Encyclopedia of Inorganic and Bioinorganic Chemistry 2005
DOI: 10.1002/9781119951438.eibc0202
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Short‐Lived Intermediates

Abstract: Methods for the generation and detection of short‐lived intermediates are discussed. These include flow systems (where a steady‐state concentration of the intermediate is monitored), flash photolysis (where the intermediate is studied in real time using a very fast detection method), and matrix isolation (where the intermediate is preserved by trapping in a solid, inert host at low temperature and where conventional spectroscopic methods are used for detection). Many of the classical experiments utilizing thes… Show more

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“…The experimental determination of reaction intermediates has traditionally relied on spectroscopic approaches usually including ultraviolet-visible absorption (UV), nuclear magnetic resonance (NMR), Raman, electron spin resonance (ESR), and infrared (IR) spectroscopies. For directly investigating short-lived species related to the chemical reaction, different sophisticated methods have been developed by using cryogenic matrix-spectroscopic techniques [ 7 ] or combining them with some special procedures like pulse radiolysis/flash photolysis (fast detection in real time based on high power light pulses), matrix isolation (stabilization by chemical trapping or low temperature) and flow systems (monitoring of steady-state intermediate concentration) [ 8 , 9 ]. Recently more fast spectroscopic methods based on high-speed (pico-through microsecond) spectroscopy have been proposed for directly observing the generation and decomposition of transient species in aqueous solution [ 10 , 11 ].…”
Section: Introductionmentioning
confidence: 99%
“…The experimental determination of reaction intermediates has traditionally relied on spectroscopic approaches usually including ultraviolet-visible absorption (UV), nuclear magnetic resonance (NMR), Raman, electron spin resonance (ESR), and infrared (IR) spectroscopies. For directly investigating short-lived species related to the chemical reaction, different sophisticated methods have been developed by using cryogenic matrix-spectroscopic techniques [ 7 ] or combining them with some special procedures like pulse radiolysis/flash photolysis (fast detection in real time based on high power light pulses), matrix isolation (stabilization by chemical trapping or low temperature) and flow systems (monitoring of steady-state intermediate concentration) [ 8 , 9 ]. Recently more fast spectroscopic methods based on high-speed (pico-through microsecond) spectroscopy have been proposed for directly observing the generation and decomposition of transient species in aqueous solution [ 10 , 11 ].…”
Section: Introductionmentioning
confidence: 99%
“…Using electronic structure methods, calculated infrared transitions derived from the Hessian can be utilized to predict thermodynamic properties like the enthalpy of formation and reaction barriers via the vibrational contributions to the molecular partition function at a given temperature. [2][3][4][5][6] As well, computational approaches can aid in experiments where the resolution is insufficient or there are difficulties in isolating the molecule, such as for diatomics, amino acids, metalligand interactions, 7 or even short-lived molecules like transition states in a chemical reaction or radical complexes, 8 facilitating the interpretation and assignment of vibrational features. [9][10][11][12][13][14] Computational chemistry methods generally employ a harmonic approximation to predict vibrational spectra.…”
Section: Introductionmentioning
confidence: 99%
“…Vibrational interactions are critical to the understanding of infrared absorption, reaction mechanisms, and kinetics as well as characterizing the interstellar medium with infrared spectrographs like the Near Infrared Spectrograph (NIRSpec) on the James Webb Space Telescope. Using electronic structure methods, calculated infrared transitions derived from the Hessian can be utilized to predict thermodynamic properties like the enthalpy of formation and reaction barriers via the vibrational contributions to the molecular partition function at a given temperature 2–6 . As well, computational approaches can aid in experiments where the resolution is insufficient or there are difficulties in isolating the molecule, such as for diatomics, amino acids, metal–ligand interactions, 7 or even short‐lived molecules like transition states in a chemical reaction or radical complexes, 8 facilitating the interpretation and assignment of vibrational features 9–14 …”
Section: Introductionmentioning
confidence: 99%