ABSTRACT
I. Introduction ...................................................................................................................... 306
A. Principles of Isotope Effects in Infrared Spectroscopy
and Molecular Dynamics ......................................................................................... 306
B. Intramolecular Dynamics and Isotope Selective Spectroscopic Techniques:
An Overview ............................................................................................................ 308
II. Intramolecular Redistribution Processes: From High-Resolution Spectroscopy
to Ultrafast Intramolecular Dynamics ............................................................................. 311
A. Intramolecular Quantum Dynamics and Molecular Spectroscopy ......................... 311
B. Spectroscopic States and Intramolecular Dynamics:
An Intuitive Perspective........................................................................................... 313
1. General Aspects................................................................................................. 313
2. An Example of Two-Level Dynamics.............................................................. 314
3. Coupling Many Levels in a Multistate Dynamics............................................ 316
III. The Experimental Approach to Infrared Spectroscopy with Mass
and Isotope Selection (IRSIMS)...................................................................................... 317
IV. Mass Selective Overtone Spectroscopy by Vibrationally Assisted Dissociation
and Photofragment Ionization: OSVADPI ...................................................................... 320
A. Mechanism of Vibrationally Assisted Dissociation and
Photofragment Ionization......................................................................................... 320
B. Isotopomer Selective Overtone Spectroscopy of the N
¼ 4
CH Chromophore Absorption of CHCl
................................................................. 323
C. Isotopomer Selective Overtone Spectroscopy of the N
¼ 4
CH Chromophore Absorption of CHCl
: A Hierarchy of Time Scales
and Isotope Effects in Intramolecular Vibrational Energy
Redistribution (IVR) ................................................................................................ 325
V. Isotope Selective Overtone Spectroscopy by Resonantly Enhanced
Two-Photon Ionization of Vibrationally Excited Molecules .......................................... 329
A. Overview .................................................................................................................. 330
B. Mechanism of Resonantly Enhanced Two-Photon Ionization
of Vibrationally Excited Molecules......................................................................... 331
C. The N ¼ 2 NH Chromophore Absorption of Aniline Isotopomers Near
6750 cm
: Isotope Effects and Vibrational Mode Specificity in IVR
and Tunneling Processes.......................................................................................... 334
D.
