EE1 2007: Solution to homework assignment 7 Problem 1: A simple function that is frequently used to describe the potential energy

of rare gas dimers (such as Ar2 ) is the Lennard-Jones potential 12 6 U (r) = 4 r r where r is the distance between the two atoms and the two parameters, and depend on which atoms are involved. The shape of the curve is qualitatively similar to the Morse potential curve, but is more appropriate for van der Waals interactions (while Morse is more appropriate for molecules with a covalent bond between atoms). In each one of the questions (a-e) below you should give an expression that contains the parameters of the potential function, and , and possibly also the mass of the two atoms, m1 and m2 . (a) What is the distance rb at which the potential energy is smallest (the bond length) and nd the value of the potential energy at that distance (the binding energy of the dimer). (b) Expand U (r) in a Taylor series about r = rb up to second order and give an expression for the force constant, k , of the harmonic oscillator approximation to U (r). (c) Assuming the Harmonic Oscillator approximation is good enough for the ground state, what is the dissociation energy of a dimer described by a Lennard-Jones potential (that is, what is the minimum energy required to break the dimer a part)? (d) A dimer initially in the ground state can get excited to the rst excited state as it collides with a surface (for example, the walls of the container). What is the energy required to excite the dimer from the ground vibrational state to the rst vibrational excited state assuming the harmonic oscillator approximation is valid? (e) What is the rst anharmonic correction term to the energy of the dimer (that is, next term beyond the harmonic oscillator term in the Taylor expansion of the Lennard-Jones potential function)? Solution: (a) At the minimum, the rst derivative is zero. Find Jones potential, and then set it to zero to nd rb . dU = 4 dr 12 12 6 + 6 r13 r7
dU dr

by dierentiating the expression for the Lennard-

24 r

12

This must be zero when r = rb , so rb must satisfy 2 That is The potential energy at the minimum is U (rb ) U (rb ) = 4 21/6
12

12

rb = 21/6

21/6

= 4

1 1 4 2

(b) Let x = r rb and V (x) = U (r). Need to expand V (x) up to and including the second order term in a Taylor series dV x2 d2 V V (x) = V (0) + x (0) + (0) dx 2 dx2 = + 0 + 1 2 kx 2

V where k = d dx2 (0). The rst derivative term vanishes because x = 0 corresponds to a minimum of the V (x) function. This is a potential energy function for a harmonic oscillator with a spring constant k . In oder to get an expression for the spring constant in terms of the potential parameters and and the atomic masses m1 and m2 , nd the second derivative

k =

d2 U d2 V (0) = (rb ) = 4 2 dx dr2 = 4 2 rb 4 (21/6 )2 12 13 rb

12 13
12

12 rb 14 rb

67
6

6 8 rb

67 1 2
2

= =

12 13

67

1 2

4 72 36 (39 21) = 1/3 2 = 2/3 2 21/3 2 2 2

(c) The dissociation energy is the energy needed to bring the dimer up from the ground state to the state of two separated atoms. Ed = E2Ar EAr2 The energy of two separated atoms is E2Ar = limr U (r) = 0 and the energy of the ground state is
EAr2 = + h 2 k

where k is given by the expression obtained in (b) and is the reduced mass of the dimer

= m1 m2 /(m1 + m2 ). It is important to add to the zero point energy of the harmonic oscillator, which is the energy of the ground state with respect to the potential energy minimum. (d) The energy required to excite a harmonic oscillator from a stationary state to the next higher state is k

E = h = h

where the expression for k is given in part (b) and the expression for is given in part (c). (e) The rst anharmonic correction term to the harmonic oscillator approximation to the Lennard-Jones potential is the third order term in the Taylor expansion, the next term after the second order expansion given in part (b). This is x3 d3 U E = (rb ) . 3! dr3 The expression for the third derivative can be obtained by dierentiating the second derivative given in part (b). 12 6 d3 U ( r ) = 4 12 13 14 + 6 7 8 . b 9 dr3 rb 15 rb Now plug in rb = 21/6 and simplify.