Threshold photoelecron spectroscopy; Photoionization mass spectrometry; Jahn-Teller splitting; Double excitation; Autoionization; Ab initio calculation; Dissociaitve photoionization; Dissociative autoionization; CH3Cl
Abstract :
[en] The threshold photoelectron spectroscopic (TPES) and the photoionization mass spectrometric (PIMS) study of Methyl Chloride (CH3Cl) in the 8-20 eV photon energy is presented. The interpretation and assignments are supported by ab initio calculations. The detailed analysis of the TPES shows numerous features in the Jahn-Teller split ground X2E(2A'-2A") state of CH3Cl+ and a new continuus band peaking at 13.4 eV. These were assigned to both direct ionization and autoionizing transitions. The transitions to the A2A1 and to the B2E states undergo a large enhancement ascribed to important autoionizing contributions. Based on the present calculations, the weak to very weak signals in the 19-26 eV photon energy range were mainly assigned to 2a1-1 ionization and to double excitations described essentially by 2e-2, 4a11 and 1e-1, 2e-1, 4a11 configurations. The PIMS study allowed us to investigate in detail the ionization and dissociation of CH3Cl+ into CH2+, CH3+, CHCl+ and CH2Cl+ from threshold up to 20 eV photon energy. At the onset, the CH3+, CHCl+ and CH2Cl+ fragment ion production is correlated to the ground state of CH3Cl+ and all fragment ions have to appear through dissociative autoionization from the 2e->3p Rydberg state. This interpretation is supported by the photoabsorption spectrum (PAS) measured recently in the same photon energy range. At higher energies, beside direct dissociation of the A2A1 and B2E states of CH3Cl+ autoionization also contributes to the fragmentation in all decay channels. For CH3+ the photoion-pair process is analyzed and detailed assignments are proposed on the basis of recent PAS data.
Research Center/Unit :
Laboratoire de Dynamique Moléculaire, BESSY
Disciplines :
Chemistry
Author, co-author :
Locht, Robert ; Université de Liège - ULiège > Département de Chimie (Faculté des sciences) > Laboratoire de Dynamique Moléculaire (Sciences)
Leyh, Bernard ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de dynamique moléculaire
Hoxha, A.
Dehareng, Dominique ; Université de Liège - ULiège > Centre d'ingénierie des protéines
Hottmann, K.
Jochims, H.-W.; Freie Universität Berlin > Institut für Physikalische Chemie
Baumgärtel, H.; Freie Universität Berlin > Institut für Physikalische Chemie
Language :
English
Title :
About the Photoionization of Methyl Chloride. A Threshold Photoelectron Spectroscopic and Photoionization Mass Spectrometric investigation.
Alternative titles :
[fr] De la photoionisation du Chlorure de Méthyle. Une étude par spectroscopie photoélectronique de seuil et par photoionisation.
Tsuda S., Hamill W.H. J. Chem. Phys. 1964, 41:2713.
Olney T.N., Cooper G., Chan W.F., Burton G.R., Brion C.E., Tan K.H. Chem. Phys. 1996, 205:421.
Locht R., Leyh B., Hottmann K., Baumgärtel H. Chem. Phys. 1997, 220:217.
Hoxha A., Locht R., Leyh B., Dehareng D., Hottmann K., Jochims H.W., Baumgärtel H. Chem. Phys. 2000, 260:237.
Moore C.E. Ionization Potentials and Ionization Limits from the Analyses of Optical Spectra, NSRD-NBS 34 (Sept.), US Dept. Commerce Nat. Bur. Stand., US Govt. Print. Off., Washington, DC 20402; 1970.
Locht R., Leyh B., Denzer W., Hagenow G., Baumgärtel H. Chem. Phys. 1991, 155:407.
Frisch M.J., Trucks G.W., Schlegel H.B., Gill P.M.W., Johnson G.G., Robb M.A., Cheeseman J.R., Keith T.A., Petersson G.A., Montgomery J.A., Raghavachari K., Al-Laham M.A., Zakrzewski V.G., Ortiz J.V., Foresman J.B., Cioslowski J., Stefanov B.B., Nanayakkara A., Challacombe M., Peng C.Y., Ayala P.Y., Chen W., Wong M.W., Andres J.L., Replogle E.S., Gomperts R., Martin R.L., Fox D.J., Binkley J.S., Defrees D.J., Baker J., Stewart J.P., Head-Gordon M., Gonzalez C., Pople J.A. GAUSSIAN94 Revision D.4, Gaussian Inc., Pittsburgh, PA; 1996.
Hegarty D., Robb M.A. Mol. Phys. 1979, 38:1795.
Eade R.H.E., Robb M.A. Chem. Phys. Lett. 1981, 83:362.
Karlsson L., Jadrny R., Mattsson L., Chau F.T., Siegbahn K. Phys. Scripta 1977, 16:225.
Wu C.Y., Lee L.C., Judge D.L. J. Chem. Phys. 1979, 71:5221.
Mohr P.J., Taylor B.N. J. Phys. Chem. Ref. Data 1999, 28:1713.
Locht R., Momigny J. Int. J. Mass Spectrom. Ion Phys. 1971, 7:121.
Locht R., Schopman J. Int. J. Mass Spectrom. Ion Phys. 1974, 15:361.
Koopmans T. Physica's Grav. 1933, 1:104.
Von Niessen W., Åsbrink L., Bieri G. J. Electron. Spectrosc. Rel. Phenom. 1982, 26:173.
Kimura K., Katsumata S., Achiba Y., Yamazaki T., Iwata S. Handbook of He(I) Photoelectron Spectra of Fundamental Organic Molecules, Japan Sci. Soc. Press, Tokyo and Halstaed Press, New York; 1981.
Locht R., Leyh B., Hoxha A., Dehareng D., Jochims H.W., Baumgärtel H. Chem. Phys. 2000, 257:237.
Lias S.G., Bartmess J.E., Liebman J.F., Holmes J.L., Levin R.D., Mallard W.G. J. Phys. Chem. Ref. Data 1988, 17(SUPPL. 1).
Rodriquez C.F., Bohme D.K., Hopkinson A.C. J. Phys. Chem. 1996, 100:2942.
Locht R., Hoxha A., Leyh B., Lorquet J.C., Lorquet A.J. to be published.
Eland J.H.D., Frey R., Kuestler A., Schulte H., Brehm B. Int. J. Mass Spectrom. Ion Phys. 1976, 22:155.
Ruscic B., Litorja M., Asher R.L. J. Phys. Chem. A 1999, 103:8625.
Herzberg G. Molecular Spectra and Molecular Structure. III. Electronic Spectra and Electronic Structure of Polyatomic Molecules, Van Nostrand, Princeton, NJ; 1967.
Locht R., Momigny J. Int. J. Mass Spectrom. Ion Process 1986, 71:141.
Locht R., Momigny J. Photopysics and Photochemistry above 6 eV , Elsevier, Amsterdam; 1985, 171.
Locht R., Momigny J., Rühl E., Baumgärtel H. Chem. Phys. 1987, 117:305.
Weitzel K.M., Güthe F., Mähnert J., Locht R., Baumgärtel H. Chem. Phys. 1995, 201:287.
