Cyanates and Their Thio Derivatives: Volume 1 (1977)

Chapter 1 digital constitution of the cyanato and thiocyanato groups—ground kingdom and excited states (pages 1–68): Klaus Wittel, James L. Meeks and visible P. McGlynn
Chapter 2 Structural chemistry of the cyanates and their thio derivatives (pages 69–129): Istvan Hargittai and Iain C. Paul
Chapter three Stereochemical and conformational facets of cyanates and comparable teams (pages 131–152): George C. Corfield
Chapter four The optical rotatory dispersion and round dichroism of the cyanates and similar teams (pages 153–190): C. Toniolo
Chapter five Detection and backbone of cyanates, isocyanates, isothiocyanates, and thiocyanates (pages 191–236): David A. Ben?Efraim
Chapter 6 Thermochemistry of cyanates, isocyanates, and their thio derivatives (pages 237–271): Robert Shaw
Chapter 7 Mass spectra of cyanates, isocyanates, and comparable compounds (pages 273–293): okay. A. Jensen and Gustav Schroll
Chapter eight Hydrogen bonding and complicated formation (pages 295–319): Dusan Hadzi and Svetozar Milicev
Chapter nine The electrochemistry of cyanates and similar compounds (pages 321–342): Ole Hammerich and Vernon D. Parker
Chapter 10 Photochemistry of cyanates and comparable teams (pages 343–356): R. Jahn and U. Schmidt
Chapter eleven Radiation chemistry of natural compounds containing OCN, CNO, SCN, and CNS teams (pages 357–379): Abraham Horowitz
Chapter 12 Kinetics and mechanisms of reactions of cyanates and similar compounds (pages 381–444): Dion E. Giles
Chapter thirteen Acyl and thioacyl derivatives of isocyanates, thiocyanates and isothiocyanates (pages 445–506): Otohiko Tsuge
Chapter 14 Syntheses and makes use of of isotopically labelled cyanates and comparable teams (pages 507–548): Alberto Ceccon and Umberto Miotti
Chapter 15 Pyrolytic reactions of cyanates and comparable compounds (pages 549–567): Nestor Barroeta
Chapter sixteen Syntheses and preparative functions of cyanates (esters of cyanic acid) (pages 569–618): okay. A. Jensen and Arne Holm

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Example text

Core. which also forms a basis for E 3 / ? , gives, via the$irect product, the states A, X + and C of C : , . It is in this way that the right hand set of states of Figure 9 has been consfructed. The connection of the (A, I)states on the left with the (Q, w) states on the right may now be completed by making use of the noncrossing rule. These connections provide a simple schematization of the effects of increasing spin-orbital coupling. Spin-orbit interaction not only produces a splitting of the (A, I)states but also mixes different (A, C) states of the same double group species.

Possible to draw a few strai_ehtforward conclusions without doing any computations whatsoever. These are: (i) The coefficients of the contaminants which are admixed into the nominal states will be small. Hence. we may neglect the 'X- w 3 X - zpolarized part since it is of 2nd order in these coefficients. Thus, the So T, event will be (s, y) polarized. e.. Iin an MO excitation sense). All such events are usually of fairly low intensity. Hence. since that which may be'stolen' is small. the 'stealing' cannot ever confer a massive 'allowedness' on the T, ++So event.

Consequently, when the lead cation associates with NCOand the electrons disperse over the whole of the Pb (NC0 )2 complex, the Electronic structure of the cyanato and thiocyanato groups 49 TABLE 1 1 . Experimental data for lowest energy absorption and emission processes, 'X+ ++ X L X + ,in ~ y a n a t e s ~ ~and . " thiocyanates7' System imax(nin) NaOCN KOCN Cd(NCO)? H g(N C O)? Pb(NCO), 300 300 295 285 300 HNCO CH3NCO C6HSNCO - KSCN Zn(NCS)2 Cd(NCS)2 AgNCS Pb( NCS)2 Absorption j . 7 x lo-' lo-' - lo-' 3 x lo-' 7 10-3 - I 26 -r ~ G U R E17.

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