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# Discrete breathers in polyethylene chain

## I Introduction

Localized excitations in nonlinear systems (solitons, polarons, breathers) became the subject of growing interest during last decades. Discrete breathers, or intrinsic localized modes correspond to shortwave length periodic vibrations which can not be revealed in continuum model of the chain. Intensive study of the breathers has an origin in pioneer work of Sievers and Takeno p1 . Their existence is proved by corresponding theorem p2 ; p3  and numerous numerical investigations p4 . Now their role in mechanisms of the energy relaxation in molecular systems becomes rather clarified p5 ; p6 ; p7 .

However all these results relate to simple one-dimensional systems. Meantime it should be waited that similar elementary excitations can exist in more realistic discrete nonlinear models p8 . The necessary conditions for their existence are discreteness of the system leading to boundedness of phonon frequency spectrum and amplitude dependence of eigenfrequencies caused by nonlinearity. These conditions are satisfied for polymeric molecules. For example, anharmonic potential of C—H valence bond in carbon-hydrogen chains leads to existence of high-frequency localized vibrations of such bonds p8 . Naturally, this type of breathers has to be present in polyethylene (PE) chain but corresponding frequencies are very high ($`3100`$ cm-1). We will discuss the breathers caused by the backbone vibrations of PE chains which correspond to much more less frequencies because they arise due to coordinated changes of C—C valence bonds and CCC-valence angles.

## II Model of macromolecular chain in PE crystal

Nonlinear dynamics of planar PE macromolecule has been considered in p9 ; p10  where a detail consideration of the transzigzag model is presented. This is a reason for only short its description which is given below

PE crystal consists of parallely packed zigzag chains \[PE macromolecules (CH2)\]. The structure of the crystal is schematically plotted at Fig. 1. Every PE macromolecule in the crystal has a transzigzag conformation. It means that backbone of the chain has a planar zigzag structure with equilibrium length $`\rho _0=1.53`$ Å of valence bond H2C–CH2 and value $`\theta _0=113^{}`$ of valence angle CH2–CH2–CH2. All macromolecules are situated in parallel planes. The crystalline structure is characterized by angle $`\theta _0`$ and three periods: $`a=4.51`$ Å, $`b=7.031`$ Å, $`c=2\rho _0\mathrm{sin}(\theta _0/2)=2.552`$ Å .

Let us consider the dynamics of PE macromolecule and will take into account its interaction with six neighbor chains which being considered as immobile (approximation of immobile neighbor chains). Because the motion of hydrogen atoms with respect to backbone chain is not significant when studying low energy nonlinear dynamics, we will consider every CH2-group as a united particle.

Let us introduce the local coordinate system presented at Fig. 1. Then the Hamiltonian of the chain can be written as follows

$`H={\displaystyle \underset{n}{}}\{{\displaystyle \frac{1}{2}}M(\dot{u}_n^2+\dot{v}_n^2+\dot{w}_n^2)+V(\rho _n)+U(\theta _n)`$
$`+W(\delta _n)+Z(u_n,v_n,w_n)\},`$ (1)
where the first term describes the kinetic energy of $`n`$th unit, the second the deformation energy of the $`n`$th valence bond, the third the deformation energy of the $`n`$th valence angle, the fourth the deformation energy of $`n`$th torsional angle, and the last term the energy of interaction of the $`n`$th unit with the six neighboring chains (substrate potential), $`M=14m_p`$ is the mass of the united atom ($`m_p`$ is the proton mass).

The length of $`n`$th valence bond is

$$\rho _n=(a_{n,1}^2+a_{n,2}^2+a_{n,3}^2)^{1/2},$$

where $`a_{n,1}=u_n+u_{n+1}l_x`$, $`a_{n,2}=v_n+v_{n+1}`$, $`a_{n,3}=w_{n+1}w_n+l_z`$ \[$`l_x=\rho _0\mathrm{cos}(\theta _0/2)`$ and $`l_z=\rho _0\mathrm{sin}(\theta _0/2)`$ – transversal and longitudinal step of the zigzag chain\]. The cosine of the $`n`$-th valence angle is

$$\mathrm{cos}(\theta _n)=\left(a_{n1,1}a_{n,1}+a_{n1,2}a_{n,2}a_{n1,3}a_{n,3}\right)/\rho _{n1}\rho _n,$$

and the cosine of the $`n`$th torsional angle is

$$\mathrm{cos}(\delta _n)=\left(b_{n,1}b_{n+1,1}b_{n,2}b_{n+1,2}+b_{n,3}b_{n+1,3}\right)/\beta _n\beta _{n+1},$$

where

$`b_{n,1}`$ $`=`$ $`a_{n1,2}a_{n,3}+a_{n,2}a_{n1,3},`$
$`b_{n,2}`$ $`=`$ $`a_{n1,1}a_{n,3}+a_{n,1}a_{n1,3},`$
$`b_{n,3}`$ $`=`$ $`a_{n1,2}a_{n,1}a_{n,2}a_{n1,1},`$
$`\beta _n`$ $`=`$ $`\left(b_{n,1}^2+b_{n,2}^2+b_{n,3}^2\right)^{1/2}.`$
Potentials of valence bond, valence angle, and torsion angle are accepted in the form

$`V(\rho _n)`$ $`=`$ $`D_0\left\{1\mathrm{exp}[\alpha (\rho \rho _0)]\right\}^2,`$
$`U(\theta _n)`$ $`=`$ $`{\displaystyle \frac{1}{2}}\gamma (\mathrm{cos}\theta \mathrm{cos}\theta _0)^2,`$
$`W(\delta _n)`$ $`=`$ $`C_1+C_2\mathrm{cos}\delta _n+C_3\mathrm{cos}3\delta _n,`$
where the parameters $`D_0=334.72`$ kJ/mol, $`\alpha =1.91`$ Å-1, $`\gamma =130.122`$ kJ/mol, $`C_1=8.37`$ kJ/mol, $`C_2=1.675`$ kJ/mol, $`C_3=6.695`$ kJ/mol. The substrate potential

$`Z(u,v,w)=\epsilon _w\mathrm{sin}^2(\pi w/l_z)`$
$`+{\displaystyle \frac{1}{2}}K_u\left[1+\epsilon _u\mathrm{sin}^2(\pi w/l_z)\right]\left\{u{\displaystyle \frac{1}{2}}l_x\left[1\mathrm{cos}(\pi w/l_z)\right]\right\}^2`$
$`+{\displaystyle \frac{1}{2}}K_v\left[1+\epsilon _v\mathrm{sin}^2(\pi w/l_z)\right]v^2,`$
where the parameters $`\epsilon _u=0.0674265`$ kJ/mol, $`\epsilon _v=0.0418353`$ kJ/mol, $`\epsilon _w=0.1490124`$ kJ/mol, $`K_u=2.169513`$ kJ/Å mol2, $`K_v=13.683865`$ kJ/Å mol2. Detail substantiation of chosen potentials is presented in p10 .

## III Linear oscillations of transzigzag

Small-amplitude vibrations of isolated transzigzag were considered in p11 ; p12 ; p9  and vibrations with account of interaction with immobile surrounding chains – in p10 .

Small-amplitude vibrations can be divided on planar (in the zigzag plane) and transversal ones. In turn, the plane motions are divided on low-frequency acoustic and high-frequency optic vibrations. Accordingly, one can separate three dispersion curves corresponding to 1) plane acoustic phonons $`\omega =\omega _a(q)`$, 2) plane optic phonons $`\omega =\omega _o(q)`$, 3) transversal phonons $`\omega =\omega _t(q)`$. These curves with account of interchain interaction are presented at Fig. 2 (a).

For isolated chain (substrate potential $`Z(u,v,w)0`$) the acoustic phonons have the frequency spectrum $`0\omega _a228.75`$ cm-1, torsional (transversal) phonons – spectrum $`0\omega _t243.85`$ cm-1, and optic phonons – spectrum $`838.47`$ cm$`{}_{}{}^{1}\omega _o1168.11`$ cm-1. Interaction with surrounding chains leads only to a shift to right of low boundary of acoustic and transversal phonons: $`19.05`$ cm$`{}_{}{}^{1}\omega _a229.54`$ cm-1; $`52.43`$ cm$`{}_{}{}^{1}\omega _t249.43`$ cm-1; $`838.69`$ cm$`{}_{}{}^{1}\omega _o1168.27`$ cm-1.

## IV Localized nonlinear vibrations of PE chain

The equations of motion corresponding to Hamiltonian (1) have the form

$`M\ddot{u}_n={\displaystyle \frac{H}{u_n}},M\ddot{v}_n={\displaystyle \frac{H}{v_n}},M\ddot{w}_n={\displaystyle \frac{H}{w_n}},`$ (2)
$`n=0,\pm 1,\pm 2,\mathrm{}.`$
Complexity of this system does not allow to find its analytic solution. Thefore we used a numerical procedure.

The finite chain consisting of $`N=200`$ CH2 groups was considered. The viscous friction providing adsorption of phonons was introdused on the boundaries of the chain. The system of equations (2) with $`n=1,2,\mathrm{},N`$ was integrated numerically with breather-like initial condition. If a discrete breather can exist in the chain it can manifest itself in irradiation of superfluous (non-breather part of initial excitation) phonons.

Numerical modelling has shown that only one type of localized periodic vibrations exists caused by tension-compression of valence C—C bonds with coordinated change of valence angles in the plane of transzigzag – see Fig. 3 (b) (c). The vibration occurs in the plane of trans-zigzag with nodes displacements perpendicular to main backbone axis \[Fig. 3 (a)\].

These vibrations are stable excitations, which are characterized by frequency $`\omega `$, energy $`E`$ and dimensional width

$$L=2\left[\underset{n=1}{\overset{N}{}}(nn_c)^2p_n\right]^{1/2},$$

where the point $`n_c=_nnp_n`$ determines the position of the vibrations center and sequence $`p_n=_nE_n/E`$ – the distribution density of energy along the chain. Essential nonlinearity of these vibrations is manifested in decrease of its frequency with amplitude growth. So, the revealed excitation is actually discreet breather.

Dependence of energy $`E`$ and width of the breather $`L`$ on its frequency $`\omega `$ is presented at Fig. 4. The frequency spectrum of the breather has situated near low boundary of optic phonons. It is a reason why weak intermolecular interaction with surrounding chains do not practically effect on such excitations. If in isolated chain its frequency $`\omega _b=817`$ cm$`{}_{}{}^{1}\omega <\omega _o(0)=838`$ cm-1, in the chain surrounding by immobile neighbor chains — $`\omega _b=820`$ cm$`{}_{}{}^{1}\omega <\omega _o(0)=839`$ cm-1. When frequency decreases the energy of breather increases monotonically and its width decreases monotonically.

The frequency of breather has to be separated from the frequencies of small amplitude linear vibrations. One could expect also the existence of low-frequencies breathers with frequencies near upper boundary of transversal phonons $`\omega >\mathrm{max}\omega _t(q)`$ and high-frequency breathers with frequencies near upper boundary of optical phonons $`\omega >\omega _o(\pi )`$. But numerical analysis has shown that such localized excitations are absent.

## V Thermal vibrations of trans-zigzag as origin of discrete breathers

Let us consider the thermal vibrations of trans-zigzag. With this goal we analyze the finite chain consisting of N segments. Their $`N_0`$ segments near boundary (from both sides) are situated into heat bath with temperature $`T`$. The dynamics of the system is described by the systems of Langevin equations

$`M\ddot{u}_n={\displaystyle \frac{H}{u_n}}+\xi _n\mathrm{\Gamma }_nM\dot{u}_n,`$
$`M\ddot{v}_n={\displaystyle \frac{H}{v_n}}+\eta _n\mathrm{\Gamma }_nM\dot{u}_n,`$ (3)
$`M\ddot{w}_n={\displaystyle \frac{H}{w_n}}+\zeta _n\mathrm{\Gamma }_nM\dot{u}_n,`$
$`n=1,2,\mathrm{},N,`$
where the Hamiltonian of the system $`H`$ is given by Eq. (1), $`\xi _n`$, $`\eta _n`$, and $`\zeta _n`$ are random normally distributed forces describing the interaction of $`n`$th molecule with a thermal bath, the coefficient of friction $`\mathrm{\Gamma }_n=0`$ for $`N_0<nNN_0`$ and $`\mathrm{\Gamma }_n=\mathrm{\Gamma }`$ for $`nN_0`$ and $`NN_0<nN`$. Coefficient of friction $`\mathrm{\Gamma }=1/t_r`$, where $`t_r`$ – the relaxation time of the velocity of the molecule. The random forces $`\xi _n`$, $`\eta _n`$, and $`\zeta _n`$ have the correlation functions

$`\xi _n(t_1)\xi _m(t_2)=\eta _n(t_1)\eta _m(t_2)=\zeta _n(t_1)\zeta _m(t_2)=`$
$`2M\mathrm{\Gamma }k_BT\delta _{nm}\delta (t_1t_2),`$
$`\xi _n(t_1)\eta _m(t_2)=\xi _n(t_1)\zeta _m(t_2)=\eta _n(t_1)\zeta _m(t_2)=0,`$
$`1n,mN_0,NN_0<n,mN,`$
where $`k_B`$ is Boltzmann’s constant and $`T`$ is the temperature of heat bath.

The system (3) was integrated numerically by the standard forth-order Runge-Kutta method with a constant step of integration $`\mathrm{\Delta }t`$. Numerically, the delta function was represented as $`\delta (t)=0`$ for $`|t|>\mathrm{\Delta }t/2`$ and $`\delta (t)=1/\mathrm{\Delta }t`$ for $`|t|\mathrm{\Delta }t/2`$, i.e. the step of numerical integration corresponded to the correlation time of the random force. In order to use the Langevin equation, it is necessary that $`\mathrm{\Delta }tt_r`$. Therefore we chose $`\mathrm{\Delta }t=0.001`$ ps and the relaxation time $`t_r=0.1`$ ps.

Let us consider a frequency distribution of kinetic energy of thermal vibrations. For this goal the system (3) was integrated numerically for $`N=500`$, $`N_0=N/2`$. While choosing the initial conditions as corresponding to ground state of the chain the system was integrated during $`t=10t_r`$ to bring it in the thermal equilibrium. After that we calculated the density of molecules kinetic energy distribution on frequencies $`p(\omega )`$. To increase an accuracy, the density of distribution was calculated using 1000 independent realizations of the chain thermalization. The profile of the density of distribution for different values of temperature is presented at Fig. 2 (it is accepted that $`p(\omega )𝑑\omega =3`$).

For temperature $`T=1`$ K the density of distribution coincides practically with corresponding density for linearized system, so anharmonicity is here not essential. All vibrations are linear and only phonons are thermalized. With further increasing of temperature the amplitude of thermal vibrations also increases so their anharmonism is manifested. For $`T=100`$ K we see a shift of density behind the low boundary of the spectrum of optic phonons which becomes more pronounced with further increase of the temperature. High frequency vibrations in this region can be identified as breathers because they arise in the frequency region $`[\omega _b,\omega _o(0)]`$, corresponding to this type of excitations. The part of energy corresponding to breathers may be found as

$$p_b=_{\omega _b}^{\omega _o(0)}p(\omega )𝑑\omega .$$

The contribution of the breathers in thermal energy increases with growth of temperature (for $`T=1`$ K it is $`p_b=0.002`$, for $`T=100`$ K — $`p_b=0.106`$), has a maximal value $`p_b=0.115`$ for $`T=200`$ K and then decreases (for $`T=300`$ K the breathers contribution corresponds to $`p=0.083`$).

Let us isolate the breathers from thermal vibrations. With this goal we consider the chain consisting $`N=500`$ segments with boundary cites $`(N_0=50)`$ embedded to the heat bath with temperature $`T`$. After thermalization, we put the temperature of thermal bath $`T=0`$ and consider the irradiation of heat energy from internal region $`(N_0<n<NN_0)`$. The relaxation process for $`T=200`$ K is shown at Fig. 5. We see a formation of several mobile localized excitations. Their detail analysis leads to conclusion that they are discrete breathers with frequencies $`\omega \omega _b`$. So, one can observe the presence of breathers in thermal vibrations.

Let us consider the interaction of discrete breather with thermal phonons. The stationary discrete breather with frequency $`\omega =820.5`$ cm-1 was situated in the center of finite chain ($`N=200`$), their edges ($`N_0=10`$) being situated in thermal bath ($`T=10`$ K). As we can see from Fig. 6 the breaking of breather is observed just as the center of the chain is thermalized (the energy loss is 50% for 20 ps).

Probability of thermally activated formation of discrete breathers in the chain grows with increasing of the temperature. Therefore their concentration has to increase when temperature grows. However in a thermalized chain the breather has a finite time of life, decreasing with growth of the temperature. It is reason for non-monotones dependence of the concentration of breathers $`p_b`$ upon temperature $`T`$ — it increases when $`T200`$ K and decreases for $`T>200`$ K with maximal magnitude for $`T=200`$ K. Numerical study shows that the breathers may be better separated from thermal vibration namely when $`T=200`$ K.

One can see from Fig. 2 that revealed breathers is a unique type of stable localized periodic excitations in thermalized chain for given parameters of the crystal. Besides the breathers only vibrations with frequencies possessing to spectrum of linear oscillations can be thermalized. It confirms the conclusions with respect to existence of only one stable type of discrete breathers corresponding to localized oscillations of valence C—C bonds. The breathers present in thermalized chain even for sufficiently small temperatures.

## VI Conclusion

Stable localized nonlinear vibrations which are discrete breathers can exist in polymer crystal. In PE macromolecule they are planar vibration of transzigzag with periodic deformation of valence bonds C—C and valence angles CCC. The breathers present in thermalized chain and their contribution in heat capacity may be essential.