Detailed Contents 1441
32.6.2 Gyro-Rotors and 2D-Local Mode Analogy ..................... 510
32.6.3 Multiple Gyro-Rotor RES and Eigensurfaces ................... 511
References ........................................................................ 512
33
Radiative Transition Probabilities
David L. Huestis ................................................................... 515
33.1 Overview .................................................................. 515
33.1.1 Intensity versus Line-Position Spectroscopy .................. 515
33.2 Molecular Wave Functions in the Rotating Frame ..................... 516
33.2.1 Symmetries of the Exact Wave Function ...................... 516
33.2.2 Rotation Matrices ............................................... 517
33.2.3 Transformation of Ordinary Objects into the Rotating Frame 517
33.3 The Energy–Intensity Model ............................................. 518
33.3.1 States, Levels, and Components ............................... 518
33.3.2 The Basis Set and Matrix Hamiltonian ......................... 518
33.3.3 Fitting Experimental Energies .................................. 520
33.3.4 The Transition Moment Matrix ................................. 520
33.3.5 Fitting Experimental Intensities ............................... 520
33.4 Selection Rules ........................................................... 521
33.4.1 Symmetry Types ................................................. 521
33.4.2 Rotational Branches and Parity ................................ 521
33.4.3 Nuclear Spin, Spatial Symmetry, and Statistics ............... 522
33.4.4 Electron Orbital and Spin Angular Momenta .................. 523
33.5 Absorption Cross Sections and Radiative Lifetimes .................... 524
33.5.1 Radiation Relations ............................................. 524
33.5.2 Transition Moments ............................................. 524
33.6 Vibrational Band Strengths .............................................. 525
33.6.1 Franck–Condon Factors ......................................... 525
33.6.2 Vibrational Transitions .......................................... 526
33.7 Rotational Branch Strengths ............................................ 526
33.7.1 Branch Structure and Transition Type ......................... 526
33.7.2 Hönl–London Factors ........................................... 527
33.7.3 Sum Rules ........................................................ 528
33.7.4 Hund’s Cases ..................................................... 528
33.7.5 Symmetric Tops .................................................. 530
33.7.6 Asymmetric Tops ................................................ 530
33.8 Forbidden Transitions .................................................... 530
33.8.1 Spin-Changing Transitions ..................................... 530
33.8.2 Orbitally-Forbidden Transitions ............................... 531
33.9 Recent Developments .................................................... 531
References ........................................................................ 532
34
Molecular Photodissociation
Abigail J. Dobbyn, David H. Mordaunt, Reinhard Schinke .................... 535
34.1 Observables ............................................................... 537
34.1.1 Scalar Properties ................................................ 537
34.1.2 Vector Correlations .............................................. 537
Detailed Cont.