Advances in Molecular Spectroscopy (eBook)

Front Cover 1
Advances in Molecular Spectroscopy 4
Copyright Page 5
Table of Contents 20
FOREWORD 6
PRESIDENTIAL ADDRESS 10
PART I: 
34 
CHAPTER 1. EXPERIMENTS AND CORRELATIONS ON MOLECULAR STRUCTURE 36
REFERENCES 48
CHAPTER 2. 
49 
INTRODUCTION 49
FORMAL BASIS 50
SOME EXAMPLES 54
REFERENCES 61
CHAPTER 3. 
62 
REFERENCES 66
CHAPTER 4. 
67 
CHAPTER 5. ROTATORY DISPERSION AND THE VIBRATING MOMENTUM OF OPTICALLY ACTIVE ABSORPTIONS BANDS 68
REFERENCES 80
CHAPTER 6. IFRARED STRUCTURAL STUDIES BEYOND FIFTY MICRONS 82
INTRODUCTION 82
PURE ROTATIONAL SPECTRA IN THE FAR INFRARED 83
VIBRATIONAL SPECTRA IN THE FAR INFRARED 83
HINDERED ROTATION 85
MOLECULES WITH INVERSION 87
DOUBLE MINIMA IN QUASI-LINEAR MOLECULES 90
REFERENCES 92
CHAPTER 7. ASSIGNMENT OF INFRARED BANDS AND THE APPROXIMATE CALCULATION OF NORMAL VIBRATIONS 93
INTRODUCTION 93
HYDROGEN DEFORMATION VIBRATIONS 94
SKELETAL VIBRATIONS 98
AMIDE 
99 
REFERENCES 102
PART II: 
104 
CHAPTER 8. EXPERIMENTAL DETERMINATION OF RAMAN INTENSITIES 105
CHAPTER 9. SPETTRI RAMAN E ASSOCIAZIONI MOLECOLARI DELLA PIRIDINA IN SOLUZIONI 
106 
BIBLIOGRAFIA 122
DISCUSSIONE 122
CHAPTER 10. 
123 
CHAPTER 11. 
124 
REFERENCES 128
CHAPTER 12. REFLEXIONSSPEKTROSKOPIE UND IHRE ANWENDUNGEN 129
BEISPIELE 130
LITERATURVERZEICHNIS 136
CHAPTER 13. MESURES PAR RÉFLEXION DANS LE SPECTRE INFRAROUGE 137
I - AVANTAGES ET UTILISATIONS DES SPECTRES INFRAROUGES PAR RÉFLEXION 137
II - TECHNIQUES POUR L'OBTENTION DES SPECTRES PAR RÉFLEXION ET QUELQUES RÉSULTATS EXPÉRIMENTAUX 138
Ill - MESURES DES CONSTANTES OPTIQUES PAR RÉFLEXION 144
IV - COMPARAISON DES DIFFÉRENTES MÉTHODES DE MESURE PAR RÉFLEXION DES CONSTANTES OPTIQUES 152
REFERENCES 153
DISCUSSION 153
CHAPTER 14. QUELQUES PROGRÉS RÉCENTS DANS L'ÉTUDE DES SPECTRES RAMAN 154
1. INTRODUCTION 154
2. TECHNIQUES EXPÉRIMENTALES 154
3. DÉTERMINATION DES FRÉQUENCES 157
4. MESURES DES INTENSITIÉS 159
5. EXPRESSION DES 
161 
6. CALCUL DES INTENSITES 164
7. EFFET RAMAN DES CRISTAUX 167
BIBLIOGRAPHIE 169
DISCUSSION 170
CHAPTER 15. 
171 
CHAPTER 15. MICROWAVE SPECTROSCOPIC STUDIES OF NEAR-LINEAR MOLECULES OF THE TYPE H2XYZ 172
1. ROTATIONAL CONSTANTS AND MOLECULAR GEOMETRY 173
2 . NUCLEAR QUADRUPOLE SPLITTINGS 175
3. MOLECULAR DIPOLE MOMENTS 176
4. CENTRIFUGAL DISTORTION EFFECTS 176
5. SPECTRA OF VIBRATIONALLY-EXCITED MOLECULES 178
REFERENCES 179
CHAPTER 16. 
181 
REFERENCES 191
DISCUSSION 191
CHAPTER 17. 
193 
INTRODUCTION 193
PERTURBATION METHODS 197
MAGNETIC EQUIVALENCE AND CHOICE OF BASIS FUNCTIONS 198
SYMMETRICAL EQUIVALENCE 202
PARTIAL ANALYSES WHICH DO NOT REQUIRE SOLVING THE SCHRÖDINGER EQUATION 202
THE MOMENT 
205 
ISOTOPIC SUBSTITUTION AND MULTIPLE IRRADIATION 206
ACKNOWLEDGEMENT 206
REFERENCES 207
DISCUSSION 207
PART III: 
208 
SECTION I: GENERAL THEORIES 
208 
CHAPTER 18. ULTRAVIOLET EMISSION SPECTRA OF 
209 
CHAPTER 19. EFFECTS OF CENTRIFUGAL STRETCHING ON THE INTENSITY OF ROTATIONAL LINES 
209 
CHAPTER 20. CONTRIBUTI AD UNO SVILUPPO MODERNO DEL CONCETTO DI COORDINAZIONE 210
(A) IONE COMPLESSO [Mo(CN)8]4- CONSIDERATO SECONDO LA SIMMETRIA DEL GRUPPO Vd - DODECAEDRO (III). 213
(B) IONE COMPLESSO [Mo(CN)8]4- SECONDO LA SIMMETRIA DEL GRUPPO C2v-PRISMA TRIGONALE A FACCE RETTANGOLARI CENTRATE (IV) 219
(C) IONE COMPLESSO [Mo(CN)8]4- SECONDO LA SIMMETRIA DEL GRUPPO D4d-ANTIPRISMA TETRAGONALE DI ARCHIMEDE. (V) 223
APPENDICE 226
BIBLIOGRAFIA 228
CHAPTER 21. THE HALF-LIFE OF THE METASTABLE LEVEL A3S OF THE NITROGEN MOLECULE 230
I. INTRODUCTION 230
II. EXPERIMENT 231
III. RESULTS 232
REFERENCES 233
CHAPTER 22. AUTOMATISCHE MOLEKÜLMODELLRECHNUNG MIT DER PERM 234
SCHRIFTTUM 241
DISCUSSION 242
CHAPTER 23. CALCULATION OF THE p ELECTRON ENERGY OF AROMATIC IONS WITH AN ODD NUMBER OF ELECTRONS: SOME REMARKS ON THE JAHN—TELLER EFFECT 243
REFERENCES 247
CHAPTER 24. RELATIONS ENTRE LES FRÉQUENCES DE VIBRATION DE VALENCE vc=o ET LA STRUCTURE ELECTRONIQUE DES COMPOSÉS CARBONYLÉS 248
CHAPTER 25. POLARIZATIONS OF ELECTRONIC TRANSITIONS 
249 
RESULTS 250
REFERENCES 252
CHAPTER 26. THE SPECTRA OP TETRAHEDRAL 
253 
1. INTRODUCTION 253
2. EXPERIMENTAL 253
3. THEORETICAL 256
4. INTERPRETATION AND DISCUSSION 257
5. CONCLUSIONS 258
REFERENCES 259
DISCUSSION 259
CHAPTER 27. APPLICATION OF THE ORBITAL VALENCY FORCE FIELD TO ALLENE, KETENE AND DIAZOMETHANE 260
REFERENCES 267
DISCUSSION 268
CHAPTER 28. COEFFICIENTS D'INTERACTION ENTRE LA VIBRATION ET LA ROTATION ET COEFFICIENTS DU POTENTIEL ANHARMONIQUE DES MOLÉCULES A SYMMETRIE AXIALE 269
CHAPTER 29. CALCUL APPROCHÉ DES FRÉQUENCES DE VIBRATION NORMALES DES BENZÉNES MONOSUBSTITUÉS A L'ÉTAT FONDAMENTAL 270
INTRODUCTION 270
PRINCIPE DU CALCUL 270
RECHERCHE DE L'ÉQUATION SÉCULAIRE 271
RÉSOLUTION DES EQUATIONS SÉCULAIRES 272
DONNÉES NUMÉRIQUES 273
RESULTATS ET DISCUSSION 273
CONCLUSION 276
BIBLIOGRAPHIE 276
CHAPTER 30. ACCURATE THEORETICAL RESULTS FOR THE GROUND STATE OF THE HYDROGEN MOLECULE 277
SELF-CONSISTENT-FIELD MOLECULAR ORBITALS 277
CORRELATED ORBITALS 279
CONFIGURATION INTERACTION WITH r12 280
QUADRUPOLE MOMENT 282
DISCUSSION 282
CHAPTER 31. THE ROLE OP THE SPIN-SPIN INTERACTION IN THE MULTIPLET SPLITTING OF THE 4. STATE OF THE 0+2 MOLECULE 284
REFERENCES 287
DISCUSSION 287
CHAPTER 32. THE ORIENTATION OF ELECTRONIC TRANSITION MOMENTS IN SOME ANTHRAQUINONE DERIVATIVES 288
REFERENCES 292
CHAPTER 33. 
293 
DISCUSSION 293
CHAPTER 34. SPECTRES DE VIBRATION DU MÉTHANOL ET CALCUL DE SON CHAMP DE FORCE 295
DISCUSSION 295
CHAPTER 35. CALCULATION OF SOME p-ELECTRON STATES IN FURAN AND THIOPHENE USING VALENCE BOND APPROXIMATION 296
REFERENCES 298
CHAPTER 36. ON THE APPLICATION OF THE ADDITIVE STATISTICAL METHOD FOR THE STUDY OF FLUORESCENT AND ABSORPTION SPECTRA 299
REFERENCES 319
CHAPTER 37. 
321 
REFERENCES 322
DISCUSSION 323
CHAPTER 38. THE CALCULATION OF ACCURATE NORMAL COORDINATES 324
DISCUSSION 325
CHAPTER 39. UN METODO APPROSSIMATO PER IL CALCOLO DELLE FREQUENZE DI VIBRAZIONE DI MOLECOLE CONTENENTI GRUPPI METILICI 326
BIBLIOGRAFIA 329
CHAPTER 40. ORDRE DE GRANDEUR DES DIVERSES CORRECTIONS A L'ÉNERGIE DE VIBRATION-ROTATION 330
CHAPTER 42. BAND SHAPES OF INDUCED ROTATIONAL AND VIBRATIONAL SPECTRA OF HOMONUCLEAR MOLECULES 331
I. ROTATIONAL ABSORPTION 331
2. VIBRATIONAL ABSORPTION 336
REFERENCES 337
DISCUSSION 337
CHAPTER 43. HYPERCONJUGATION IN SIMPLE HETERO-NUCLEAR MOLECULES 338
REFERENCES 340
CHAPTER 44. CALCOLO DELLE PERTURBAZIONI INTRODOTTE NELLO SPETTRO ULTRAROSSO DEI COMPLESSI DEL TIPO Me(CN)6 DALLA PRESENZA DI ISOTOPI E DAL CAMPO CRISTALLINO 341
CHAPTER 45. CALCUL DE L'INFLUENCE DES EFFETS DE DISPERSION SUR LE DISPLACEMENT DE LA FRÉQUENCE FONDAMENTALE DE VIBRATION DE HC1 EN SOLUTION 343
CHAPTER 46. KRAFTKONSTANTEN VON PHOSPHORSÄUREDERIVATEN BERECHNET NACH EINER RELAXATIONSMETHODE 344
1. GRUNDSCHWINGUNGEN 344
2. DIE SCHWINGUNGSGLEICHUNGEN 346
3 DAS RECHENVERFAHREN
4. DIE KRAFTKONSTANTEN 352
5. BINDUNGSZUSTAND 353
LITERATUR 354
DISCUSSION 355
CHAPTER 47. RELATIONS AMONG POTENTIAL ENERGY CURVES OF DIATOMIC MOLECULES 356
INTRODUCTION 356
PERFECT-PAIRING APPROXIMATION 357
MODIFIED PERFECT PAIRING 359
CONCLUSIONS 363
REFERENCES 363
CHAPTER 48. FONCTIONS POTENTIELLES DE VIBRATION DE QUELQUES MOLECULES ET RADICAUX LIBRES 364
1. INTRODUCTION 364
2. CALCUL DES FONCTIONS POTENTIELLES 364
DISCUSSION 367
DISCUSSION 368
DISCUSSION 372
DISCUSSION 376
BIBLIOGRAPHIE 376
CHAPTER 49. FORCE FIELD CALCULATIONS ON A NUMBER OF HIGHLY SYMMETRICAL MOLECULES OF GENERAL FORMULA X4Y6Z4 378
INTRODUCTION 378
CALCULATIONS 379
VALENCY FORCE FIELD 380
EXTENDED FORCE FIELD 381
CONCLUSIONS 385
ACKNOWLEDGEMENTS 386
REFERENCES 386
DISCUSSION 386
SECTION (II.1.): U.V. SPECTRA AND EMISSION SPECTRA 387
CHAPTER 50. THE SPECTROSCOPY AND PHOTOCHEMISTRY 
387 
REFERENCES 395
CHAPTER 51. ULTRAVIOLET EMISSION SPECTRA OF THE HYDROGEN HALIDES 396
DISCUSSION 396
CHAPTER 52. SPETTRI DI ASSORBIMENTO DI SOLUZIONI DI SALI COMPLESSI. NOTA III. DERIVATI DEL MOLIBDENOTTOCIANURO: K2Mo(CN)2(OH)2.3H20 397
CHAPTER 53. L'ASSORBIMENTO NELL'ULTRAVIOLETTO DI MOLECOLE CONTENENTI L'OSSIMMINO-GRUPPO 398
BIBLIOGRAFIA 405
CHAPTER 54. THE ABSORPTION SPECTRA AND PHOTOIONIZATION OF POLYATOMIC MOLECULES IN THE VACUUM ULTRAVIOLET 406
CHAPTER 55. 
407 
CHAPTER 56. 
408 
REFERENCES 409
DISCUSSION 409
CHAPTER 57. SPETTRI D'ASSORBIMENTO U. V. DI SOLUZIONI DI SALI COMPLESSI 410
PARTE SPERIMENTALE 411
DISCUSSIONE DEI RISULTATI 417
BIBLIOGRAFIA 419
CHAPTER 58. 
420 
THE GOLDSTEIN-KAPLAN SYSTEM 420
NEW INFRARED SYSTEM 421
REFERENCES 422
DISCUSSION 423
CHAPTER 59. ASYMMETRIC ANNELLATION EFFECTS AND THE ENERGY LEVELS IN THE ACENE SERIES 424
REFERENCES 429
CHAPTER 60. 
430 
CHAPTER 61. EFFET DE MONOSUBSTITUTION SUR LES SPECTRES ÉLECTRONIQUES DU BENZÈNE. ÉTUDE A L'ÉTAT GAZEUX 431
INTRODUCTION 431
TRANSITION 1B2u–1A1g DU BENZÈNE. EFFET DE SUBSTITUTION 431
PARTIE EXPÉRIMENTALE 434
RÉSULTATS OBTENTUS ET DISCUSSION 434
BIBLIOGRAPHIE 444
DISCUSSION 445
CHAPTER 62. 
446 
REFERENCES 450
DISCUSSION 450
CHAPTER 63. 
451 
DISCUSSION 451
CHAPTER 64. EFFETS DE MILIEUX RIGIDES SUR LES SPECTRES ÉLECTRONIQUES DU BENZÈNE 452
INTRODUCTION 452
PARTIE EXPÉRIMENTALE 452
SPECTRES D'ABSORPTION 453
EFFET DE CC14 SUR L'ABSORPTION 456
SPECTRES DE LUMINESCENCE 458
PHOSPHORESCENCE 461
EFFET DE CC14 SUR LES SPECTRES DE LUMINESCENCE 461
EFFET DE L'OXYGENE ET DU CC14 463
AUTRE ARGUMENT CONTRE L'HYPOTHESE DE HAM 465
STRUCTURES DES SPECTRES EN MILIEU RIGIDE 466
BIBLIOGRAPHIE 467
CHAPTER 65. SPETTRI IN U.V. DI ARIL-SOLFONATI 469
BIBLIOGRAFIA DI TABELLA 1 474
BIBLIOGRAFIA 475
CHAPTER 66. FLUORESZENZSPEKTRUM UND FRANCK-CONDON-PRINZIP IN LÖSUNGEN AROMATISCHER VERBINDUNGEN 476
EINLEITUNG 476
EXPERIMENTELLES 478
WELLENZAHLVERSCHIEBUNGEN 478
INTENSITÄTSÄNDERUNGEN 484
SCHLUSS 489
LITERATUR 490
CHAPTER 67. ON THE TRANSITIONS n-p* OF SOME N - OXIDES OF HETEROCYCLIC BASES 491
REFERENCES 498
DISCUSSION 498
CHAPTER 68. THE ROTATIONAL STRUCTURE OF THE VIBRATIONLESS BAND IN THE n.. ELECTRONIC TRANSITIONS OF PYRAZINE AND 8-TETRAZINE 499
REFERENCES 503
CHAPTER 69. 
504 
PARTE SPERIMENTALE 505
RISULTATI 507
CONSIDERAZIONI TEORICHE PRELIMINARI 514
BIBLIOGRAFIA 516