Polarization of a linear chain of atoms by External Electric Fields Patrick M.

Thornton
An external electric field will cause a distortion in the electron cloud of an atom. This distortion, or polarization, of the electron cloud will result in an induced electric dipole in the target atom. The magnitude of the induced dipole is proportional to the magnitude of the net external field acting on this atom. The linear Polarizability of a single atom can be described by = , where is the electric field vector and is the vector of the induced dipole in the target atom. This description is the first term in the Taylor approximation, therefor it must be understood that for more extreme field strengths, the actual trend may not follow this model. Now, notice that the direction of the induced electric dipole is in the direction of the net external field. This model is appropriate when describing the Polarizability of a single atom; however to describe the effective Polarizability of a system of atoms, a new relation must be formed. This new relation is needed because the induced diploes produce their own Electric Field which will alter the external electric field at all positions.

The linear Polarizability constant of a single atom for electric field strengths up to a critical value are directly proportional to the net electric field strength at that point. The proportionality constant is intrinsic to a specific atom and its electron cloud configuration. The Polarizability constant of an atom is given in units of m3 or (Cm2/V). It can be assumed that an un-bonded carbon atom and one that is sp2 hybridized, as is the case with Graphene, may have slightly different Polarizability constants. In my analysis I will be ignoring any quantum effects and only focusing on the mathematical representation of an arrangement of dipoles in 2-dimensional space. The first case that I will approach is a linear chain of atoms aligned in the y-direction which will be

denoted by . The Electric Field will be described by its angle in relation to the x-direction which will be denoted by . In this case we will assume an infinite chain of atoms separated from one another by distance s. I will start by expanding and manipulating the expression: = ext (Eq. 1)

Now we can describe the net external field at the target location with the vector sum of the external field of the system and the electric fields created by every single Electric dipole. = ( ext + p) (Eq. 2)

The Electric field produced by a dipole is given by the vector equation: (

( )

(Eq. 6)

(Eq. 3)

In this equation p is the vector of the electric dipole moment, is the unit vector of the position vector from the dipole in question to the target atom, the r in the denominator is the magnitude of the distance from the dipole in question and the target atom, and (1/40) is a constant. We now must find a mathematical relationship that accounts for the contribution of all dipoles in this system. The ______________ I decided to break the Dipole electric field Equation into its and components. The above equation for the Electric field from a dipole at a given point can be manipulated to create more simplified expression for the and directions. With some manipulation you can derive the and equations of the dipole field. Ep = And Ep = (Eq. 5) (Eq. 4)

This relationship accounts for all instances of r that occur above and below the point of reference. It can be further simplified to the form of: = Where: The summation of n-3 from 1 to is convergent but only exists as a numerical value. These changes can be applied back to those and equations to yield the Ep and Ep from the Eq. 2. E = And E =

(Eq. 7)

(Eq. 8)

(Eq. 9)

These Equations can subsequently be substituted into Eq. 2 to yield the full relation of the dipole arrangement. ( And (

Now we must find a way to mathematically account for the field contribution of all of the dipoles. Symmetry is critical to understanding this problem. The magnitude and direction of every induced dipole in this system are identical because from every point of reference, there are infinite dipoles above and below the target atom. Also, at the point of reference the external field is of the same magnitude and direction at all points.

(Eq. 10)

(Eq. 11)

This can be solved for the and component of the induced dipole and simplified to:

To begin to account for every dipole, I modified the only variable between the equations for each individual dipole. In each field equation, the only variable is r-3, I changed this term to:

)
)

(Eq. 12)

And

)
)

(Eq. 13)

K=(

(Eq. 18)

These above equations relate the and components of the external field to the and components of the induced dipoles. In both cases we have a single constant to define the Polarizability in the and directions. We can investigate the deviation of the magnitude and direction of the induced dipole form the eternal field. The and components of the induced dipoles will not vary by the same constant. The form of equations 12 and 13 mirrors the form of the original formulation. Recall: = ext (Eq. 1)

This term, which I will refer to as K, will describe the variation of the angle from the angle . The initial approximation of the polarizability of a single atom uses only the first term in the Taylor approximation of the actual relationship. Therefore, it must be understood that this description of the polarization is only appropriate for non-extreme electric fields. Therefore it should be assumed that

This difference in Polarizability in the and directions will result in a variation of the angle of the induced dipole from the angle of the external field. We will begin to quantify this variation by describing the resulting angle of the induced dipole (Eq. 14) Then substituting the px and py values obtained in equations 12 and 13. For clarity I substituted:

With the above restrictions in place, we can investigate the implication of different values of K and thus, different external parameters on this system. On the stated interval for the value of K will range from 1 to infinity, increasing continuously from the point K=1 when = 0 to infinity as approaches 1. Solving k with on the interval (0, 1)

(Eq. 15)

Obtaining: ( In terms of : (( ) ) (Eq. 17) ) ( ) (Eq. 16) Now using this range of values for K, let us observe the impact of changing the external parameters of the system. Increasing the linear polarizability or decreasing the distance between atoms in this system will lead to an increasd K value.

Where is the angle between the direction and the external electric field vector. Notice term:

Here is a plot of , the angle of the induced dipole; with respect to , the angle of the external electric field.

induced dipoles all carry different magnitudes and directions so a new approach must be taken. Once again we will start with the general equation that defines the polarizability of an item. = ext This will then be expanded to: ( )

Where is the vector of the induced at target dipole . Where is the electric field strength at target from the point charge q. And where the term accounts for the electric field The line for K=1 gives the relationship between the angles as 1:1 this would assume no net influence from other dipoles. For values of K that are greater than 1 the angle of the induced dipole begins to diverge from the angle of the external field. Also, it can be observed that by increasing the value of K the variation of the angle from the angle will also increases in a much more drastic manner. For large values of K, a notable phenomenon becomes apparent. With the application of a slightly angled external field at a given threshold, the material may react by immediately polarizing to a vertical alignment. This result could be described as a Polarization Catastrophe. This response may have potential applications for use as a detector of certain external electric field conditions. contribution from all dipoles j which are not i. is a rank 2 tensor. With a little rearranging we can see that

Then:

Where; { }

We can then substitute: Point charge System So: Next we will analyze a system similar to the first. This new systems electric field is generated by a point charge q with a perpendicular distance R0 from one atom in the chain. This atom will be n=0. Atoms above will be numbered 1,2,3, ect. and atoms below will be numbered -1,-2,-3 ect. In the case of an electric field induced by a point charge, the ( ) ( )

Now we have the opportunity to solve this equation for the vector value of the induced dipoles at each atom. We first must find an equation for and . we can describe the electric field contribution from the point charge by the vector equation:

(Eq. x)

Now we can recombine our equations to find the expression describing the dipole moment at each location in the chain. Solving for (
:

This equation can be integrated into the problem by describing with the internal parameters of distance in the problem, R0 being the horizontal distance and sn describing the vertical distance for each atom in the chain. With these substitutions we find: Now let d*= s / R0 :
( ( ) ( ) ) ( ( ) ( ) ( ) )

( (

) ) )

[ ]

Now that we have an expression for the electric field contribution from the point charge, we need to define the term. For this let us recall the meaning of this term in the overall problem. , is the electric field streingth at a target atom from the source atom . Recall, this equation was given by: Now let: (
( )

( )

(Eq. 3)

Solving for (

Where is a vector of ones. Now: Or: ( (

) (

( )

( )