原子分子光谱学.pptVIP

wbt * Chapter 10. REMPI, ZEKE, and MATI Spectroscopies Resonance-enhanced multiphoton ionization (REMPI) spectroscopy involves more than one photons in the ionization process. In general, the REMPI process occurs by a resonant m-photon excitation from a ground electronic state to an excited (ro)vibronic state. from a ground electronic state to an excited state and n photons from the neutral excited state to and ionic state. More (n) additional photons are then absorbed and the molecule is ionized. The probability of ionization is enhanced by the fact that the first m photons are resonant with an intermediate state. 10.1 REMPI spectroscopy Most commonly used is resonance-enhanced two-photon ionization, termed (1+1’) R2PI. The great advantages of the REMPI technique, compared to other approaches such as laser-induced fluorescence (LIF) are its (1) mass selectivity and (2) its state selectivity. 1C and 2C-REMPI spectra of phenol?N2 E2 = 31521 cm-1 Ref.: K. Müller-Dethlefs, J. Chem. Phys. 109, 9244 (1998). Goals EE, IE, vibrations in the S1 and D0 states D-substitution effect on transition energy and vibration site-specific electronic transition IAMS, Academia Sinica, Taiwan, 台灣 中研院原分所 MATI spectroscopy of aniline isotopomers What we have known S1 ← S0 at ~ 294 nm (4.19 eV), IE = 7.720 eV theoretic prediction: (a) S1 ← S0 ~ ring, (b) ionization ~  the removal of an electron from the amino part (experimental evidence is not yet available) cation data of deuterated species are not yet available Approaches preparation of C6H5NH2, C6H5NHD, C6H5ND2,  C6D5NH2, C6D5NHD, C6D5ND2 1C-R2PI and MATI experiments Preparation of C6H5NHD and C6H5ND2 (Mass 93) (Mass 95) (Mass 94) Preparation of C6H5NHD and C6H5ND2 (Mass 93) (Mass 95) (Mass 94) Relative Intensity Mass / amu TOF spectra of deuterium substituted aniline isotopomers λ = 293.94 nm λ = 292.54 nm λ = 292.48 nm 93 ? C6H5NH2+ 94 ? C6H5NHD+ 98 ? C6D5NH2+ 99 ? C