Ellis A.M., Feher M., Wright T. Electronic and Photoelectron Spectroscopy: Fundamentals and Case Studies
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Index
285
photodetachment spectroscopy, see negative ion
photoelectron spectroscopy
photodiode 88
photodiode array 88
photodissociation spectroscopy 187
photoelectron spectroscopy 4, 102–107
photoionization 4, 102
photolysis 72
photomultiplier tube (PMT) 88, 90, 92
photon, angular momentum 63
point group symmetry 18, 251–252
polarization functions 237
population inversion 54, 79
potential energy curve 25, 58, 233
potential energy surface 233
predissociation 76, 91
pressure broadening, see broadening
principal axes 44
principal quantum number 15
propynal
ab initio calculations 157
asymmetric rotor 168
dispersed fluorescence spectroscopy 162
electronic origin (0
0
0
) transition 160
electronic states 159
equilibrium structure 159
isotope substitution 159
non-radiative relaxation 162
perpendicular versus parallel character
167
π* ← n transition 157
rotational constants 168
rotational structure in LIF excitation spectrum
165–167
supersonic (jet) cooling 161
vibrational frequencies 163
vibrational modes 158
vibrational progressions 159
vibronic coupling 163
pulsed lasers 71
pulsed valve 71
Q-branch transitions 63
Q-switch, see laser
R-branch transitions 63
radiative lifetime 55
reduced mass, µ 26
reducible representation 21, 254
relativistic effects 232
resonance condition 3, 4
resonance-enhanced multiphoton ionization (REMPI)
spectroscopy 94–96
rigid rotor, diatomic 40–43
rotational angular momentum 40, 48
rotational constant, diatomic 41
rotational constant, linear polyatomic molecules 47
rotational constant, symmetric top 48
rotational contour 143
rotational energy levels
asymmetric top 49, 277–279
diatomics 41
linear polyatomic molecules 47
spherical top 49
symmetric tops 47–49
rotational quantum number, diatomic 41
rotational structure 5
rotational wavefunction 57
rotations, of molecules 40–50
Russell–Saunders (LS) coupling 16, 17, 245
Rydberg state 110, 180
Schr¨odinger equation 7, 9
vibrating diatomic 26
vibrating polyatomic 33
selection rules 55
electronic transitions 57–58
rotational 63–64
self-consistent field (SCF) method 235
semiempirical calculations 237
sequence bands 161
simulation, of rotational structure 178, 183, 202,
277–280
single vibronic level fluorescence spectroscopy, see
dispersed fluorescence spectroscopy
skimmer 188
Slater determinant 234
space quantization 14, 42
SPARTAN program 240
spatial symmetry 20
SpecView program 281
spherical top 45
spin angular momentum 14
electron spin quantum numbers s, m
s
15
nuclear spin quantum numbers 271
total spin quantum number S 16
spin multiplicity 17, 21
spin–orbit coupling 17, 21, 190
spin–rotation interaction 183, 199, 275
spin wavefunctions, singlet and triplet cases 267
spontaneous emission 53, 54, 80
Stark effect 42
stimulated emission 53, 79
stimulated emission pumping (SEP) spectroscopy
96
supersonic expansion (jet) 68–72, 120, 138
Mach disk 71
Mach number 69
pulsed 71
symmetric top, oblate 45
symmetric top, prolate 45
symmetries, of molecular vibrations 34, 37
symmetries, of vibrational wavefunctions 37–38
symmetry, see point group symmetry
symmetry element 249
axis of improper rotation (S
n
) 250
axis of rotational symmetry (C
n
) 250
centre of symmetry 250
plane of symmetry (mirror plane) 249
symmetry operation 18, 249
identity operation (E) 251
symmetry orbital 136
synchrotron radiation 105
time-of-flight mass spectrometer 188
transition energy 5
286 Index
transition line strength 279
transition moment 51–53, 57
and symmetry 56
photoionization 117
units 230
van der Waals complexes, production of 71
variation theorem 234
vertical ionization energy 116
vibrational
angular momentum, see angular momentum
energy levels 26
frequency 26
normal coordinates 33, 34–36
progression 115, 126, 131
quantum number 26, 34
structure 5
wavefunction 27, 34, 61
vibrations 24–39
vibronic coupling 123, 141, 163, 208
vibronic state 140
Walsh diagram 136
wavefunction 7
wavenumber 230
wave–particle duality 8
Zeeman effect 43
zero electron kinetic energy (ZEKE) spectroscopy 4,
107–109, 171
ZEKE–PFI spectroscopy 110
zero-point energy 27
zero-point fluctuations 54