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D. P. Craig - Molecular Quantum Electrodynamics

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D. P. Craig Molecular Quantum Electrodynamics
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    Molecular Quantum Electrodynamics
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Of equal value to students and experts, this self-contained, systematic introduction features formal derivations of the quantized field matrix elements for numerous laser-molecule interaction effects: one- and two-photon absorption and emission, Rayleigh and Raman scattering, linear and nonlinear optical processes, the Lamb shift, and much more.

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Table of Contents APPENDIX 1 Proofs of Three Identities for - photo 1
Table of Contents

APPENDIX 1
Proofs of Three Identities for Non-Commuting Operators
Identity I

If A and B are two non-commuting operators, a c -number, then

A11 Proof We first prove A11 for the case when FB Bn A11 then - photo 2

(A1.1)

Proof

We first prove (A1.1) for the case when F(B) = Bn. (A1.1) then becomes,

A12 The proof of A12 is immediate if the right-hand side of A12 is - photo 3

(A1.2)

The proof of (A1.2) is immediate if the right-hand side of (A1.2) is written as

Molecular Quantum Electrodynamics - image 4

(A1.3)

and use is made of

Molecular Quantum Electrodynamics - image 5

(A1.4)

To prove the general identity (A1.1), it is assumed that F ( B ) admits a power series expansion in B :

Molecular Quantum Electrodynamics - image 6

(A1.5)

Then the left-hand side of (A 1.1 ) may be written

which on using A12 becomes A16 the right hand side of A11 - photo 7

which on using (A1.2) becomes

A16 the right hand side of A11 Identity II If A and B are two - photo 8

(A1.6)

the right hand side of (A1.1).

Identity II

If A and B are two non-commuting operators, then

Molecular Quantum Electrodynamics - image 9

(A1.7)

Proof

Let

Molecular Quantum Electrodynamics - image 10

(A1.8)

where is a real variable. Expanding F () as a power series in ,

Molecular Quantum Electrodynamics - image 11

(A1.9)

Clearly

Molecular Quantum Electrodynamics - image 12

(A1.10)

The first derivative is

Al11 so that A112 Using A112 A113 H - photo 13

(Al.11)

so that

A112 Using A112 A113 Hence A114 Th - photo 14

(A1.12)

Using (A1.12)

A113 Hence A114 The result A17 follows Identity III If A - photo 15

(A1.13)

Hence,

A114 The result A17 follows Identity III If A and B are - photo 16

(A1.14)

The result (A1.7) follows.

Identity III

If A and B are non-commuting operators such that

Molecular Quantum Electrodynamics - image 17

(A1.15,)

then

Molecular Quantum Electrodynamics - image 18

(A1.16)

Proof

Let

Molecular Quantum Electrodynamics - image 19

(A1.17)

where is a real variabe. Then

A118 Usin Identity II A17 A119 Since A B commutes with - photo 20

(A1.18)

Usin Identity II (A1.7),

A119 Since A B commutes with AB they may be treated as - photo 21

(A1.19)

Since ( A + B ) commutes with [ A,B ], they may be treated as commuting variables and (A1.18) may be integrated to give

A120 When 1 A120 becomes A121 Therefore A122 - photo 22

(A1.20)

When = 1, (A1.20) becomes

A121 Therefore A122 The second part of A116 follows directly - photo 23

(A1.21)

Therefore

A122 The second part of A116 follows directly from A122 by - photo 24

(A1.22)

The second part of (A1.16) follows directly from (A1.22) by interchanging A and B in (A1.22)

APPENDIX 2
Rotational Averaging of Tensors

Let the components of an nth rank tensor T with respect to a space-fixed frame be If T refers to a molecular property it is conveniently expressed with respect - photo 25 If T refers to a molecular property, it is conveniently expressed with respect to a molecule-fixed frame through the relation

A21 where is the cosine of the angle between the space-fixed axis ip and - photo 26

(A2.1)

where Picture 27 is the cosine of the angle between the space-fixed axis ip and the molecule-fixed axis p. The Latin and Greek indices refer to space-fixed and molecule-fixed frames respectively. From (A2.1) it is seen that a rotational average of Picture 28 requires the rotational average of the direction cosine product By expressing the direction cosines in terms of Euler angles the rotational - photo 29 By expressing the direction cosines in terms of Euler angles, the rotational average can be obtained from

A22 where and are the Euler angles relating the two frames The - photo 30

(A2.2)

where , , and are the Euler angles relating the two frames. The trigonometric averaging procedure, though simple to use for tensors of low rank, becomes tedious for high n. A non-trigonometric procedure will now be outlined and results given for tensors up to rank 6.

Let us denote the rotational average Molecular Quantum Electrodynamics - image 31

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