The v6 = 1 and v6 = 2 vibrational states of DCF3 |
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Authors: | Petr Pracna,Hans Bü rger |
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Affiliation: | a J. Heyrovský Institute of Physical Chemistry, v.v.i., Academy of Sciences of the Czech Republic, Dolejškova 3, 18223 Prague, Czech Republic b Laboratoire de Mathématiques, Physique et Systèmes, Université de Perpignan, 52 avenue Paul Alduy, FR-66860 Perpignan Cedex, France c Anorganische Chemie, FB C, Bergische Universität, D-42097 Wuppertal, Germany |
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Abstract: | The high-resolution infrared spectra of DCF3 were reinvestigated in the ν6 fundamental band region near 500 cm−1 and around 1000 cm−1 with the aim to assign and analyze the overtone level of the asymmetric CF3 bending vibration v6 = 2.The present paper reports on the first study of both its sublevels (A1 and E corresponding to l = 0 and ±2, respectively) through the high-resolution analysis of the overtone band and the hot and bands.The well-known “loop method”, applied to and , yielded ground state energy differences Δ(K, J) = E0(K, J) − E0(K − 3,J) for the range of K = 6 to 30.In the final fitting of molecular parameters, we used the strategy of fitting all upper state data together with the ground state rotational transitions.This is equivalent to that calculating separately the and coefficients of the K-dependent part of the ground state energy terms from the combination loops.All rotational constants of the ground state up to sextic order could be refined in the calculation.This led to a very accurate determination of C0 = 0.18924413(25) cm−1, , and also .In the course of analyzing simultaneously the overtone band together with the and ν6 bands, the original assignment of the fundamental ν6 band [Bürger et al., J. Mol. Spectrosc. 182 (1997) 34-49] was found to be incompatible with the present one. Assignments of the (k + 1, l6 = +1)/(k − 1,l6 = −1) levels had to be interchanged, which changed the value of Cζ6 = −0.14198768(26) cm−1 and the sign of the combination of constants C − B − Cζ in the v6 = 1 level to a negative value. |
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Keywords: | Deuterated fluoroform Hot bands Overtone bands &lsquo Lonely&rsquo levels Axial ground state constants |
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