Lennard-Jones Potential play sheet

A common INTER-molecular potential is the Lennard-Jones potential. (Lennard-Jones is one man who appended his wife's name to his own name.) This potential is commonly called the "6-12 potential" for obvious reasons. It is suitable for induced dipole - induced dipole interactions.

:= 1 := 1

One "LJ" unit of length is the distance at which the potential goes through zero. One "LJ" unit of energy is the absolute value of the energy of maximum attraction.

1. POTENTIAL (Solid line)

12 6 vlj ( r) := 4 r r
flj ( r) := d vlj ( r) dr
48 24 d ( vlj ( r) ) 13 7 dr r r

2. FORCE (dashed)

When the force is > 0 the nuclei are subjected to a force to increase the relative separation, r. When the force is < 0 the nuclei are subjected to a force to decrease the relative separation. The force is zero at the potential minimum [r = 21/6] and is maximally attractive at the potential inflection.
3

vlj ( r) flj ( r)
0

3 0.75

1.25

1.5

1.75

r
Plot in "LJ" units. This plot is then valid for all molecules which interact via induced dipoles. The questions are then: How does one scale the distance and energy axes for any given molecule?

UNITS
1. The number density. Consider one particle in a box of with linear dimension if lc = the lattice constant 1 1

( lc) :=

lc

LC ( rho) :=

rho

0.333333

For example what size lattice do we need to get a density of 0.2?

LC ( 0.2) = 1.71

This little calculator is useful for generating "box size" for simulations at different densities! 2. Energy and Temperature The average <KE> = (1/2)<v2 > = (3/2)T therefore T = (2/3) <KE> = (1/3)<v2 > Therefore a KE = 1 = 1.5 ===> T=2/3 T = 80K T=1 T = 119K

Now if you start calculations with velocity vectors of equal magnitude, <v2 > = <v>2 . While this will not be true as the sumulation runs, you can estimate T as ~ (1/3)*vinit2 . 3. Planck's constant Logic: calculate thermal wavelength of Ar at 120K in SI (SI) = 2.52x10-11 m = 0.0742 calculate thermal wavelength of Ar at T=1 in LJ (LJ) = h * 0.399 Therefore h(LJ) = 0.186 4. Time Use uncertainly relation. Logic: Calculate t (sec) if E is 119K, result 4.03 x10-13 . but = 0.186 t (LJ) = h/1 therefore 0.186 unit of LJ time = 4.03 x10-13 and thus 1 t (LJ) = 2.2 ps Some LJ conversions from 2nd Virial coefs. molecule Ne Ar Kr Xe Air N2 O2 CO CO2 NO N2 0 CH4 CF4 /k 35.6 120 171 220 99.2 95.1 117.5 100.2 189 131 189 148.2 152.5 ( ) 2.75 3.4 3.6 4.1 3.52 3.70 3.58 3.76 4.49 3.17 4.59 3.82 4.7 bo (cc/mole) 26.2 49.8 58.9 86.9 55.1 63.8 57.8 67.2 113.9 40 1.22 70.2 131.0

The second virial Coefficient of a LJ fluid

A. Calculate the Mayer f function f ( r , T) := e
2 1.5 1 0.5 f ( x , 1) 0 0.5 1 1.5

sig := 1 1

vlj ( r) T

B. Calculate the virial coefficient by integration B ( T) := 2 0

1000

f ( x , T) x dx

C. Reduce by the high T limit of 4* the volume of a single object. sig Vo := 3 2

4
3

b ( T) :=

B ( T)
4 Vo

b ( y)
4

10