation of the LHCb spectrometer  is that now the RICH 1 photo detectors will be placed in a region where the magnetic field strength is about 40 mT. We have studied the sensitivity of the MaPMT to longitudinal and transverse magnetic fields up to $`B=35`$ mT. A set-up with 4 LEDs has been built to allow for a diffuse illumination of the MaPMT. The APVm read-out system was used.

We observe that the gain and the collection efficiency of a MaPMT decreases with increasing $`B`$ field. At $`B=3`$ mT, this effect is already sizable for the two edge rows of the tube. Averaged for all pixels of a tube the number of measured photo electrons for $`B3`$ mT is below 90% of that measured at 0 mT. The MaPMT can be shielded by enclosing it laterally with a $`\mu `$-metal case. This shielding should extend beyond the photo cathode of the tube. In Figure 6 we show the measured number of photo electrons for all pixels of a MaPMT relative to its value at 0 mT for the following set-ups: No shielding, 0.9 mm thick shielding extending by 13 mm and 20 mm, and 1.8 mm thick shielding extending by 13 mm and 20 mm. We observe that the shielding of the tube is effective. Already for the single 0.9 mm thick shielding the MaPMT functions in longitudinal magnetic fields up to 10 mT.

We have also studied the behaviour of the MaPMT in transverse fields. These measurements show that the MaPMT is insensitive to transverse magnetic fields up to 25 mT.

## 6 Conclusions

Using particle beams at the SPS at CERN we have successfully tested a 3x3 array of multianode photomultiplier tubes. We have demonstrated that by means of lenses mounted in front of the closely packed MaPMTs the Cherenkov photons are focused onto the sensitive area of the devices. Using a laboratory with LED light sources we have studied the performance and the signal shape of the MaPMTs in detail. A change in the focusing of the photo electrons onto the first dynode improved the homogeneity of the gain and of the light collection. The gain and width of the signal as well the signal loss have been measured for voltages between $`700`$ and $`1000`$ V. We have demonstrated that running the MaPMT at lower gains significantly increases the signal loss below threshold. Finally, we have evaluated the sensitivity of the MaPMT to longitudinal and transverse magnetic fields up to 35 mT.

## 7 Acknowledgements

I thank Reinhardt Chamonal, Stephan Eisenhardt, and Dave Websdale for the help in preparing this talk. This workshop was dedicated to the memory of Tom Ypsilantis whom I had the privilege to work with.


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# Granular clustering in a hydrodynamic simulation

## Abstract

We examine the hydrodynamics of a granular gas using numerical simulation. We demonstrate the appearance of shearing and clustering instabilities predicted by linear stability analysis, and show that their appearance is directly related to the inelasticity of collisions in the material. We discuss the rate at which these instabilities arise and the manner in which clusters grow and merge.

One of the key differences between a granular material and a regular fluid is that the grains of the former lose energy with each collision, while the molecules of the latter do not. Even when the inelasticity of the collisions is small, it can give rise to dramatic effects, such as the Maxwell Demon effecteggers  and, the topic of this paper, the phenomenon of granular clustering. Experimentskudrolli ; olafsen  and molecular dynamics simulationsgoldhirsch  alike show that low-density collections of grains (“granular gases”) in the absence of gravity do not become homogeneous with time, but instead form denser clusters of stationary particles surrounded by a lower density region of more energetic particles. A kinetic explanation for this behavior is that, when a particle enters a region of slightly higher density, it has more collisions, loses more energy, and so is less able to leave that region. This increases the local density and makes it more likely that additional particles are captured in the same way.

We are interested in describing this clustering behavior using hydrodynamics. There is considerable workkinetic  deriving granular hydrodynamics from kinetic theory, focusing on analytical treatments of the long-wavelength behavior of the system. Goldhirsch and Zanettigoldhirsch , for instance, describe clustering as the result of a hydrodynamic instability: a region of slightly higher density has more collisions, so more energy is lost and the region has a lower “temperature”temperature . Less temperature results in less pressure, and this lower pressure region in turn attracts more mass from the surrounding higher-pressure regions. Their paper uses long-wavelength stability analysis to show that, in a system of hydrodynamic equations similar to Eq. 1 below, higher-density regions do indeed have lower pressure, fueling the instability.

In this paper, we study the hydrodynamics of granular clustering in zero gravity, by using numerical simulation. Our motivation is to determine whether a coarse-grained description, in terms of local particle, momentum, and energy densities, can be used to treat characteristic behaviors of granular materials as a self-contained dynamical systemfn-turbulence . We show that the instabilities predicted by linear analysis do arise in our simulations, and discuss how the onset of these instabilities depends on the inelasticity of collisions in the material. We also show the manner in which clusters develop.

We begin with a number density field $`\rho `$, a flow velocity field $`𝐮`$, and a “temperature”temperature  field $`T`$. These are related by a standard set of hydrodynamic equations for granular materials, introduced by Haffhaff :

$`{\displaystyle \frac{\rho }{t}}`$ $`=`$ $`_i(\rho u_i)`$ (1)
$`{\displaystyle \frac{(\rho u_i)}{t}}`$ $`=`$ $`_iP_j(\rho u_iu_j)+_j(\eta _{ijkl}_ku_l)`$ (2)
$`{\displaystyle \frac{T}{t}}`$ $`=`$ $`_i(u_iT)+{\displaystyle \frac{1}{\rho }}_i(\stackrel{~}{\kappa }_iT)`$ (4)
$`+{\displaystyle \frac{1}{\rho }}\eta _{ijkl}(_iu_j)(_ku_l)\stackrel{~}{\gamma }T.`$
where repeated indices are summed over, and where $`P`$ is the pressure, $`\stackrel{~}{\kappa }`$ is the bare thermal conductivity, and $`\eta _{ijkl}=\stackrel{~}{\eta }(\delta _{ik}\delta _{jl}+\delta _{il}\delta _{kj}+\delta _{ij}\delta _{kl})`$ is the isotropic bare viscosity tensor. These equations bear much in common with those for normal fluidskim . The most important addition is that of the term $`\stackrel{~}{\gamma }T`$, which accounts for the inelasticity of collisions; the parameter $`\stackrel{~}{\gamma }`$ is proportional to $`(1r^2)`$, where $`r`$ is the coefficient of restitution. Using kinetic theory resultshaff , the transport coefficients are chosen to depend on temperature and density:

$`\stackrel{~}{\kappa }=\kappa T^{1/2}`$ (5)
$`\stackrel{~}{\eta }=\eta \rho T^{1/2}`$ (6)
$`\stackrel{~}{\gamma }=\gamma T^{1/2}.`$ (7)
Typically, work in granular hydrodynamics is done in low-density regimes, where grains may be treated as point particles interacting via collisions. When simulating aggregation, however, one must take excluded volume into account. We do this by introducing a barrier in the pressure $`P(\rho )`$ at some maximum (close-packed) density $`\rho _0`$. This is in addition to the usual hydrodynamic pressure $`\rho T`$. We choose in particular the simple quadratic form

$$P=\rho T+U(\rho ^2\rho _0^2)\theta (\rho \rho _0),$$
(8)
where $`U`$ is a positive parameter, $`\theta (x)`$ is the unit step function, and $`\rho _0`$ is the close-packed density. This method, which we introduced in an earlier paperhill , is a simple way to model the incompressibility of the system at high densitiesgollub .

We evaluate our equations in two dimensions using a finite-difference Runge-Kutta method, on a square lattice with periodic boundary conditions. (See footnote fn-method  for more details.) The lattice spacing is chosen to be large enough so that each site contains a number of grains, and we can consider the density to be a continuous variable. We start with random initial conditions $`\rho =0.1+0.001r_1(z,x)`$, $`u_z=r_2(z,x)`$, $`u_x=r_3(z,x)`$, and $`T=1+0.1r_4(z,x)`$, where $`r_i(z,x)`$ are random numbers chosen between $`1`$ and $`1`$. The model’s other parameters for the data presented here are $`\eta _0=25`$, $`\kappa _0=1`$, $`U=4\times 10^4`$, $`\rho _0=0.2`$, and $`\gamma `$ taking on several different values. All numbers given here are in dimensionless unitsfn-units . Our time step in these units is $`\mathrm{\Delta }t=10^3`$.

We begin with a system that is $`64\times 64`$ in size. The homogeneous state with which we initialize our system is already a solution to the equations above. In this initial homogeneous cooling state, the velocity and all gradients vanish, and the temperature decays with time due to the inelasticity. Eq.1 reduces to

$$\frac{T}{t}=\gamma T^{3/2},$$
(9)
which yields Haff’s cooling law, $`T(t)=T(0)(1+t/t_0)^2`$. This state is seen universally in simulationsDB97 ; LH99 ; NBC02 ; McY96 , but only initially, for it is unstable to hydrodynamic modesgoldhirsch , resulting in a long-range shear flow followed by the clustering instability mentioned above.

Figure 1 shows the decay of the average temperature as a function of time in our simulation, for three different values of the inelasticity parameter $`\gamma `$. The initial decay approximately follows the predicted $`2`$ exponent, while for later times the temperature decays at a slower rate as the instabilities agitate the systemLH99 ; NBC02 . In the limit of low inelasticity, the maximal rate of decay more closely approaches Haff’s predicted inverse-square behavior (Fig. 2). (Note, however, that the temperature will not decay at all in a completely elastic system.) In more inelastic systems, the hydrodynamic instabilities kick in sooner and compromise the homogeneity of the system. One could characterize the time it takes for the instabilities to emerge by the time it takes for the temperature to reach its fastest decay rate. Figure 3 shows that this onset time decreases with respect to the inelasticity parameter as a power-law with an exponent of $`4/3`$.

The first instability that is predicted to dominate the homogeneous solution is a hydrodynamic shearing mode: two bands of material moving in opposite directions. This has been seen in several molecular dynamic simulationsDB97 ; McY96 , Fig. 4 shows how it has developed in our system as two horizontal shear bands.

Figure 5 shows that our system develops a clustering instability as well. Note that the single cluster takes on a compact shape, which is surprising given that there is no surface tension in our model. If clusters are supposed to grow by accretion, then one would expect a ramified structure. This puzzle becomes clearer as we consider a larger system after further evolution. Figure 6 shows that clusters first form in these compact shapes, but as time goes on they reach out to their neighbors, stretching into the more stringlike forms seen in simulationgoldhirsch . In hindsight, we are able to see this behavior in the smaller system as well, where the single cluster interacts with itself through the periodic boundaries.

Finally, to demonstrate that this clustering instability is the result of the inelastic parameter, we compare the width of the density distribution for inelastic systems with the distribution for the elastic case $`\gamma =0`$ (Fig.7). In the absence of inelasticity, the density distribution collapses to a delta function, indicating complete homogeneity.

Our results show that the shearing and clustering instabilities, identified by Goldhirsch and Zanetti using a simplified version of the above equations, exist in the complete nonlinear granular hydrodynamic equations 1. Haff’s cooling law is obeyed in the limit of small inelasticity, but in general the instabilities become relevant before the system has a chance to completely homogenize. The power-law dependence of the onset time for these instabilities on the inelasticity, and the $`4/3`$ exponent in particular, are interesting; we have not found any reference to these in the literature. Also interesting is the way in which these clusters develop from compact structures into networks which span the system. It is not clear whether an individual cluster begins to stretch out because of the proximity of its neighbors, or because of effects due to its increasing surface size. One can imagine that the behavior of this system could change as we alter the total amount of mass in the system.

We thank Professor Todd DuPont for his assistance in constructing our simulations, and Professors Heinrich Jaeger, Sidney Nagel, and Thomas Witten for helpful conversations. This work was supported by the Materials Research Science and Engineering Center through Grant No. NSF DMR 9808595.


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# Theory of excited state absorptions in phenylene-based 𝜋-conjugated polymers

## I Introduction

The applications of $`\pi `$-conjugated polymers in optical emission devices such as organic light emitting diodes Friend et al. (1999) and laser active media Tessler et al. (1996); Hide et al. (1996); Frolov et al. (1997) have led to intensive investigations of photoluminescent materials like PPP and PPV, their derivatives, and structurally related ladder type materials. Nonlinear spectroscopy, including both ultrafast photoinduced absorption (PA) measurements Yan et al. (1994); Hsu et al. (1994); Leng et al. (1994); Frolov et al. (2000, 2001); Klimov et al. (1998); Kraabel et al. (2000); Silva et al. (2001); Gadermaier et al. (2002a, b) and third order nonlinear optical measurements like electroabsorption (EA) Leng et al. (1994); Liess et al. (1997); Martin et al. (1999), third harmonic generation (THG) Mathy et al. (1996) and two-photon absorption (TPA) Frolov et al. (2001); Baker et al. (1993); Lemmer et al. (1993) have been carried out extensively to probe the even parity excited states that are dark under one–photon excitation but are two–photon allowed. In particular, interest in PA experiments stems from the observation that PA at high energies is followed by charge separation, with the creation of charged polarons on neighboring chains. Derivatives of PPV, for example, have been investigated by Frolov et al. Frolov et al. (2000, 2001), who found two distinct PA bands in these systems, “low energy” PA1 and “high energy” PA2, occurring at $``$ 0.8 eV and $``$ 1.3 – 1.4 eV, respectively. Frolov et al. ascribe PA1 to the excited state absorption from the optical 1Bu state to the so-called mAg state (where m is a chain length dependent unknown quantum number), whose nature has been discussed extensively by theorists in the context of nonlinear spectroscopy of both luminescent polymers like PPV as well as nonluminescent linear chain polyacetylenes and polydiacetylenes Dixit et al. (1991); Chandross et al. (1999); McWilliams et al. (1991); Soos and Kepler (1991); Abe et al. (1992); Beljonne et al. (1997); Yaron (1996); Race et al. (2001). PA2 has been ascribed by Frolov et al. to the excited state absorption to a higher energy kAg state (where k is again an unknown quantum number), whose counterpart does not exist in the linear chain polymers, according to these authors. Interestingly, the relaxation dynamics of PA1 and PA2 are very different: while the mAg decays back to the optical 1Bu exciton by internal conversion, the kAg undergoes a different relaxation pathway that leads to dissociation into long-lived polaron pairs that are probably interchain. Based on this, the authors have speculated that the electronic character of the kAg is different from the mAg.

Similar behavior have been observed by several different groups Klimov et al. (1998); Kraabel et al. (2000); Silva et al. (2001); Gadermaier et al. (2002a, b), who have studied both PPV derivatives and structurally related materials like polyfluorene, ladder-type PPP and oligomers of the latter. There exist apparent subtleties in comparing some of these experimental results with those of Frolov et al. Frolov et al. (2000, 2001), as the PA measurements in some of these cases were carried out only in the high energy region ($`>`$ 1.4 eV) Gadermaier et al. (2002a, b), and therefore the induced absorption termed PA1 by these latter authors actually corresponds to PA2 of Frolov et al. Frolov et al. (2000, 2001) (see section V for details). Apart from this difference in nomenclature, the fundamental observation in all cases appear to be the same, viz., Ag states beyond some threshold energy mediate interchain charge–transfer. As an aside, we remark that it has also been claimed from ultrafast PA measurements in the wavelength region of infrared active vibrational modes that charge carriers are generated directly at the optical threshold, and that the quantum efficiency of charge generation is wavelength independent Moses et al. (2000); Miranda et al. (2001). This last conclusion has, however, been challenged by Silva et al. Silva et al. (2001), whose demonstrations that ultrafast photogeneration of charge carriers in a polyfluorene derivative is a consequence of sequential absorption to an Ag state that is at nearly twice the energy of the optical exciton (note that this is different from the kAg), and that there occur negligible yield of polarons under continuous wave conditions (where excitation to high energy Ag states does not occur) argue against the direct photogeneration scenario. The occurrence of EA Liess et al. (1997); Österbacka et al. (2002) and TPA Frolov et al. (2001) at the same energy where PA2 occurs are yet other demonstrations of the existence of a kAg state that is dipole-coupled to the 1Bu. Recent photo-current excitation cross-correlation experiments Zenz et al. (2001); Müller et al. (2001) also support the sequential absorption picture. We shall therefore make no further comments on the experiments by Moses et al. Moses et al. (2000); Miranda et al. (2001), which in any case is of secondary interest of this work; our primary interest is to understand the different electronic natures of the mAg and the kAg at a qualitative level.

Initial progress in theoretical understanding of possibly different classes of even parity states in phenylene-based conjugated polymers was made by Chakrabarti and Mazumdar Chakrabarti and Mazumdar (1999), who examined the excited states of biphenyl and triphenyl within the Pariser–Parr–Pople model Pariser and Parr (1953); Pople (1954). Although many–body techniques used by these authors were accurate (exact and quadruple–CI, hereafter QCI), the basis sets used were limited and included only the degenerate pairs of highest occupied molecular orbitals (HOMOs) and lowest unoccupied molecular orbitals (LUMOs) of benzene. Each pair of degenerate MOs consists of a delocalized MO and a localized MO, with the $`\pi `$ electron densities vanishing on the para carbon atoms in the latter Rice and Gartstein (1994); Cornil et al. (1994); Chandross et al. (1994); Shimoi and Abe (1996). Chakrabarti and Mazumdar showed that the two-photon states in these molecules were not only superpositions of 1e–1h and 2e–2h excitations involving the delocalized bonding ($`d`$) and antibonding ($`d^{}`$) MOs, there occurred also strong admixing with 2e–2h excitations involving localized bonding ($`l`$) and antibonding ($`l^{}`$) MOs. The authors therefore suggested that there occurred multiple kinds of Ag states in phenylene–based conjugated polymers. According to these authors, Ag states upto some threshold could qualitatively be understood within the space of $`d`$ and $`d^{}`$ MOs only. The mAg belongs to this class of Ag states. Beyond the threshold, however, there occurs a crossover to Ag states which have strong contributions from 2e–2h excitations involving $`l`$ and $`l^{}`$ MOs. We shall hereafter write such states as $`(dl^{})^2`$ and $`(ll^{})^2`$ double excitations (as opposed to the $`(dd^{})^2`$ double excitations with lower energies). Note that in all cases we do not make finer distinctions between configurations in which the hole or electron pairs occupy the same or different MOs (thus $`(dl^{})^2`$ includes the 2e–2h excitations $`(dl^{};ld^{})`$). According to these authors, the kAg belonged to this second class of Ag states. No attempt was made to explain the charge separation and the calculations were limited strictly to explaining the possible difference between the mAg and the kAg.

The calculations by Chakrabarti and Mazumdar Chakrabarti and Mazumdar (1999) are suggestive but far from complete. Firstly, all calculated Ag states appeared to have nearly equal admixtures of $`(dd^{})^2`$, $`(dl^{})^2`$, $`(ld^{})^2`$ and $`(ll^{})^2`$, which would appear to contradict the conjecture about different classes of Ag states. It was claimed that the strong mixing between different classes of 2e–2h excitations was a consequence of the severe length restrictions in the previous calculations and that with increasing conjugation length distinct Ag states dominated by different kinds of 2e–2h excitations would emerge. The actual demonstration of this requires going beyond the earlier small oligomer calculations. A second shortcoming of the earlier calculations is that they completely ignored the outer delocalized MOs of each benzene (as well as the MOs due to the vinylene segments in case of PPV). The complete band structure of PPV can be seen, for example, in reference Chandross et al., 1994, where one finds that in addition to the innermost delocalized valence and conduction bands (referred to as simply $`d`$ and $`d^{}`$ in the above, but hereafter as $`d_1`$ and $`d_1^{}`$) there occur also outer delocalized bands ($`d_2`$ and $`d_2^{}`$ ; $`d_3`$ and $`d_3^{}`$) that lie below (above) the $`l`$ ($`l^{}`$) bands (the difference between PPV and PPP is the absence of the outermost $`d_3`$ and $`d_3^{}`$ bands in PPP). The neglect of the outer $`d`$-bands raises the question whether higher energy PA is not to qualitatively different Ag states involving the localized levels, but to states that are dominated by excitations involving the outer $`d`$-bands. Finally, the previous calculations were not useful for even qualitative comparisons of relative energies and oscillator strengths of theoretical PA1 and PA2, again a consequence of the very severe length restriction.

In view of the above, we believe that a thorough and accurate theoretical investigation of the two-photon states of oligomers of PPP and PPV is in order. In the present paper, we present large scale correlated calculations employing the multireference singles and doubles configuration interaction (MRSDCI) method Buenker and Peyerimhoff (1974); Tavan and Schulten (1987) on longer oligomers of PPP and PPV within a correlated electron Hamiltonian. Unlike the previous calculations Chakrabarti and Mazumdar (1999), higher energy MOs or bands are not ignored. We take considerable care that the results we report are accurate, by imposing strict convergence criteria on our MRSDCI calculations. For PPP, calculations are presented for oligomers containing three to five benzene rings. We refer to these as PPP3, PPP4 and PPP5, respectively. In the case of PPV, we consider oligomers that terminate with benzene molecules at both ends, in order to preserve spatial symmetry, and present MRSDCI results for oligomers containing three (PPV3) and four (PPV4) benzene rings. While these oligomers are still relatively short, we believe that it is far more important to incorporate electron correlation effects to high order than to go to longer oligomers.

The results of our calculations can be summarized as follows. Firstly, our computed PA spectra resemble the experimental PA spectra qualitatively: in all cases we find the theoretical PA1 to be much stronger than PA2. We discuss why the calculated Ag states are expected to occur at energies where PA1 and PA2 are observed experimentally. Secondly, our present relatively longer chain calculations do indeed find lower and higher energy two–photon states whose 2e–2h components are significantly different, as would be required to claim that these belong to distinct classes. The different nature of the higher energy two–photon state that we believe to be the kAg may explain the charge separation from this state. While this last statement is a speculation currently, it is supported by earlier photocurrent studies Köhler et al. (1998). A third result involves our determination that the mAg is not the lowest two-photon excited state in any of the systems we have studied (i.e., the quantum number $`m>`$ 2), even though the 2Ag occurs above the 1Bu in these systems. This particular result is in agreement with other recent theoretical work based on the limited basis of $`d_1`$ and $`d_1^{}`$ bands Lavrentiev et al. (1999); Beljonne (2001). As we remark later, this may also have experimental significance. Finally, we also find that as observed before from fittings of the linear absorption in PPV films Chandross et al. (1997), the standard Ohno parameters Ohno (1964) may be too large for even qualitative fittings of the PA at high energies, and a previously used phenomenological screened Coulomb parametrization Chandross et al. (1997) gives more satisfactory results.

In the next section we present our theoretical model and discuss the details of the MRSDCI approach as adopted here. In section III we present a brief review of the theory of linear absorption in the polyphenylenes, to point out that there occur distinct classes of one–excitation in the systems of interest, thereby suggesting the idea of distinct two–excitations. In section IV we present our theoretical results. This is followed by our conclusions and discussions of the scope of future work.

## II The theoretical model and methodology

We consider oligomers of PPP and PPV within the Pariser-Parr-Pople model Hamiltonian,

$`H={\displaystyle \underset{ij,\sigma }{}}t_{ij}(c_{i\sigma }^{}c_{j\sigma }+c_{j\sigma }^{}c_{i\sigma })+`$
$`U{\displaystyle \underset{i}{}}n_in_i+{\displaystyle \underset{i<j}{}}V_{ij}(n_i1)(n_j1)`$ (1)
where $`ij`$ implies nearest neighbors, $`c_{i\sigma }^{}`$ creates an electron of spin $`\sigma `$ on the $`p_z`$ orbital of carbon atom $`i`$, $`n_{i\sigma }=c_{i\sigma }^{}c_{i\sigma }`$ is the number of electrons with spin $`\sigma `$, and $`n_i=_\sigma n_{i\sigma }`$ is the total number of electrons on atom $`i`$. The parameters $`U`$ and $`V_{ij}`$ are the on–site and long–range Coulomb interactions, respectively, while $`t_{ij}`$ is the nearest neighbor one-electron hopping matrix element that includes bond alternation and connectivity. The parametrization of the intersite Coulomb interactions is done in a manner similar to the Ohno parametrization Ohno (1964)

$$V_{i,j}=U/\kappa (1+0.6117R_{i,j}^2)^{1/2}\text{,}$$
(2)
where $`\kappa `$ is a parameter which has been introduced to account for the possible screening of the Coulomb interactions in the system Chandross et al. (1997); Castleton and Barford (2002). We have examined both the standard Ohno parameters ($`U`$ = 11.13 eV, $`\kappa `$ = 1.0), as well as a particular combination of $`U`$ and $`\kappa `$ ($`U`$ = 8.0 eV, $`\kappa `$ = 2.0) that was shown previously to be satisfactory at a semiquantitative level for explaining the full wavelength dependent ground state absorption spectrum of PPV Chandross et al. (1997). We shall hereafter refer to this second set of parameters as screened Ohno parameters. As far as the hopping matrix elements are concerned, we took $`t=2.4`$ eV for the C – C bond in benzene rings. The hopping corresponding to the interbenzene single bond in the PPP oligomers was taken to be $`t=2.23`$ eV. For the vinylene linkage of the PPV oligomers, we chose the hopping elements to be $`2.2`$ eV for the single bond, and $`2.6`$ eV for the double bond. We considered PPP and PPV oligomers in their planar configurations, with the conjugation direction along the $`x`$ axis. Thus the symmetry group of PPP oligomers is $`D_{2h}`$, while that of PPV oligomers is $`C_{2h}`$. Since both symmetry groups have inversion as a symmetry element, the many electron states of these oligomers can be classified according to this symmetry. The two-photon states of both the PPP and PPV oligomers belong to the Ag irreducible representation (irrep) of the respective symmetry group, while the one-photon states belong to the Bu irrep for PPV, and B1u ($`x`$-polarized), and B2u ($`y`$-polarized) irreps for the oligo-PPPs. Since, here we are concerned mainly with the response of these systems to the $`x`$-polarized photons, therefore, henceforth, for PPP oligomers also we will refer to the B1u states as Bu states. In all cases the calculated PA corresponds to the excited state absorption from the optical 1Bu state. In all the many-body calculations presented in this work, full use of the stated point group symmetries was made.

As stated above, the correlated electron calculations were done using the MRSDCI approach, which is a powerful CI technique Buenker and Peyerimhoff (1974) that has been used previously for linear chain polyenes by Tavan and Schulten Tavan and Schulten (1987) as well as others Beljonne et al. (1997), and by us to calculate the excited state ordering in polyphenyl- and polydiphenylacetylenes Ghosh et al. (2000). As discussed in reference Ghosh et al., 2000 we use very stringent convergence criterion for all excited states. The methodology behind the MRSDCI calculations is as follows. The calculations are initiated with a restricted Hartree-Fock (RHF) computation of the ground state of the oligomer concerned, followed by a transformation of the Hamiltonian from the site representation (Eq. 2) to the HF molecular-orbital representation. Subsequently, a singles-doubles CI (SDCI) calculation is performed, the different excited states in Ag and Bu subspaces are examined, and the Nref configuration state functions (CSFs) making significant contributions to their many-particle wave functions are identified. The next step is the MRSDCI calculation for which the reference space consists of the Nref CSFs identified in the previous step, and the overall Hamiltonian matrix now includes configurations that are singly and doubly excited with respect to these reference CSFs (thereby including the dominant triply and quadruply excited configurations). The new ground and excited states are now re-examined to identify new CSFs contributing significantly to them so as to augment the reference space for the next set of MRSDCI calculations. This procedure is repeated until satisfactory convergences in the excitation energies of the relavant states are achieved. By the time convergence is achieved typically all CSFs with coefficients of magnitude $`0.1`$ or more in the corresponding many-particle wave functions have been included in the MRSDCI reference space. Naturally, this leads to very large CI matrices. To give some idea of the highly correlated nature of the wavefunctions of the excited states we have examined and the level of accuracy in our calculations, in Table 1 we have listed the number of reference functions that were used for each symmetry subspace of PPP3, PPP4 and PPP5, respectively, as well as the overall sizes of the Hamiltonian matrix in each case (note that for PPP3 the method used was QCI rather than MRSDCI). The number of MRSDCI reference functions are larger in the Ag subspaces than in the Bu subspace because while only the 1Bu was optimized in the Bu subspace, many different Ag states (all those with significant transition dipole couplings with the 1Bu) had to be simultaneously optimized in the Ag subspace. The $`N_{ref}`$ in Table 1 should be compared to the few (usually 2 or 3) reference states that are retained in calculations of the lowest Ag states Tavan and Schulten (1987). To the best of our knowledge, the present calculations are the most accurate correlated electron calculations that incorporate the full basis set for the polyphenylenes.

## III Theory of ground state absorption and its implication

Before we present our calculations of PA, it is useful to recall the results of calculations of the ground state absorption Rice and Gartstein (1994); Cornil et al. (1994); Shimoi and Abe (1996); Chandross et al. (1994, 1997). This is because multiple classes of final states are relevant also in ground state absorption, and as we indicate below analysis of the ground state absorption strongly suggests that there should occur multiple classes of two-photon states. Within band theory ($`U`$ = 0) ground state absorption consists of 1e–1h excitations that are low energy $`d_1d_1^{}`$, high energy $`ll^{}`$, and intermediate energy $`d_1l^{}`$ and $`ld_1^{}`$, with the intermediate energy absorption band occurring exactly half way in between the low and high energy absorption band. Here we have ignored absorptions involving $`d_2`$, $`d_2^{}`$ etc. bands, as excitations involving these bands lie outside the range of experimental wavelengths. The $`d_1d_1^{}`$ and $`ll^{}`$ bands are polarized along the $`x`$-direction in PPP and predominantly along the $`x`$-direction in PPV, while the $`d_1l^{}`$ and $`ld_1^{}`$ bands are polarized along the $`y`$-direction and predominantly along the y-direction, respectively. Experimentally in PPV there occur absorptions at $``$ 2.4 eV, 3.7 eV, 4.7 eV and $``$ 6.0 eV, respectively. These have been explained within a correlated electron picture: absorptions at 2.4 eV and 6.0 eV are due to $`d_1d_1^{}`$ and $`ll^{}`$ exciton states, respectively Rice and Gartstein (1994); Cornil et al. (1994); Chandross et al. (1997); Shimoi and Abe (1996) the absorption at 3.7 eV is to a higher energy $`d_1d_1^{}`$ exciton Chandross et al. (1997); and finally, the absorption at 4.7 eV is to the “plus” linear combination of the excitations $`d_1l^{}`$ \+ $`ld_1^{}`$ Rice and Gartstein (1994); Cornil et al. (1994); Chandross et al. (1997); Shimoi and Abe (1996). The corresponding “minus” linear combination, $`d_1l^{}`$$`ld_1^{}`$, occurs also at about 3.7 eV Rice and Gartstein (1994); Cornil et al. (1994); Chandross et al. (1997); Shimoi and Abe (1996), but is forbidden in linear absorption. All of these assignments have been confirmed by polarization studies of absorptions in stretch–oriented samples Chandross et al. (1997); Comoretto et al. (2000); Miller et al. (1999).

The relevance of these known results to the present case are as follows. Energetically, the kAg in PPV is at $``$ 3.6 – 3.8 eV Frolov et al. (2000, 2001). Since ground state absorption occurs to a high energy $`d_1d_1^{}`$ excitation of Bu symmetry in this energy region, in principle, the kAg can simply be a similar $`d_1d_1^{}`$ excitation of Ag symmetry. If this were true, the mAg and the kAg would be qualitatively similar, and charge carrier creation from the kAg (but not from the mAg) can only be a consequence of possibly greater e–h separation in the kAg. An alternate possibility is that the kAg is dominated by configurations that are fundamentally different. Recall that the occurrence of the 2Ag below the 1Bu in polyacetylenes and polydiacetylenes is a general many–body phenomenon: Ag eigenstates having strong 2e–2h contributions from specific MOs can be close in energy, or can even occur below Bu eigenstates that are dominated by 1e–1h excitations involving the same MOs. Since the lowest energy 1e–1h excitations involving the $`d_1l^{}`$ and $`ld_1^{}`$ excitations (the minus linear combinations mentioned above) occur at $``$ 3.7 eV, it is to be anticipated that many-body Ag eigenstates that are dominated by $`(d_1l^{})^2`$ and $`(ld_1^{})^2`$ occur also within the same energy range. In principle then, the kAg can also be dominated by 2e–2h components involving the $`l`$ and $`l^{}`$ bands, and be qualitatively different from the mAg. As shown in the following sections, we do indeed find evidence for such Ag states with significant dipole coupling to the 1Bu.

## IV Results of correlated electron calculations

### IV.1 Choice of parameters

As we show below electron correlation effects on different kinds of CSFs are different. This necessitates proper choice of the Coulomb parameters in Eq. II. Here we show that the bare Ohno parameters are not suitable for high energy states of PPP and PPV. In Fig. 1 we show the calculated excited state absorption from the 1Bu state for PPP3, for the case of Ohno parameters, obtained with the QCI approach. The spectral features I and II are due to the 2Ag and the 4Ag states of the oligomer, respectively, while the strong feature III has contributions from both the 7Ag and the 8Ag. The close proximity of spectral feature I to the 1Bu in the theoretical spectrum makes this outside the wavelength range within which the experimental PA features are observed. In principle, it might be possible to observe this 2Ag state in TPA. In reality, Fig. 1 indicates that the strength of the TPA to the 2Ag would be rather weak. This is because the calculated PA in Fig. 1 corresponds to linear absorption from the 1Bu and hence consists of only positive terms; in contrast, the third order susceptibility corresponding to TPA contains both positive and negative terms Guo et al. (1994), and the relative strength of the 2Ag peak in Fig. 1 therefore corresponds to an upper limit for TPA. Thus only calculated PA features II and III in Fig. 1 should be compared to experiments. The relative oscillator strengths of II and III are exactly opposite to the relative oscillator strengths of PA1 and PA2, which makes the calculated PA inconsistent with experiments Frolov et al. (2000, 2001).

In order to probe this further, we have examined the final states of all PA features in considerable detail. Each of these wavefunctions is highly correlated, and is a superposition of numerous configurations. In order to obtain broad classifications of the different Ag states we expand the correlated wavefunction as,

$`|nA_g={\displaystyle \underset{i}{}}a_i|d_1d_1^{}_i+{\displaystyle \underset{j}{}}b_j|(d_1d_1^{})^2_j`$
$`+{\displaystyle \underset{k}{}}c_k|(d_1l^{})^2_k+\mathrm{}.`$ (3)
In the above nAg is an arbitrary Ag state and each term on the right hand side contains all CSFs of a given class (for example, $`|d_1d_1^{}_i`$ is the $`i`$th configuration of the type $`d_1d_1`$ whose coefficient in nAg is $`a_i`$). The right hand side of Eq. IV.1 is obviously not complete and the …. implies the existence of many other types of excitations $`d_1d_2^{}`$, $`(d_1d_2^{})^2`$, etc. Once terms have been collected in the above manner, it is possible to quantify the overall contribution of excitations of a given kind (for example, $`_i|a_i|^2`$ is the total contribution by excitations of the type $`d_1d_1^{}`$). In Table II we have given the contributions of each kind of excitation that describe the 2Ag, 4Ag, 7Ag and 8Ag wavefunctions. The overall sum of the contributions corresponding to each Ag state does not add up to 1, since we have retained only the important excitations with coefficients at least 0.1 in our expansions of the wavefunctions. As seen from Table II, the 2Ag wavefunction is very similar to the 2Ag of linear chain polyenes, in that it is predominantly a superposition of 1e–1h $`d_1d_1^{}`$ and 2e–2h $`(d_1d_1^{})^2`$ excitations. This supports the earlier application of the effective linear chain model for the description of this state in PPV and PPP Soos et al. (1992). The two states 7Ag and 8Ag also have strong contributions from $`(d_1d_1^{})^2`$, and weak contributions from $`(d_1l^{})^2`$ or $`(ld_1^{})^2`$. These states are therefore physically related to the mAg that has been discussed before in the context of nonlinear spectroscopy. In contrast to the above states, the 4Ag has much stronger contribution from $`(d_1l^{})^2`$ and $`(ld_1^{})^2`$. The occurrence of a $`(d_1l^{})^2`$ and $`(ld_1^{})^2`$ type state below the predominantly $`(d_1d_1^{})^2`$ states suggests that (a) electron correlation effects are stronger on CSFs involving the localized MOs than on CSFs involving only delocalized MOs, and (b) the bare Ohno Coulomb parameters are too strong to describe PPP or PPV films, since it is the large magnitude of the Ohno correlation parameters that causes the effective crossing of eigenfunctions of different types, which in turn leads to the reversal of the intensities of the absorption bands as a function of energy.

Although in the above we have shown the theoretical PA spectrum only for PPP3, we emphasize that identical behavior is seen with the Ohno parameters for PPP4, PPP5, PPV3 and PPV4. In all cases the intensity profile of the excited state absorption is opposite to that observed experimentally, and wavefunction analysis indicates that this is due to the ordering of the states as in the above.

That the Ohno parameters are too large for high energy states of PPV, PPP etc. was suggested earlier from calculations of ground state absorption of PPV Chandross and Mazumdar (1997). With the Ohno parameters, the calculated $`ll^{}`$ absorption (polarized along the $`x`$-direction) occurs below the calculated $`(d_1l^{}+ld_1^{})`$ absorption ($`y`$-polarized) Chandross and Mazumdar (1997), in contradiction to polarized absorption experiments Chandross et al. (1997); Comoretto et al. (2000); Miller et al. (1999). As pointed out in reference Chandross and Mazumdar, 1997, this last theoretical result was obtained even for trans-stilbene in one of the earliest computational works Beveridge and Jaffe (1965). Very recently, Castleton and Barford Castleton and Barford (2002) have done careful analysis of a very large number of high energy excited states in benzene, biphenyl and trans–stilbene using full–CI and have reached the same conclusion. Within Eq. 2, the authors suggest $`U`$ = 7.2 eV and $`\kappa `$ = 1.36 for the hydrocarbon matrix condensed phases of the above molecules, along with finer modifications of the hopping integrals. These values of $`U`$ and $`\kappa `$ are close to the $`U`$ = 8 eV and $`\kappa `$ = 2.0 that were suggested in reference Chandross and Mazumdar (1997), and that we use in our calculations in the next section. Given that our goal is semiquantitative only (recall that our calculations are for relatively short oligomers while the available experimental results include those for much longer chains) finetuning of the parameters as done by Castleton and Barford would be premature. The necessity to incorporate screening of the bare Ohno Coulomb parameters in order to fit the high energy excited states in condensed phases of conjugated polymers have also been discussed by Moore and Yaron Moore and Yaron (1998), from a different perspective.

### IV.2 PA spectra with screened Coulomb parameters

In Fig. 2 we have shown the calculated excited state absorptions for (a) PPP4, (b) PPP5, (c) PPV3 and (d) PPV4 for $`U`$ = 8.0 eV and $`\kappa `$ = 2. In all cases our abcissa is the energy scaled with respect to E(1Bu). As pointed out before Mazumdar et al. (1992), convergence in the scaled energies of high energy states with increasing chain length is not expected in this region of relatively short chain lengths. This is because the lowest energy excitations (for example, the 1Bu and the 2Ag) converge with increasing chain length much faster than the higher energy states. Taken together with the discrete nature of the excited states, this can indicate an apparent increase in the scaled energy of the high energy excited state with increasing chain length, even as the actual energy is decreasing. This is exactly what happens between PPP4 and PPP5, and between PPV3 and PPV4 in Fig. 2. Quantitative comparisons of the scaled energies of the theoretical excited state absorption bands and those of the experimental PA bands thus cannot be expected, particularly in view of the fact that the relative location of the Ag state dominated by $`(d_1l^{})^2`$ excitations is very sensitive to relatively minor changes in the Coulomb correlation parameters (see previous subsection and also below). The energies and the relative intensities of the theoretical induced absorptions are therefore for semiquantitative comparisons only. From Figs. 2(c) and 2(d), it can be concluded that PA1 in PPV derivatives is due to the calculated spectral feature II which peaks slightly below 0.4 $`\times `$ E(1Bu), which would correspond to about 0.9 eV in long chain PPV derivatives (with E(1Bu) $``$ 2.2 eV). This is quite close to experimental PA1 energy in PPV derivatives Frolov et al. (2000, 2001). We remark on the PA energies in PPP derivatives in the next section, where more detailed comparisons to experiments are made. In all cases, the theoretical PA feature I corresponds to the 2Ag (see below), and the close proximity of this state to the 1Bu again suggests that this state is outside the wavelength region within which experimental PA has been observed.

For detailed understanding, in Table III we have described the wavefunctions of each of the final Ag states corresponding to each band in the calculated PA spectra. The items in Table III are similar to those in Table II, i.e., each entry corresponds to the overall contribution of each kind of an excitation. Remarkably, the wavefunction descriptions of the different spectral features are very similar for all four systems shown in Fig. 2. Broadly speaking, there occur three distinct classes of Ag states in all four systems. These are discussed below.

The first class of states is represented by the 2Ag, which in all cases is predominantly a superposition of 1e–1h $`d_1d_1^{}`$ and 2e–2h $`(d_1d_1^{})^2`$, as with the Ohno parameters. However, compared to the bare Ohno parameters, the relative weight of the 1e–1h excitations here is larger. This is a conseqeuence of the smaller $`U`$, and is to be expected. Furthermore, the relative weight of the 1e–1h excitations is also larger in the PPP oligomers than in the PPV oligomers. This is also to be expected, based on the larger one–electron gap in PPP. The 2Ag can certainly be descibed within an effective linear chain model with large dimerization that retains only the $`d_1`$ and $`d_1^{}`$ bands, as suggested before Soos et al. (1992).

The second class of states are represented in all cases by the different Ag states that form the final states in the second and third bands in the calculated PA spectra. These have strong contributions from 2e–2h $`(d_1d_1^{})^2`$, and weak but nonzero contributions from $`(d_1l^{})^2`$ and $`(ld_1^{})^2`$. In addition, there occur also 1e–1h contributions of the type $`d_1d_2^{}`$, $`d_2d_1^{}`$, etc., and while there are subtle differences in the relative contributions by different kinds of single excitations involving low and high energy delocalized bands, the overall natures of the excitations that are the final states in absorption bands II and III are similar. The qualitative natures of these eigenstates are very similar to that of the mAg discussed in the context of nonlinear spectroscopy of polyacetylenes and polydiacetylenes. The wavefunction descriptions make it clear that very qualitatively these wavefunctions can also be described within the effective linear chain model, but with less precision than the 2Ag. Our calculated relative intensities of the 2Ag and the mAg are in qualitative agreement with other recent calculations for polyphenylenes that used a basis space of only the $`d_1`$ and $`d_1^{}`$ bands Lavrentiev et al. (1999); Beljonne (2001).

Above band III in the calculated spectra we always have a state that is qualitatively different from lower energy Ag states. This corresponds to the spectral feature IV in PPP4, PPP5 and PPV3, and the spectral feature V in PPV4. The relative weights of the two classes of 2e–2h excitations, $`(d_1d_1^{})^2`$ and $`(d_1l^{})^2`$, are reversed in this high energy state, with the former now making weak contribution and the latter a strong contribution. This qualitative difference between the Ag states at different energies is in agreement with the earlier conjecture by Chakrabarti and Mazumdar Chakrabarti and Mazumdar (1999). The clear demarkation between Ag states dominated by either $`(d_1d_1^{})^2`$ or $`(d_1l^{})^2`$, rather than nearly equal admixing, is a new result. This is an effect of increased oligomer length, as discussed above. Furthermore, we also notice that the highest energy two–photon states in Fig. 2 have the strongest 1e–1h contribution from excitations of the type $`d_1d_2^{}`$ (in the case of PPP oligomers) and $`d_1d_3^{}`$ (in the case of PPV oligomers). This is yet another difference between the mAg and the kAg. What is also significant is the weak role of $`(ll^{})^2`$ 2e–2h excitations in the Ag states included in Table III, in contrast to their relatively strong role in the high energy Ag states of biphenyl and triphenyl within the previous limited basis calculations Chakrabarti and Mazumdar (1999). This is also an effect of increased chain length, with the $`(ll^{})^2`$ 2e–2h excitations now perhaps dominating even higher energy distinct two-photon states. The weaker oscillator strength of absorption band IV, relative to the strong oscillator strength of absorption band II is easily understood from Table III: 2e–2h excitations of the type $`(d_1l^{})^2`$ have small dipole coupling with the 1Bu, which is predominantly $`d_1d_1^{}`$. Thus the dipole coupling of the Ag states responsible for absorption band IV originates mostly from the small 1e–1h contribution to this state. These highest energy Ag states are neither expected nor found in the limited basis calculations by Lavrentiev et al. Lavrentiev et al. (1999) and Beljonne Beljonne (2001).

Taken together, the results of Table III indicate the occurrence of different classes of Ag states, which are distinguished by the dominance of different types of 2e–2h excitations. With hindsight, this is perhaps not entirely surprising, as discussed in section III.

## V Conclusions and Discussions

Even as the concept of different types of two–photon states appear to be correct, it might seem that straightforward assignments of experimental PA1 and PA2 from the calculated PA spectra of Fig. 2 alone are not possible. We first discuss applications of our theory to PPV derivatives, and then to ladder PPP, etc. The strong spectral feature II in the theoretical spectra (the theoretical mAg) is certainly a component of the experimental PA1 in PPV derivatives. Beyond this there are two possibilities, viz., (i) the spectral feature III corresponds to PA2, and the spectral feature IV (V in PPV4) is too high in energy to be observed experimentally; or (ii) the spectral feature III is also a part of PA1 (especially in long chains) and it is the high energy $`(d_1l^{})^2`$ excitation that corresponds to PA2. We ascribe the $`(d_1l^{})^2`$ excitation to PA2 based on the following reasons. First, Ag states that give rise to spectral feature III occur also in linear chain polyenes Chandross et al. (1999). Their contribution to EA and TPA are vanishingly weak in long chains. In contrast, the contributions of the experimental kAg to EA and TPA in PPV derivatives are clearly visible Frolov et al. (2001); Liess et al. (1997); Österbacka et al. (2002). On the other hand, eigenstates ithat are predominantly $`(d_1l^{})^2`$ are clearly absent in polyacetylenes and polydiacetylenes, which possess only delocalized valence and conduction bands, and hence our assignment would naturally explain the absence of the kAg state in these systems Liess et al. (1997); Österbacka et al. (2002). Second, as we have already remarked, spectral feature III (but not IV) has also been found in the calculations by Beljonne Beljonne (2001), who, however, determined that in the long chain limit the energies of features II and III converge. This once again supports our assignment of the $`(d_1l^{})^2`$ excitation to PA2 (note also that the 1e–1h contributions of the highest energy two–photon states are different, further justifying the notion that these states belong to a different class from the lower energy 2Ag and the mAg). We have already pointed out that the calculated PA1 energy is reasonably close to the experimental PA1 energy in PPV derivatives. The calculated scaled energy of PA2 from Figs. 2(c) and (d), at 0.7 – 0.8 $`\times `$ E(1Bu) (again with experimental E(1Bu) = 2.2 eV in substituted PPV’s) is at 1.5 – 1.76 eV, which is a reasonably good fit to the experimental PA2 energy of 1.3 – 1.4 eV, given the very short lengths of our oligomers, and the increased difficulty of fitting of very high energy states.

As mentioned in section I, we believe that the recent experiments on a methyl–substituted ladder type PPP ($`m`$-LPPP) Gadermaier et al. (2002a) and on a ladder type oligophenyl Gadermaier et al. (2002b) have probed an energy region that is considerably above the region where the mAg occurs. The PA features that have been called PA1 in these works occur at 1.5 eV in the polymer and at 1.8 eV in the oligomer, and are therefore too high in energy to be the same as PA1 in PPV derivatives. We therefore believe that the observed lowest energy PA features actually correspond to PA2 of Frolov et al., and this is why charge separation occurs upon excitation to this energy. This assignment is supported by the observation of EA Harrison et al. (1999a) as well as TPA Harrison et al. (1999b) to a different lower energy two–photon state that occurs $``$ 0.7 eV above the 1Bu exciton in the polymer. We therefore make the testable prediction that there should occur in these systems a lower energy PA at $``$ 0.7 eV that is considerably stronger than the PAs in the 1.5 – 1.8 eV range. The scaled PA2 energy from our PPP oligomer calculations, 0.6 – 0.8 $`\times `$ E(1Bu), with experimental E(1Bu) = 2.7 eV in $`m`$-LPPP Harrison et al. (1999a), corresponds to 1.6 – 2.1 eV, once again reasonably close to the experimental value.

The above then leads to the question why dissociation of the kAg to polaron pairs is so efficient. We speculate that this is related to the specific structure of the kAg. In photoconductivity measurement on a PPV derivative it has been found that a large jump in the photoconductivity occurs at 4.7 eV, exactly where the $`d_1l^{}+ld_1^{}`$ one-photon exciton is located Köhler et al. (1998). The jump in the photoconductivity is due to a sudden increase in the interchain charge carrier generation subsequent to the excitation to this particular excited state. We speculate that there occurs a similar enhanced charge carrier generation subsequent to the sequential excitation to an Ag state that has strong contributions from $`(dl^{})^2`$ (whose energy is however lower and close to the minus combination of the one–excitations). Indeed, similar mechanism has also been suggested by Zenz et al. Zenz et al. (2001). In the original work by Köhler et al., theoretical calculations suggested that the enhanced dissociation of the $`d_1l^{}+ld_1^{}`$ state was a consequence of the highly delocalized electron–hole character of this state Köhler et al. (1998). The latter necessarily implies that the charge carriers are similarly weakly bound even in the $`(d_1l^{})^2`$ double excitation. Additional contribution to the enhanced tendency to charge separation in the case of PPVs from excitations involving $`l`$ and $`l^{}`$ bands may also come from phenyl ring rotations that occur in these excited states. Given that the charge densities on the para carbons are exactly zero for the $`l`$ and $`l^{}`$ MOs, bond orders involving the para carbon atoms in the kAg will be particularly small. This might lead to greater phenyl ring rotation in the kAg than in the 1Bu excitation. This feature of the kAg can lead to a lifetime that is longer than the mAg, and it is conceivable that the relatively long lifetime and the weak binding between the electrons and holes together contribute to the charge separation. In a recent work, one of us (S.M.) and colleagues have calculated the relative yields of singlet and triplet excitons starting from oppositely charged polarons, in the presence of interchain hopping of electrons and holes Wohlgennant et al. (2001); Tandon et al. (2003). The computational technique used to calculate charge recombination in these works can be applied also to the opposite process of photoinduced charge transfer. Photoinduced charge transfer from different classes of Ag states is of interest in the present context and is currently being investigated.

Our observation that the 2Ag is not the mAg may also have experimental significance. An early measurement detected strong two-photon fluoroscence in PPV from a state that is only 0.5 eV above the 1Bu Baker et al. (1993), and evidence for a second two–photon state slightly higher in energy. Later experiments involving nonlinear absorption have invariably found the mAg to be at least 0.8 eV above the 1Bu. It is conceivable that the low energy two–photon state found by Baker et al. is the 2Ag. A similar suggestion has also been made by Lavrentiev et al. Lavrentiev et al. (1999).

## VI Acknowledgements

Work at Arizona was partially supported by NSF DMR–0101659, NSF ECS–0108696, and the ONR. We acknowledge many useful discussions with G. Lanzani and Z.V. Vardeny.