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Matrix isolation method description

Mo2(02CCH2).. Metal compounds with multiple metal-metal bonds such as Mo2(02CCH3)4 of symmetry, have attracted much experimental and theoretical attention focussed on the description of bonding and bond strength (46-48). Their electronic structure has been investigated experimentally by various methods such as resonance Raman, photoelectron spectroscopy, ultraviolet absorption and polarization studies of the matrix isolated sample (49-56). [Pg.80]

The identification of unknown chemical compounds isolated in inert gas matrices is nowadays facilitated by comparison of the measured IR spectra with those computed at reliable levels of ab initio or density functional theory (DFT). Furthermore, the observed reactivity of matrix isolated species can in some instances be explained with the help of computed reaction energies and barriers for intramolecular rearrangements. Hence, electronic structure methods developed into a useful tool for the matrix isolation community. In this chapter, we will give an overview of the various theoretical methods and their limitations when employed in carbene chemistry. For a more detailed qualitative description of the merits and drawbacks of commonly used electronic structure methods, especially for open-shell systems, the reader is referred to the introductory guide of Bally and Borden.29... [Pg.162]

Matrix isolation-electron spin resonance. A third method used to measure HOz and ROz is matrix isolation with ESR (see earlier description of matrix isolation). Because HOz and ROz have distinct ESR signals, they can be differentiated (Mihelcic et al., 1985, 1990, 1993). For example, Fig. 11.53, part A, shows the ESR spectrum obtained when approximately... [Pg.605]

This chapter covers photochemical studies of alkenes and cycloalkenes isolated in very low temperature matrices, typically solidified noble gases or nitrogen at temperatures of 10-20 K. Under the conditions of such matrix isolation, trapped species are prevented from diffusing and are therefore prevented from undergoing bimolecular reactions. As a result, extremely reactive species can be stabihzed and investigated by a variety of normal spectroscopic methods, of which IR spectroscopy usually provides the most useful structural information. A brief description of the matrix-isolation technique and an account of its applications in several areas of organic photochemistry are given in a later chapter. [Pg.228]


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