ELECTRONIC AND PHOTOELECTRON SPECTROSCOPY
CONTENTS PART I FOUNDATIONS OF ELECTRONIC AND PHOTOELECTRON SPECTROSCOPY INTRODUCTION 1 1 THE BASICS 1 2 INFORMATION OBTAINED FROM ELECTRONIC AND PHOTOELECTRON SPECTRA ELECTRONIC STRUCTURE 2 1 ORBITALS: QUANTUM MECHANICAL BACKGROUND REFERENCES ANGULAR MOMENTUM IN SPECTROSCOPY CLASSI?CATION OF ELECTRONIC STATES 4 1 ATOMS 4 2 MOLECULES MOLECULAR VIBRATIONS 5 1 DIATOMIC MOLECULES 5 2 POLYATOMIC MOLECULES MOLECULAR ROTATIONS 6 1 DIATOMIC MOLECULES 6 2 POLYATOMIC MOLECULES TRANSITION PROBABILITIES 7 1 TRANSITION MOMENTS 7 2 FACTORIZATION OF THE TRANSITION MOMENT PART II EXPERIMENTAL TECHNIQUES THE SAMPLE 8 1 THERMAL SOURCES 8 2 SUPERSONIC JETS 8 3 MATRIX ISOLATION BROADENING OF SPECTROSCOPIC LINES 9 1 NATURAL BROADENING 9 2 DOPPLER BROADENING 9 3 PRESSURE BROADENING LASERS 10 1 PROPERTIES 10 2 BASIC PRINCIPLES 10 3 ION LASERS 10 4 ND:YAG LASER 10 5 EXCIMER LASER 10 6 DYE LASERS 10 7 TITANIUM:SAPPHIRE LASER 10 8 OPTICAL PARAMETRIC OSCILLATORS OPTICAL SPECTROSCOPY 11 1 CONVENTIONAL ABSORPTION/EMISSION SPECTROSCOPY 11 2 LASER-INDUCED ?UORESCENCE (LIF) SPECTROSCOPY 11 3 CAVITY RINGDOWN (CRD) LASER ABSORPTION SPECTROSCOPY 11 4 RESONANCE-ENHANCED MULTIPHOTON IONIZATION (REMPI) SPECTROSCOPY 11 5 DOUBLE-RESONANCE SPECTROSCOPY 11 6 FOURIER TRANSFORM (FT) SPECTROSCOPY PHOTOELECTRON SPECTROSCOPY 12 1 CONVENTIONAL ULTRAVIOLET PHOTOELECTRON SPECTROSCOPY 12 2 SYNCHROTRON RADIATION IN PHOTOELECTRON SPECTROSCOPY 12 3 NEGATIVE ION PHOTOELECTRON SPECTROSCOPY 12 4 PENNING IONIZATION ELECTRON SPECTROSCOPY 12 5 ZERO ELECTRON KINETIC ENERGY (ZEKE) SPECTROSCOPY 12 6 ZEKE–PFI SPECTROSCOPY REFERENCE FURTHER READING PART III CASE STUDIES ULTRAVIOLET PHOTOELECTRON SPECTRUM OF CO 13 1 ELECTRONIC STRUCTURES OF CO AND CO+ 13 2 FIRST PHOTOELECTRON BAND SYSTEM 13 3 SECOND PHOTOELECTRON BAND SYSTEM 13 4 THIRD PHOTOELECTRON BAND SYSTEM 13 5 ADIABATIC AND VERTICAL IONIZATION ENERGIES 13 6 INTENSITIES OF PHOTOELECTRON BAND SYSTEMS 13 7 DETERMINING BOND LENGTHS FROM FRANCK–CONDON FACTOR CALCULATIONS PHOTOELECTRON SPECTRA OF CO2, OCS, AND CS2 IN A MOLECULAR BEAM 14 1 FIRST PHOTOELECTRON BAND SYSTEM 14 2 SECOND PHOTOELECTRON BAND SYSTEM 14 3 THIRD AND FOURTH PHOTOELECTRON BAND SYSTEMS 14 4 ELECTRONIC STRUCTURES: CONSTRUCTING AN MO DIAGRAM FROM PHOTOELECTRON SPECTRA PHOTOELECTRON SPECTRUM OF NO? 15 1 THE EXPERIMENT 15 2 VIBRATIONAL STRUCTURE 15 3 VIBRATIONAL CONSTANTS 15 4 STRUCTURE DETERMINATION 15 5 ELECTRON AF?NITY AND THERMODYNAMIC PARAMETERS 15 6 ELECTRONIC STRUCTURE LASER-INDUCED ?UORESCENCE SPECTROSCOPY OF C3: ROTATIONAL STRUCTURE IN THE 300 NM SYSTEM 16 1 ELECTRONIC STRUCTURE AND SELECTION RULES 16 2 ASSIGNMENT AND ANALYSIS OF THE ROTATIONAL STRUCTURE 16 3 BAND HEAD FORMATION PHOTOIONIZATION SPECTRUM OF DIPHENYLAMINE: AN UNUSUAL ILLUSTRATION OF THE FRANCK–CONDON PRINCIPLE VIBRATIONAL STRUCTURE IN THE ELECTRONIC SPECTRUM OF 1,4-BENZODIOXAN: ASSIGNMENT OF LOW FREQUENCY MODES 18 1 AB INITIO CALCULATIONS 18 2 ASSIGNING THE SPECTRA VIBRATIONALLY RESOLVED ULTRAVIOLET SPECTROSCOPY OF PROPYNAL 19 1 ELECTRONIC STATES 19 2 ASSIGNING THE VIBRATIONAL STRUCTURE 19 3 LIF SPECTROSCOPY OF JET-COOLED PROPYNAL ROTATIONALLY RESOLVED LASER EXCITATION SPECTRUM OF PROPYNAL 20 1 ASSIGNING THE ROTATIONAL STRUCTURE 20 2 PERPENDICULAR VERSUS PARALLEL CHARACTER 20 3 ROTATIONAL CONSTANTS 20 4 EFFECTS OF ASYMMETRY ZEKE SPECTROSCOPY OF AL(H2O) AND AL(D2O) 21 1 EXPERIMENTAL DETAILS 21 2 ASSIGNMENT OF THE VIBRATIONALLY RESOLVED SPECTRUM 21 3 DISSOCIATION ENERGIES 21 4 ROTATIONAL STRUCTURE 21 5 BONDING IN AL(H2O) ROTATIONALLY RESOLVED ELECTRONIC SPECTROSCOPY OF THE NO FREE RADICAL VIBRATIONALLY RESOLVED SPECTROSCOPY OF MG+–RARE GAS COMPLEXES 23 1 EXPERIMENTAL DETAILS 23 2 PRELIMINARIES: ELECTRONIC STATES 23 3 PHOTODISSOCIATION SPECTRA 23 4 SPIN–ORBIT COUPLING 23 5 VIBRATIONAL ASSIGNMENT 23 6 VIBRATIONAL FREQUENCIES 23 7 DISSOCIATION ENERGIES 23 8 B–X SYSTEM ROTATIONALLY RESOLVED SPECTROSCOPY OF MG+–RARE GAS COMPLEXES 24 1 X 2+ STATE 24 2 A2 STATE 24 3 TRANSITION ENERGIES AND SELECTION RULES 24 4 PHOTODISSOCIATION SPECTRA OF MG+–NE AND MG+–AR VIBRONIC COUPLING IN BENZENE 25 1 THE HERZBERG–TELLER EFFECT REMPI SPECTROSCOPY OF CHLOROBENZENE 26 1 EXPERIMENTAL DETAILS AND SPECTRUM 26 2 ASSIGNMENT SPECTROSCOPY OF THE CHLOROBENZENE CATION 27 1 THE ˜X 2B1 STATE 27 2 THE ˜B STATE 28 1 EXPERIMENTAL 28 3 ROTATIONAL ENERGY LEVELS 28 4 NUCLEAR SPIN STATISTICS 28 5 SPECTRUM ASSIGNMENT 28 6 WHY IS THIS STRONGLY FORBIDDEN TRANSITION OBSERVED?