Atkins' Physical Chemistry
Atkins' Physical Chemistry
11th Edition
ISBN: 9780191092183
Author: ATKINS
Publisher: OXFORD UNIV.PRESS ACAD.UK (CC)
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Chapter 11, Problem 11F.7P
Interpretation Introduction

Interpretation:

The transition probability for the transition n=1n=2 is non-zero while the transition probability for the transition n=1n=3 is zero has to be shown.

Concept introduction:

An electronic state of energy has its own vibrational states.  The energy between the electronic states is large, followed by vibrational states and then rotational states.  During an electronic transition, electron from ground state moves straight to the excited state keeping the internuclear distance constant.

Expert Solution & Answer
Check Mark

Answer to Problem 11F.7P

The transition probability for the transition n=1n=2 is non-zero while the transition probability for the transition n=1n=3 is zero has been rightfully shown.

Explanation of Solution

The normalized wavefunction for a one-dimensional box is given below.

    ψn=2Lsin(nπxL)

Where,

  • n is the quantum number of the energy state.
  • L is the length of the box.

The wavefunction for a one-dimensional box with n=1 is given below.

    ψ1=2Lsin(πxL)

The wavefunction for a one-dimensional box with n=2 is given below.

    ψ2=2Lsin(2πxL)

The expression for transition probability (μ) is given below.

    μq=ψ1*μψ2dτ        (1)

Where

  • μ is the magnitude of the dipole moment.
  • ψ1* is the conjugate of ψ1.

The wavefunction, ψ1 is real. Therefore, the value of ψ1* is equal to ψ1.

The value of μ is equal to ex.

Substitute ψ2, μ and ψ1* in equation (1).

    μq=0L2Lsin(πxL)(ex)2Lsin(πxL)dx=2eL0Lxsin(πxL)sin(πxL)dx=2eL×120Lx(cos(πxL)cos(3πxL))dxassinAsinB=12[cos(AB)cos(A+B)]=2eL×12(0Lxcos(πxL)dx0Lxcos(3πxL)dx)

The equation given above is solved further as shown below.

    μq=2eL×12(0Lxcos(πxL)dx0Lxcos(3πxL)dx)=eL[(Lπ[xsin(πxL)]0LLπ0Lsin(πxL)dx)(L3π[xsin(3πxL)]0LL3π0Lsin(3πxL)dx)]=eL[(0+L2π2[cos(πxL)]0L)(0+L29π2[cos(3πxL)]0L)]=eL[(L2π2(cosπcos0))L29π2(cos3πcos0)]        (2)

The equation (2) was solved further as shown below.

    μq=eL[(L2π2(cosπcos0))L29π2(cos3πcos0)]=eL×L2π2[(cosπcos0)19(cos3πcos0)]=eLπ2[(11)19(11)]=16eLπ2

Therefore, the transition probability for the transition n=1n=2 is non-zero.

The wavefunction for a one-dimensional box with n=3 is given below.

    ψ2=2Lsin(3πxL)

The expression for transition probability (μ) is given below.

    μq=ψ1*μψ3dτ        (1)

Where

  • μ is the magnitude of the dipole moment.
  • ψ1* is the conjugate of ψ1.

The wavefunction, ψ1 is real. Therefore, the value of ψ1 is equal to ψ1*.

The value of μ is equal to ex.

Substitute ψ3, μ and ψ1* in equation (1).

    μq=0L2Lsin(πxL)(ex)2Lsin(3πxL)dx=2eL0Lxsin(πxL)sin(3πxL)dx=2eL×120Lx(cos(2πxL)cos(4πxL))dxassinAsinB=12[cos(AB)cos(A+B)]=2eL×12(0Lxcos(2πxL)dx0Lxcos(4πxL)dx)

The equation given above is solved further as shown below.

    μq=2eL×12(0Lxcos(2πxL)dx0Lxcos(4πxL)dx)=eL[(L2π[xsin(2πxL)]0LL2π0Lsin(2πxL)dx)(L4π[xsin(4πxL)]0LL4π0Lsin(4πxL)dx)]=eL[(0+L24π2[cos(2πxL)]0L)(0+L216π2[cos(4πxL)]0L)]=eL[(L24π2(cos2πcos0))L216π2(cos4πcos0)]        (3)

The equation (3) was solved further as shown below.

    μq=eL[(L24π2(cos2πcos0))L216π2(cos4πcos0)]=eL×L24π2[(cos2πcos0)14(cos4πcos0)]=eLπ2[(00)14(00)]=0

Therefore, the transition probability for the transition n=1n=3 is zero.

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Chapter 11 Solutions

Atkins' Physical Chemistry

Ch. 11 - Prob. 11E.2STCh. 11 - Prob. 11F.2STCh. 11 - Prob. 11A.1DQCh. 11 - Prob. 11A.2DQCh. 11 - Prob. 11A.3DQCh. 11 - Prob. 11A.1AECh. 11 - Prob. 11A.1BECh. 11 - Prob. 11A.2AECh. 11 - Prob. 11A.2BECh. 11 - Prob. 11A.3AECh. 11 - Prob. 11A.3BECh. 11 - Prob. 11A.4AECh. 11 - Prob. 11A.4BECh. 11 - Prob. 11A.5AECh. 11 - Prob. 11A.5BECh. 11 - Prob. 11A.6AECh. 11 - Prob. 11A.6BECh. 11 - Prob. 11A.7AECh. 11 - Prob. 11A.7BECh. 11 - Prob. 11A.8AECh. 11 - Prob. 11A.8BECh. 11 - Prob. 11A.9AECh. 11 - Prob. 11A.9BECh. 11 - Prob. 11A.10AECh. 11 - Prob. 11A.10BECh. 11 - Prob. 11A.11AECh. 11 - Prob. 11A.11BECh. 11 - Prob. 11A.12AECh. 11 - Prob. 11A.12BECh. 11 - Prob. 11A.1PCh. 11 - Prob. 11A.2PCh. 11 - Prob. 11A.3PCh. 11 - Prob. 11A.4PCh. 11 - Prob. 11A.5PCh. 11 - Prob. 11A.7PCh. 11 - Prob. 11A.8PCh. 11 - Prob. 11A.9PCh. 11 - Prob. 11A.11PCh. 11 - Prob. 11B.1DQCh. 11 - Prob. 11B.2DQCh. 11 - Prob. 11B.3DQCh. 11 - Prob. 11B.4DQCh. 11 - Prob. 11B.5DQCh. 11 - Prob. 11B.6DQCh. 11 - Prob. 11B.7DQCh. 11 - Prob. 11B.8DQCh. 11 - Prob. 11B.1AECh. 11 - Prob. 11B.1BECh. 11 - Prob. 11B.3AECh. 11 - Prob. 11B.3BECh. 11 - Prob. 11B.4BECh. 11 - Prob. 11B.5AECh. 11 - Prob. 11B.5BECh. 11 - Prob. 11B.6AECh. 11 - Prob. 11B.6BECh. 11 - Prob. 11B.7AECh. 11 - Prob. 11B.7BECh. 11 - Prob. 11B.8AECh. 11 - Prob. 11B.8BECh. 11 - Prob. 11B.9AECh. 11 - Prob. 11B.9BECh. 11 - Prob. 11B.10AECh. 11 - Prob. 11B.10BECh. 11 - Prob. 11B.11AECh. 11 - Prob. 11B.11BECh. 11 - Prob. 11B.12AECh. 11 - Prob. 11B.12BECh. 11 - Prob. 11B.13AECh. 11 - Prob. 11B.13BECh. 11 - Prob. 11B.14AECh. 11 - Prob. 11B.14BECh. 11 - Prob. 11B.1PCh. 11 - Prob. 11B.2PCh. 11 - Prob. 11B.3PCh. 11 - Prob. 11B.4PCh. 11 - Prob. 11B.5PCh. 11 - Prob. 11B.6PCh. 11 - Prob. 11B.7PCh. 11 - Prob. 11B.8PCh. 11 - Prob. 11B.9PCh. 11 - Prob. 11B.10PCh. 11 - Prob. 11B.11PCh. 11 - Prob. 11B.12PCh. 11 - Prob. 11B.13PCh. 11 - Prob. 11B.14PCh. 11 - Prob. 11C.1DQCh. 11 - Prob. 11C.2DQCh. 11 - Prob. 11C.3DQCh. 11 - Prob. 11C.4DQCh. 11 - Prob. 11C.1AECh. 11 - Prob. 11C.1BECh. 11 - Prob. 11C.2AECh. 11 - Prob. 11C.2BECh. 11 - Prob. 11C.3AECh. 11 - Prob. 11C.3BECh. 11 - Prob. 11C.4AECh. 11 - Prob. 11C.4BECh. 11 - Prob. 11C.5AECh. 11 - Prob. 11C.5BECh. 11 - Prob. 11C.6AECh. 11 - Prob. 11C.6BECh. 11 - Prob. 11C.7AECh. 11 - Prob. 11C.7BECh. 11 - Prob. 11C.8AECh. 11 - Prob. 11C.8BECh. 11 - Prob. 11C.2PCh. 11 - Prob. 11C.3PCh. 11 - Prob. 11C.4PCh. 11 - Prob. 11C.5PCh. 11 - Prob. 11C.6PCh. 11 - Prob. 11C.7PCh. 11 - Prob. 11C.8PCh. 11 - Prob. 11C.9PCh. 11 - Prob. 11C.10PCh. 11 - Prob. 11C.11PCh. 11 - Prob. 11C.12PCh. 11 - Prob. 11C.13PCh. 11 - Prob. 11C.15PCh. 11 - Prob. 11C.17PCh. 11 - Prob. 11C.18PCh. 11 - Prob. 11C.19PCh. 11 - Prob. 11D.1DQCh. 11 - Prob. 11D.2DQCh. 11 - Prob. 11D.3DQCh. 11 - Prob. 11D.1AECh. 11 - Prob. 11D.1BECh. 11 - Prob. 11D.2AECh. 11 - Prob. 11D.2BECh. 11 - Prob. 11D.3AECh. 11 - Prob. 11D.3BECh. 11 - Prob. 11D.4AECh. 11 - Prob. 11D.4BECh. 11 - Prob. 11D.5AECh. 11 - Prob. 11D.5BECh. 11 - Prob. 11D.6AECh. 11 - Prob. 11D.6BECh. 11 - Prob. 11D.7AECh. 11 - Prob. 11D.7BECh. 11 - Prob. 11D.2PCh. 11 - Prob. 11E.1DQCh. 11 - Prob. 11E.1AECh. 11 - Prob. 11E.1BECh. 11 - Prob. 11E.2AECh. 11 - Prob. 11E.2BECh. 11 - Prob. 11E.3AECh. 11 - Prob. 11E.3BECh. 11 - Prob. 11E.1PCh. 11 - Prob. 11E.2PCh. 11 - Prob. 11F.1DQCh. 11 - Prob. 11F.2DQCh. 11 - Prob. 11F.3DQCh. 11 - Prob. 11F.4DQCh. 11 - Prob. 11F.5DQCh. 11 - Prob. 11F.6DQCh. 11 - Prob. 11F.1AECh. 11 - Prob. 11F.1BECh. 11 - Prob. 11F.2AECh. 11 - Prob. 11F.2BECh. 11 - Prob. 11F.3AECh. 11 - Prob. 11F.3BECh. 11 - Prob. 11F.4AECh. 11 - Prob. 11F.4BECh. 11 - Prob. 11F.5AECh. 11 - Prob. 11F.5BECh. 11 - Prob. 11F.6AECh. 11 - Prob. 11F.6BECh. 11 - Prob. 11F.7AECh. 11 - Prob. 11F.7BECh. 11 - Prob. 11F.8AECh. 11 - Prob. 11F.8BECh. 11 - Prob. 11F.9AECh. 11 - Prob. 11F.9BECh. 11 - Prob. 11F.10AECh. 11 - Prob. 11F.10BECh. 11 - Prob. 11F.11AECh. 11 - Prob. 11F.11BECh. 11 - Prob. 11F.12AECh. 11 - Prob. 11F.12BECh. 11 - Prob. 11F.13AECh. 11 - Prob. 11F.13BECh. 11 - Prob. 11F.1PCh. 11 - Prob. 11F.2PCh. 11 - Prob. 11F.3PCh. 11 - Prob. 11F.4PCh. 11 - Prob. 11F.5PCh. 11 - Prob. 11F.6PCh. 11 - Prob. 11F.7PCh. 11 - Prob. 11F.8PCh. 11 - Prob. 11F.9PCh. 11 - Prob. 11F.10PCh. 11 - Prob. 11F.11PCh. 11 - Prob. 11F.12PCh. 11 - Prob. 11G.1DQCh. 11 - Prob. 11G.2DQCh. 11 - Prob. 11G.3DQCh. 11 - Prob. 11G.4DQCh. 11 - Prob. 11G.5DQCh. 11 - Prob. 11G.1AECh. 11 - Prob. 11G.1BECh. 11 - Prob. 11G.2AECh. 11 - Prob. 11G.2BECh. 11 - Prob. 11G.1PCh. 11 - Prob. 11G.2PCh. 11 - Prob. 11G.3PCh. 11 - Prob. 11G.4PCh. 11 - Prob. 11G.5PCh. 11 - Prob. 11G.6PCh. 11 - Prob. 11.1IACh. 11 - Prob. 11.5IACh. 11 - Prob. 11.8IA
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