Vibrational Spectroscopy - NUI Galway National University of 振动光谱-高威国立大学.pptVIP

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Vibrational Spectroscopy - NUI Galway National University of 振动光谱-高威国立大学.ppt

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Vibrational Spectroscopy - NUI Galway National University of 振动光谱-高威国立大学

Vibrational Spectroscopy IR Spectroscopy (of various forms, e.g. RAIRS, ATR) Electron Energy Loss Spectroscopy ( EELS ) IR Spectroscopy Transmission IR Spectroscopy : studies where large surface area permits high concentration of adsorbed species. Diffuse Reflectance IR Spectroscopy ( DRIFTS ) : diffusely scattered IR collected, refocused and analysed. Employed with high surface area samples not sufficiently transparent to be studied in transmission. Reflection-Absorption IR Spectroscopy ( RAIRS ) : IR specularly reflected from front face of a highly-reflective sample, such as a metal single crystal surface. Multiple Internal Reflection Spectroscopy ( MIR ) : IR passed through IR transmitting sample and undergoes total internal reflection. IR radiation may be absorbed by species adsorbed on the solid surface - alternative name of Attenuated Total Reflection (ATR). RAIRS RAIRS surface selection rule only those vibrational modes which give rise to an oscillating dipole perpendicular (normal) to the surface are IR active and give rise to an observable absorption band. Surface selection rule RAIRS examples HCN (a) 0.15 L HCN at 100 KThe HCN molecules are weakly coordinated to the surface in a linear end-on fashion via the nitrogen; the n(H-CN) mode is seen at 3302 cm-1 but the n(C-N) mode is too weak to be seen and the d(HCN) mode expected at ca. 850 cm-1 is forbidden by the surface selection rule. The overtone of the bending mode, 2d(HCN), is however allowed and is evident at ca. 1580 cm-1. (b) 1.50 L HCN at 100 KHigher exposures lead to the physisorption of HCN molecules into a second layer. These molecules are inclined to the surface normal and the HCN bending mode (~ 820 cm-1) of these second layer molecules is no longer symmetry forbidden. Hydrogen bonding between molecules in the first and second layers also leads to a noticeable broadening of the n(H-CN) band to lower wavenumbers.(c) 30 L HCN at 200 KAt the higher temperature of 200 K onl