A femtosecond velocity map imaging study on B-band predissociation in CH3I. I. The band origin

Gitzinger, Gregory; Corrales Castellanos, María Eugenia; Loriot, Vincent; Amaral Mathon, Gabriel; Nalda Míguez, Rebeca de; Bañares Morcillo, Luis

A femtosecond velocity map imaging study on B-band predissociation in CH3I. I. The band origin

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Official URL

https://doi.org/10.1063/1.3455207

Publication date

2010

Authors

Gitzinger, Gregory

Corrales Castellanos, María Eugenia

Loriot, Vincent

Amaral Mathon, Gabriel

Nalda Míguez, Rebeca de

Bañares Morcillo, Luis

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URI

https://hdl.handle.net/20.500.14352/94589

Citation

G. Gitzinger, M. E. Corrales, V. Loriot, G. A. Amaral, R. de Nalda, L. Bañares; A femtosecond velocity map imaging study on B-band predissociation in I. The band origin. J. Chem. Phys. 21 June 2010; 132 (23): 234313. https://doi.org/10.1063/1.3455207

Abstract

A femtosecond pump-probe experiment, coupled with velocity map ion imaging, is reported on the second absorption band (B-band) of CH3I. The measurements provide a detailed picture of real-time B-band predissociation in the band origin at 201.2 nm. Several new data are reported. (i) A value of 1.5±0.1 ps has been obtained for the lifetime of the excited state, consistent within errors with the only other direct measurement of this quantity [A. P. Baronavski and J. C. Owrutsky, J. Chem. Phys. 108, 3445 (1998)]. (ii) It has been possible to measure the angular character of the transition directly through the observation of fragments appearing early with respect to both predissociation lifetime and molecular rotation. (iii) Vibrational activity in CH3 has been found, both in the umbrella (ν2) and the symmetric stretch (ν1) modes, with estimates of relative populations. All these findings constitute a challenge and a test for much-wanted high level ab initio and dynamics calculations in this energy region.