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This document summarizes key aspects of ultraviolet photoelectron spectroscopy (UPS). UPS uses ultraviolet radiation to eject valence electrons from atoms or molecules. The binding energies of these electrons range from 5-30 eV. Higher resolution spectra can be obtained with UV radiation compared to x-rays. Transitions from the neutral ground vibrational state to vibrational states of the ion result in a series of equally spaced bands. The intensity of these bands depends on the Franck-Condon principle and is highest when the ion bond length matches the neutral species. UPS can provide information about bond strengths and lengths based on the electron being removed.
This document summarizes key aspects of ultraviolet photoelectron spectroscopy (UPS). UPS uses ultraviolet radiation to eject valence electrons from atoms or molecules. The binding energies of these electrons range from 5-30 eV. Higher resolution spectra can be obtained with UV radiation compared to x-rays. Transitions from the neutral ground vibrational state to vibrational states of the ion result in a series of equally spaced bands. The intensity of these bands depends on the Franck-Condon principle and is highest when the ion bond length matches the neutral species. UPS can provide information about bond strengths and lengths based on the electron being removed.
This document summarizes key aspects of ultraviolet photoelectron spectroscopy (UPS). UPS uses ultraviolet radiation to eject valence electrons from atoms or molecules. The binding energies of these electrons range from 5-30 eV. Higher resolution spectra can be obtained with UV radiation compared to x-rays. Transitions from the neutral ground vibrational state to vibrational states of the ion result in a series of equally spaced bands. The intensity of these bands depends on the Franck-Condon principle and is highest when the ion bond length matches the neutral species. UPS can provide information about bond strengths and lengths based on the electron being removed.
II-MSc.CHEMISTRY Ultra violet photo electron spectroscopy is a technique in which an ultra violet radiation is used to eject the valence electron of an atom or a molecule. The binding energy of electrons in the valence level of an atom is nearly 5-30 eV. It is possible to eject electrons with the x-ray radiation but the higher resolution is obtained with ultra violet radiation. The fine structure of band can only be observed at higher resolution which results from transitions to more than one vibrational level in the ion. Transitions originate from v=0 state in a neutral molecule to one of the vibrational state of the ion results a series of approximately equally spaced bands in the spectrum. These transitions are governed by franck condon principle. The intensity will be high where the bond length of the ion is closest to that in the neutral species. The bond length and the other properties in turn depend on what sort of electron is ionized. If an non bonding orbital is removed, there is virtually no change in the bond strength or length The bond becomes stronger; the bondlength becomes shorter. The potential well for the ion is rather deeper and narrower than that of the molecule,and the vibrational frequency increases; hence there is increase in the bond length. The bond becomes weaker and longer bond length. The decrease in bond strength results in a wider and shallower potential well, with a lower frequency than that of the neutral molecule. CO has totally 10 valence electrons(6 from O and 4 from C ) the outer 8 of which occupy the molecular orbitals 2σ(2)2π(4)2n(2) ; n represents the non bonding electron.
The 14eV band has no fine structure –represents the
removal of an electron from the non bonding orbital. The band at 16.5eV with its associated fine structure arises from 2pπ bonding orbital which is high in energy than 2sσ the latter gives rise to 19.7eV. The vibrational space is observed to be 1549cmˉ1for the 16.5eV band and the 1706cmˉ1 for the 19.7 eV band; both of these values are significantly lower than that of the fundamental frequency of the free molecule indicating the removal electron from the bonding orbital. The spacing of the lines for the 14.0eV band is about 2200cmˉ1, which indicates the removal of electron from the non bonding orbital. Two effects: i) spin orbit coupling may take place and results in the additional splitting of bands, ii) if an electron is removed from degenerate level the resulting ion may initially be in a degenerate level and subsequent distortion of the ion may lead to the removal of the degeneracy and the splitting is known as Renner Teller effect for linear molecule and Jahn Teller effect for non linear molecule. It is a technique in which x-ray radiation is used to eject the core electrons. Although such electrons play a little role in the chemical bonding different chemical environment can induce the small changes in their binding energies. During the bond formation there will be change in the distribution of the electrons and hence produces effective changes in the nuclear charge bound by the electrons. EXAMPLE:1 C-F The highly electronegative F attracts the electrons and so reduces the electron density around the carbon nucleus ; the carbon is less shielded than in the free state and is nuclear charge is increased. The core carbon electrons experience an increased nuclear force and so have a higher binding energy. This phenomenon is known as the chemical shift. Example 2: N₂O It is a linear molecule N-N-O and so the central nitrogen experiences a greater reduction of electron density and hence more strongly bound core electrons . The central atom is assigned to be at412.6eV peak and the end atom to the 408.7eV peak. In general, the XPES splittings are usually so small that they cannot be resolved and appear as slightly broadening of the bands Fundamental of molecular spetroscopy Colin N. Banwell and Elaine M. Mc cash Fourth Edition Tata Mc Graw Hill Edition. Pg No. 194-197. THANK YOU ALL