CALCULATION OF NMR AND EPR PARAMETERS

By Z. HIINA

PART A INTRODUCTORY CHAPTERS INTRODUCTION: THE QUANTUM CHEMICAL CALCULATION OF NMR AND EPR PARAMETERS THEORY OF NMR PARAMETERS FROM RAMSEY TO RELATIVITY, 1953 TO INTRODUCTION SPIN–SPIN COUPLING CHEMICAL SHIFTS GENERAL ASPECTS FROM 1983 TO HISTORICAL ASPECTS OF EPR PARAMETER CALCULATIONS THE EFFECTIVE SPIN HAMILTONIAN CONCEPT FROM A QUANTUM CHEMICAL PERSPECTIVE FUNDAMENTALS OF NONRELATIVISTIC AND RELATIVISTIC THEORY OF NMR AND EPR PARAMETERS CLASSICAL THEORY OF THE INTERACTION OF A CHARGED PARTICLE WITH AN ELECTROMAGNETIC FIELD QUANTUM MECHANICAL HAMILTONIANS IN A TIME-INDEPENDENT ELECTROMAGNETIC FIELD PERTURBATION THEORY OF MAGNETIC EFFECTS NON-RELATIVISTIC THEORY OF EPR AND NMR PARAMETERS RELATIVISTIC THEORY OF MAGNETIC PROPERTIES THE LEADING RELATIVISTIC CORRECTIONS CONCLUDING REMARKS PART B NMR PARAMETERS, METHODOLOGICAL ASPECTS CHEMICAL SHIFTS WITH HARTREE–FOCK AND DENSITY FUNCTIONAL METHODS LINEAR RESPONSE AND THE GAUGE ORIGIN PROBLEM DETERMINATION OF THE FIRST-ORDER ORBITALS DISTRIBUTED GAUGE ORIGINS, IGLO AND GIAO APPROACHES DISTRIBUTED GAUGE ORIGINS IN REAL SPACE, A “CONTINUOUS SET OF GAUGE TRANSFORMATIONS” BEYOND PURE DENSITY FUNCTIONAL THEORY CONCLUSIONS SPIN–SPIN COUPLING CONSTANTS WITH HF AND DFT METHODS THE CALCULATION OF INDIRECT NUCLEAR SPIN–SPIN COUPLING CONSTANTS EXAMPLES OF APPLICATIONS ELECTRON-CORRELATED METHODS FOR THE CALCULATION OF NMR CHEMICAL SHIFTS THEORETICAL BACKGROUND ELECTRON-CORRELATED TREATMENT OF NMR CHEMICAL SHIFTS SPECIAL DEVELOPMENTS NUMERICAL RESULTS SUMMARY AND OUTLOOK SEMIEMPIRICAL METHODS FOR THE CALCULATION OF NMR CHEMICAL SHIFTS METHODS REPRESENTATIVE APPLICATIONS CONCLUDING REMARKS: LIMITATIONS OF SEMIEMPIRICAL METHODS FOR THE CALCULATION OF NMR PARAMETERS CONTENTS RO-VIBRATIONAL CORRECTIONS TO NMR PARAMETERS PERTURBATION THEORY OTHER APPROACHES FOR CALCULATING VIBRATIONALLY AVERAGED NMR PROPERTIES EXAMPLES OF VIBRATIONAL CONTRIBUTIONS TO NMR PROPERTIES SUMMARY MOLECULAR DYNAMICS AND NMR PARAMETER CALCULATIONS EXAMPLES SUMMARY AND CONCLUSIONS USE OF CONTINUUM SOLVENT MODELS IN MAGNETIC RESONANCE PARAMETER CALCULATIONS GENERAL FEATURES OF CONTINUUM MODELS APPLICATIONS OF CONTINUUM MODELS TO THE PREDICTION OF NMR PARAMETERS APPLICATIONS OF CONTINUUM MODELS TO THE PREDICTION OF EPR PARAMETERS PERTURBATIONAL AND ECP CALCULATION OF RELATIVISTIC EFFECTS IN NMR SHIELDING AND SPIN–SPIN COUPLING NUCLEAR SHIELDING AND SPIN–SPIN COUPLING ELECTRONIC HAMILTONIAN NON-RELATIVISTIC CONTRIBUTIONS RELATIVISTIC KINEMATICS AND THE SPIN–ZEEMAN EFFECT SPIN–ORBIT COUPLING RELATIVISTIC CORRECTIONS TO SHIELDING AND COUPLING CALCULATION OF HEAVY-NUCLEUS CHEMICAL SHIFTS RELATIVISTIC ALL-ELECTRON METHODS METHODOLOGICAL ASPECTS COMPUTATIONAL RESULTS RELATIVISTIC CALCULATIONS OF SPIN–SPIN COUPLING CONSTANTS OF HEAVY NUCLEI CALCULATIONS OF MAGNETIC RESONANCE PARAMETERS IN SOLIDS AND LIQUIDS USING PERIODIC BOUNDARY CONDITIONS CLUSTER APPROACHES TO EXTENDED SYSTEMS THE LIMITATIONS OF THE CLUSTER APPROACH INFINITE CRYSTALS, PERIODIC BOUNDARY CONDITIONS MAGNETIC RESONANCE PARAMETERS WITHIN PERIODIC BOUNDARY CONDITIONS APPLICATIONS OF THE PLANEWAVE-GIPAW METHOD WORK IN PROGRESS AND FUTURE CHALLENGES CONCLUSION CALCULATION OF NUCLEAR QUADRUPOLE COUPLING CONSTANTS NUCLEAR QUADRUPOLE MOMENTS FIELD GRADIENTS FROM AB INITIO CALCULATIONS FIELD GRADIENTS FROM DENSITY FUNCTIONAL CALCULATIONS INTERPRETATION OF NMR CHEMICAL SHIFTS NONRELATIVISTIC CASE RELATIVISTIC EFFECTS INTERPRETATION OF INDIRECT NUCLEAR SPIN–SPIN COUPLING CONSTANTS THE DIRAC VECTOR MODEL OF SPIN–SPIN COUPLING DECOMPOSITION INTO INDIVIDUAL CONTRIBUTIONS VISUALIZATION OF COUPLING BY REAL-SPACE FUNCTIONS FIRST-PRINCIPLES CALCULATIONS OF PARAMAGNETIC NMR SHIFTS PARAMAGNETIC SHIELDING TENSOR: THE GENERAL CASE TREATMENT PARAMAGNETIC SHIELDING FOR AN ISOLATED KRAMERS DOUBLET STATE PRACTICAL APPLICATIONS PART C NMR PARAMETERS, APPLICATIONS NMR PARAMETERS IN PROTEINS AND NUCLEIC ACIDS CHEMICAL SHIFTS, CLASSICAL MODELS CHEMICAL SHIFTS CALCULATIONS ON POLYPEPTIDES AND PROTEINS CHEMICAL SHIFTS IN NUCLEIC ACIDS INDIRECT SPIN–SPIN COUPLINGS IN BIOMOLECULES CHARACTERIZING TWO-BOND NMR 13C–15N, 15N–15N, AND 19F–15N SPIN–SPIN COUPLING CONSTANTS ACROSS HYDROGEN BONDS USING AB INITIO EOM-CCSD CALCULATIONS DISCUSSION CALCULATION OF NMR PARAMETERS IN CARBOCATION CHEMISTRY ALKYL AND CYCLOALKYL CATIONS BICYCLIC AND POLYCYCLIC CARBOCATIONS VINYL CATIONS P-STABILIZED CARBOCATIONS HETEROATOM STABILIZED CARBOCATIONS AROMATICITY INDICES FROM MAGNETIC SHIELDINGS AN OVERVIEW OF AROMATICITY INDICES BASED ON MAGNETIC SHIELDING APPLICATIONS OUTLOOK FULLERENES EFFICIENT COMPUTATION OF NMR PARAMETERS OF FULLERENES AND THEIR DERIVATIVES CLASSICAL IPR FULLERENES 13C NMR SPECTRA OF ISOMERIC FULLERENE ADDITION COMPOUNDS ENDOHEDRAL FULLERENES FULLERENE DIMERS AND DIMER-LIKE COMPOUNDS SOLID STATE NMR OF FULLERENES SUMMARY AND PERSPECTIVES NMR OF TRANSITION METAL COMPOUNDS LIGAND CHEMICAL SHIFTS METAL CHEMICAL SHIFTS SPIN–SPIN COUPLING CONSTANTS MISCELLANEOUS CONCLUSION AND OUTLOOK CHARACTERIZATION OF NMR TENSORS VIA EXPERIMENT AND THEORY MAGNETIC SHIELDING AND CHEMICAL SHIFTS NUCLEAR SPIN–SPIN COUPLING NMR SPECTRA OF QUADRUPOLAR NUCLEI IN SOLIDS CALCULATIONS OF NUCLEAR MAGNETIC RESONANCE PARAMETERS IN ZEOLITES THEORETICAL METHODS NMR OF FRAMEWORK ELEMENTS: STRUCTURE CHARACTERIZATION 1H NMR: ACIDITY AND PROTON TRANSFER NMR STUDIES OF GUEST MOLECULES IN ZEOLITES: IN SITU NMR PART D EPR PARAMETERS, METHODOLOGICAL ASPECTS DFT CALCULATIONS OF EPR HYPERFINE COUPLING TENSORS THE PERFORMANCE OF THE MODEL AB INITIO POST-HARTREE–FOCK CALCULATIONS OF HYPERFINE COUPLING TENSORS AND THEIR COMPARISON WITH DFT APPROACHES PROBLEMS APPEARING IN MR-CI COMPUTATIONS OF AISO ERROR CANCELLATIONS IN COMPUTATIONS OF AISO WITH DFT ALTERNATIVE FERMI CONTACT OPERATORS FOR EPR AND NMR DERIVATION OF NEW ALTERNATIVE OPERATORS FORMAL PROPERTIES OF SHORT-RANGE ALTERNATIVE OPERATORS EPR CALCULATIONS NMR CALCULATIONS CALCULATION OF EPR G-TENSORS WITH DENSITY FUNCTIONAL THEORY THE PHYSICAL ORIGIN OF THE G-TENSOR DFT EXPRESSIONS FOR G-TENSORS OF ISOLATED MOLECULES NUMERICAL PERFORMANCE OF THE DFT APPROACHES AB INITIO CALCULATIONS OF G-TENSORS GERALD H LUSHINGTON ZERO-FIELD SPLITTING ZERO-FIELD SPLITTINGS IN EPR SPECTROSCOPY THEORY OF ZERO-FIELD SPLITTINGS CALCULATION OF ZERO-FIELD SPLITTINGS PART E EPR PARAMETERS, APPLICATIONS COMPUTATION OF HYPERFINE COUPLING TENSORS TO COMPLEMENT EPR EXPERIMENTS INSIGHT GAINED FROM A CONVENTIONAL AB INITIO APPROACH BENCHMARK RESULTS USING CONVENTIONAL METHODS ON STATIC GAS-PHASE STRUCTURES THE PERFORMANCE OF CONTRACTED POPLE BASIS SETS FOR SMALL RADICALS CONSISTING ONLY OF FIRST-ROW ATOMS DENSITY FUNCTIONAL THEORY: AN ALTERNATIVE TO A CONVENTIONAL AB INITIO APPROACH CONSIDERATION OF ENVIRONMENTAL EFFECTS ILLUSTRATION OF THE APPLICATIONS OF DFT METHODS TO BIOLOGICAL RADICALS APPLICATIONS TO EPR IN BIOINORGANIC CHEMISTRY BIOLOGICAL METAL SITES CONCLUDING REMARK