The unique properties and applications of transition metal compounds have long fascinated both physicists and chemists. This volume presents theoretical and experimental studies for a deeper understanding of the electronic and vibronic properties of these compounds. In particular, an introduction into properties of spin sublevels of dd*, dÂ*, and ÂÂ* states is given, and a modern ligand field theory based on the Angular Overlap Model is presented. In experimental case studies it is shown how to characterize different types of electronic transitions using modern methods of laser spectroscopy. Consequences of spin-orbit coupling, zero-field splittings, spin-lattice relaxations, chromophore-matrix interactions, Herzberg-Teller/Franck-Condon activities, and localization/delocalization properties are treated.
An advanced-level textbook of inorganic chemistry for the graduate (B.Sc) and postgraduate (M.Sc) students of Indian and foreign universities. This book is a part of four volume series, entitled "A Textbook of Inorganic Chemistry – Volume I, II, III, IV". CONTENTS: Chapter 1. Stereochemistry and Bonding in Main Group Compounds: VSEPR theory; dπ -pπ bonds; Bent rule and energetic of hybridization. Chapter 2. Metal-Ligand Equilibria in Solution: Stepwise and overall formation constants and their interactions; Trends in stepwise constants; Factors affecting stability of metal complexes with reference to the nature of metal ion and ligand; Chelate effect and its thermodynamic origin; Determination of binary formation constants by pH-metry and spectrophotometry. Chapter 3. Reaction Mechanism of Transition Metal Complexes – I: Inert and labile complexes; Mechanisms for ligand replacement reactions; Formation of complexes from aquo ions; Ligand displacement reactions in octahedral complexes- acid hydrolysis, base hydrolysis; Racemization of tris chelate complexes; Electrophilic attack on ligands. Chapter 4. Reaction Mechanism of Transition Metal Complexes – II: Mechanism of ligand displacement reactions in square planar complexes; The trans effect; Theories of trans effect; Mechanism of electron transfer reactions – types; outer sphere electron transfer mechanism and inner sphere electron transfer mechanism; Electron exchange. Chapter 5. Isopoly and Heteropoly Acids and Salts: Isopoly and Heteropoly acids and salts of Mo and W: structures of isopoly and heteropoly anions. Chapter 6. Crystal Structures: Structures of some binary and ternary compounds such as fluorite, antifluorite, rutile, antirutile, crystobalite, layer lattices- CdI2, BiI3; ReO3, Mn2O3, corundum, pervoskite, Ilmenite and Calcite. Chapter 7. Metal-Ligand Bonding: Limitation of crystal field theory; Molecular orbital theory: octahedral, tetrahedral or square planar complexes; π-bonding and molecular orbital theory. Chapter 8. Electronic Spectra of Transition Metal Complexes: Spectroscopic ground states, Correlation and spin-orbit coupling in free ions for Ist series of transition metals; Orgel and Tanabe-Sugano diagrams for transition metal complexes (d1 – d9 states); Calculation of Dq, B and β parameters; Effect of distortion on the d-orbital energy levels; Structural evidence from electronic spectrum; John-Tellar effect; Spectrochemical and nephalauxetic series; Charge transfer spectra; Electronic spectra of molecular addition compounds. Chapter 9. Magantic Properties of Transition Metal Complexes: Elementary theory of magneto - chemistry; Guoy’s method for determination of magnetic susceptibility; Calculation of magnetic moments; Magnetic properties of free ions; Orbital contribution, effect of ligand-field; Application of magneto-chemistry in structure determination; Magnetic exchange coupling and spin state cross over. Chapter 10. Metal Clusters: Structure and bonding in higher boranes; Wade’s rules; Carboranes; Metal carbonyl clusters - low nuclearity carbonyl clusters; Total electron count (TEC). Chapter 11. Metal-π Complexes: Metal carbonyls: structure and bonding; Vibrational spectra of metal carbonyls for bonding and structure elucidation; Important reactions of metal carbonyls; Preparation, bonding, structure and important reactions of transition metal nitrosyl, dinitrogen and dioxygen complexes; Tertiary phosphine as ligand.
Contents: G. Blasse, "Vibrational Structure in the" "Luminescence Spectra of Ions in Solids."- A. Ceulemans, "The Doublet States in Chromium(III) Complexes." "A Shell-Theoretic View."- H.-H. Schmidtke, "Vibrational Progressions in Electronic" "Spectra of Complex Compounds Indicating Strong Vibronic" "Coupling."- P.E. Hoggard, "Sharp-Line Electronic Spectra and Metal-Ligand" "Geometry."- M. Colombo, A. Hauser, H.U. GA1/4del, "Competition" "Between Ligand Centered and Charge Transfer Lowest Excited" "States in bis Cyclometalated Rh3+ and Ir3+ Complexes."- D. Wexler, J.I. Zink, C. Reber, "Spectroscopic Manifestations of" "Potential" "Surface Coupling Along Normal Coordinates in " "Transition" " Metal Complexes."
Contents: G. Blasse, Vibrational Structure in the Luminescence Spectra of Ions in Solids.- A. Ceulemans, The Doublet States in Chromium(III) Complexes. A Shell-Theoretic View.- H.-H. Schmidtke, Vibrational Progressions in Electronic Spectra of Complex Compounds Indicating Strong Vibronic Coupling.- P.E. Hoggard, Sharp-Line Electronic Spectra and Metal-Ligand Geometry.- M. Colombo, A. Hauser, H.U. Güdel, Competition Between Ligand Centered and Charge Transfer Lowest Excited States in bis Cyclometalated Rh3+ and Ir3+ Complexes.- D. Wexler, J.I. Zink, C. Reber, Spectroscopic Manifestations of Potential Surface Coupling Along Normal Coordinates in Transition Metal Complexes.
Computational Photochemistry, Volume 16 provides an overview of general strategies currently used to investigate photochemical processes. Whilst contributing to establishing a branch of computational chemistry that deals with the properties and reactivity of photoexcited molecules, the book also provides insight into the conceptual and methodological research lines in computational photochemistry. Packed with examples of applications of modelling of basic photochemical reactions and the computer-aided development of novel materials in the field of photodegradation (paints), photoprotection (sunscreens), color regulation (photochromic devices) and fluorescent probes, this book is particularly useful to anyone interested in the effect of light on molecules and materials.* Provides an overview of computational photochemistry, dealing with principles and applications* Demonstrates techniques that can be used in the computer-aided design of novel photo responsive materials* Written by experts in computational photochemistry
Transition metal and rare earth compounds are investigated intensively because of important questions concerning fundamental research problems. More recently also their enormous potential for the development of new materials for photophysical and photochemical applications has been explored. Thus, it is important to focus on a deeper understanding of the elctronic energies, transition prohabilities, intermolecular interactions, etc.. This task has been accomplished by leading researchers in the field. They present introductions into, but also detailed reviews of the current state of knowledge of three different subjects.
Informal, effective undergraduate-level text introduces vibrational and electronic spectroscopy, presenting applications of group theory to the interpretation of UV, visible, and infrared spectra without assuming a high level of background knowledge. 200 problems with solutions. Numerous illustrations. "A uniform and consistent treatment of the subject matter." — Journal of Chemical Education.
