In:
The Journal of Chemical Physics, AIP Publishing, Vol. 104, No. 13 ( 1996-04-01), p. 4961-4977
Abstract:
The CaOD à 2Π(100)/(020)–X̃ 2Σ+(020)/(000) bands have been rotationally analyzed via high resolution laser excitation. All measured line positions have been included in a global matrix deperturbation that takes account of the Renner–Teller, spin–orbit, and Fermi resonance interactions occurring in the Ã(100)(020) 2Π vibronic manifold. The corresponding bands of CaOH were studied previously; in the present work, two new CaOH subbands, Ã(020)κ 2Π–X̃(020), were recorded, and the complete data set for CaOH has been refitted using the improved model reported in this paper. The Fermi resonance parameter for CaOD has been determined as ‖W1‖=5.2707(22) cm−1; for CaOH, the newly determined value, ‖W1‖=10.3256(5) cm−1 is very close to that determined originally. The (100)∼(020) Fermi interaction in the X̃ 2Σ+ state has also been investigated for both isotopomers. The vibrational dependence of the Renner–Teller parameter εω2 has been characterized, yielding values of the anharmonic quartic parameter, ĝ4=−0.1002(3) and −0.0666(5) cm−1 for CaOH and CaOD, respectively. The ‘‘harmonic’’ Renner–Teller parameters are thus deduced as εω2=−35.6622(19) and −26.5605(31) cm−1 for CaOH and CaOD, respectively. The equilibrium bond lengths, molecular force constants and Coriolis coupling constants for both the à and X̃ states have been evaluated.
Type of Medium:
Online Resource
ISSN:
0021-9606
,
1089-7690
Language:
English
Publisher:
AIP Publishing
Publication Date:
1996
detail.hit.zdb_id:
3113-6
detail.hit.zdb_id:
1473050-9
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