Missing levels lead to additional lines: the influence of nuclear spin statistics on femtosecond degenerate four wave mixingspectroscopy of polyatomic systems

文献情報

出版日 2005-09-23

DOI 10.1039/B510363K

インパクトファクター 3.676

著者

C. Riehn, M. I. Kunitski, V. V. Matylitsky, M. F. Gelin, B. Brutschy

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要旨

We present the results of comprehensive experimental and theoretical studies of the effect of nuclear spin statistics on the structure of rotational recurrences in femtosecond degenerate four-wave mixing (fs DFWM) spectra of asymmetric top molecules. New recurrences of J-type with a period of 1/[4(B + C)] are identified in fs DFWM spectra of near-prolate tops SO2 [H. M. Frey, P. Beaud, T. Gerber, B. Mischler, P. P. Radi and A. P. Tzannis, J. Raman Spectrosc., 2000, 31, 71] and NO2 [I. Pastirk, M. Comstock and M. Dantus, Chem. Phys. Lett., 2001, 349, 71]. Our measurements of the asymmetric oblate-like top CH3NO2 revealed new recurrences of A-type with a period of 1/(8A), A, B and C being the rotational constants.The incorporation of nuclear spin statistics into the fs DFWM simulation-fitting code allowed us to successfully reproduce all these new features and the subsequent theoretical analyses uncovered mechanisms of their appearance. The nuclear spin statistics is shown to have a profound effect on fs DFWM spectra of asymmetric top species, notably with several zero spin nuclei.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

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