Excited States in Quantum Chemistry: Theoretical and Experimental Aspects of the Electronic Structure and Properties of the Excited States in Atoms, Molecules and Solids (Nato Science Series C:, 46)

It is undoubtedly true that much of the progress in the quant~m theory of matter is due to the remarkable success of the independent particle model (IPM)--especially in describing ground states. However, the accurate experimental results of the last 10 years or so, on a variety of spectroscopic phenomena and chemical processes which involve the Excited State, and the related failure of the IPM to reproduce accurately--in many cases, even qualitatively--the observed data, have sent to theorists a clear message: There is need to create and/or apply general and useful approaches to the many-electron problem of the excited state which go beyond the IPM, treat electron correlation and relativity and explain or predict all relevant physical or chemical information with consistent accuracy. This book contains articles devoted mainly to some of the most important new developments in Quantum Chemistry concerning the theoretical foundations and the computational implementation of many-body approaches to the quantitative and detailed under­ standing of the electronic excited states of atoms, molecules and solids. Furthermore, it contains experimental and pheno­ menological articles on Photoelectron and Auger spectroscopy, Lifetime measurements and Organic Photochemistry. In combination or individually, these articles constitute a good description of some current theoretical and experimental work on the electronic structure and spectroscopy of atoms, molecules, polymers, surfaces, metal oxides and amorphous solids. Front Matter....Pages i-ix Experimental Studies of Atomic and Molecular Lifetimes....Pages 1-34 Excitation Energies and Transition Moments from the Polarization Propagator....Pages 35-43 Accuracy, Timing and General Applicability of the MRD-CI Method....Pages 45-61 Calculation of Vibrational Wavefunctions and Energies Using MRD-CI Techniques....Pages 63-77 CI Calculations of Vertical Excitation Energies and Oscillator Strengths for Rydberg and Valence States of Molecules....Pages 79-103 Theory of the Electronic Structure of Excited States in Small Systems with Numerical Applications to Atomic States....Pages 105-142 Many-Body Theory of Photoabsorption in Atoms and Molecules....Pages 143-182 On Green’s Function Methods for the Study of Ionic States in Atoms and Molecules....Pages 183-272 Auger Electron Spectra from Free Atoms and Molecules....Pages 273-295 Many Body Perturbation Methods for the Calculation of Excited States....Pages 297-316 The Calculation of Atomic and Molecular Electron Binding Energies....Pages 317-328 Theory of One Electron Binding Energies Including Correlation, Relativistic and Radiative Effects: Application to Free Atoms and Metals....Pages 329-359 Atomic Photoionization Cross Sections....Pages 361-382 Theory of Atomic and Molecular Non-Stationary States Within the Coordinate Rotation Method....Pages 383-402 Use of CI Methods for the Study of Molecular Dissociation Processes in Various Electronic States....Pages 403-416 The Role of the Excited State in Organic Photochemistry....Pages 417-435 Excitons in Solids....Pages 437-456 Aspects of the Theory of Disordered Systems....Pages 457-469 Excited States of Transition Metal Oxides....Pages 471-493 Electronic Structure and Excited States of Polymers....Pages 495-529 Theory of Surface States and Chemisorption....Pages 531-556 Back Matter....Pages 557-572 Proceedings of the NATO Advanced Study Institute, Kos, Greece, June 4-18, 1978