Tautomerism : methods and theories

摘要: Preface TAUTOMERISM: INTRODUCTIN, HISTORY, AND RECENT DEVELOPMENTS IN EXPERIMENTAL THEORETICAL METHODS The Definition and Scope of Tautomerism: Principles Practicalities Causes Reversal in Tautomeric Form: Aromatic Resonance Lone-Pair Dipolar Repulsion Selective Stabilization Through "Far" Intramolecular Hydrogen Bonding Changes Form Brought About by Electronegative Substituents Influence Solvent on Equilibrium: Historical Overview an Analytical Problem Short Tautomerization Dynamics Conclusions Outlook ABSORPTION UV-vis SPECTROSCOPY CHEMOMETRICS: FROM QUALITATIVE CONCLUSIONS TO QUANTITATIVE ANALYSIS Introduction Quantitative Analysis Equilibria Real Systems Concluding Remarks STUDIES OF PHOTOINDUCED NH TAUTOMERISM BY STATIONARY TIME-RESOLVED FLUORESCENCE TECHNIQUES Photoinduced Proton/Hydrogen Atom Transfer Fluorescence Techniques for Studying Tautomerism Bifunctional NH/N Azaaromatics Ab initio DFT Computational Methods as a Tool Biophysics FEMTOSECOND PUMP-PROBE Ultrafast Pump-Probe Spectroscopy from Reaction Mechanism Reaction-Path-Specific Wavepacket Double ESIPT Internal Conversion Summary NMR STUDY SOLUTION THE SOLID STATE Methodologies to Study Types Studied ISOTOPE EFFECTS ON CHEMICAL SHIFTS AS A TOOL TAUTOMERIC EQUILIBRIA Experimental Requirements Isotope Effects Chemical Shifts Secondary Equilibrium CS Primary Solid State Theoretical Calculations Examples TAUTOMER-SELECTIVE NUCLEOBASES, ISOLATED GAS PHASE Guanine Adenine Cytosine Uracil Thymine Base Pairs DIRECT EVIDENCE SOLID-STATE DIFFRACTION METHODSD: ISOMERS, EQUILIBRIA, KINETICS Application X-Ray Diffraction Proton Other Used Reactions DYNAMICS GROUND- EXCITED-STATE INTRAMOLECULAR PROTON TRANSFER REACTIONS Transition Theory Two Role the Friction Coordinate: Basics Polarization Fluctuations An Electronic Rearrangement Rug that Ties (Classical) Room Together Quantum Classical Decay Coupling Motion: Simple Example Nonlinear Optics Femtochemistry FORCE FIELD TREATMENT HYDROGEN MOLECULAR SYSTEMS Approaches with MMPT Applications Discussion SCOPE LIMITATIONS LSER TAUTOMER RATIO Taft-Kamlet Methodology Case Histories Field "BASICITY METHOD" FOR ESTIMATING RATIO: RADICAL RE-APPRAISAL Protocol Derivation Correction Factors Regularities Revealed Complicating Use "Basicity Method" Problems Which Is Inapplicable QUANTUM CALCULATION Procedures Index