Computational Strategies for Spectroscopy

Computational spectroscopy is a rapidly evolving field that is becoming a versatile and widespread tool for the assignment of experimental spectra and their interpretation as related to chemical physical effects. This book is devoted to the most significant methodological contributions in the field, and to the computation of IR, UV-VIS, NMR and EPR spectral parameters with reference to the underlying vibronic and environmental effects. Each section starts with a chapter written by an experimental spectroscopist dealing with present challenges in the different fields; comprehensive coverage of conventional and advanced spectroscopic techniques is provided by means of dedicated chapters written by experts. Computational chemists, analytical chemists and spectroscopists, physicists, materials scientists, and graduate students will benefit from this thorough resource.

Contributors vii Preface xi Introduction to Electron Paramagnetic Resonance 1 Marina Brustolon and Sabine Van Doorslaer Challenge of Optical Spectroscopies 11 Ermelinda M. S. Maçôas Quest for Accurate Models: Some Challenges From Gas-Phase Experiments on Medium-Size Molecules and Clusters 25 Maurizio Becucci and Giangaetano Pietraperzia Part I Electronic and Spin States 1 UV–Visible Absorption and Emission Energies in Condensed Phase by PCM/TD-DFT Methods 39 Roberto Improta 2 Response Function Theory Computational Approaches to Linear and Nonlinear Optical Spectroscopy 77 Antonio Rizzo, Sonia Coriani, and Kenneth Ruud 3 Computational X-Ray Spectroscopy 137 Vincenzo Carravetta and Hans Ågren 4 Magnetic Resonance Spectroscopy: Singlet and Doublet Electronic States 207 Alfonso Pedone and Orlando Crescenzi 5 Application of Computational Spectroscopy to Silicon Nanocrystals: Tight-Binding Approach 249 Fabio Trani Part IIA Effects Related to Nuclear Motions: Time-Independent Models 6 Computational Approach to Rotational Spectroscopy 263 Cristina Puzzarini 7 Time-Independent Approach to Vibrational Spectroscopies 309 Chiara Cappelli and Malgorzata Biczysko 8 Time-Independent Approaches to Simulate Electronic Spectra Lineshapes: From Small Molecules to Macrosystems 361 Malgorzata Biczysko, Julien Bloino, Fabrizio Santoro, and Vincenzo Barone Part IIB Effects Related to Nuclear Motions: Time-Dependent Models 9 Efficient Methods for Computation of Ultrafast Time- and Frequency-Resolved Spectroscopic Signals 447 Maxim F. Gelin, Wolfgang Domcke, and Dassia Egorova 10 Time-Dependent Approaches to Calculation of Steady-State Vibronic Spectra: From Fully Quantum to Classical Approaches 475 Alessandro Lami and Fabrizio Santoro 11 Computational Spectroscopy by Classical Time-Dependent Approaches 517 Giuseppe Brancato and Nadia Rega 12 Stochastic Methods for Magnetic Resonance Spectroscopies 549 Antonino Polimeno, Vincenzo Barone, and Jack H. Freed Index 583