Abstract
The radial couplings between the adiabatic states dissociating into Rb(5s, 5p, 4d, 6s, 6p, 5d, 7s, 6d) + Li(2s, 2p), \({\mathrm{Li}}^{+} +{ \mathrm{Rb}}^{-}\) and \({\mathrm{Li}}^{-} +{ \mathrm{Rb}}^{+}\) determined from accurate diabatic and adiabatic previous data for the LiRb molecule. The accuracy of adiabatic and diabatic results is shown by a comparison with previous ab initio calculations and experimental results. To evaluate the radial couplings we have used two methods which are numerical differentiation of the rotation matrix connecting the diabatic and adiabatic representations and the Hellmann-Feynman expression. The first and second derivatives present many peaks, associated to neutral-neutral and ionic-neutral crossings in the diabatic representation. These peaks can be interpreted from the diabatic potential energy curves. The radial coupling is then used to determine the adiabatic correction for several electronic states of LiRb molecule. This correction is about 100 cm− 1 for some electronic states around particular distances related to avoided crossings and peaks of the second derivative. It is added to the Born-Oppenheimer potential energy curves to estimate the change in spectroscopic constants, which is significant mainly for the higher excited states. The vibrational levels are evaluated using corrected and uncorrected potential energies to determine the vibronic shift for the 1Σ+ and 3Σ+ states. This shift, which is the difference between the adiabatic levels and the corrected ones, has been determined for 20 singlet and triplet Σ+ states. A shift of order 10 cm− 1 for some vibrational levels is observed, which shows the breakdown of the Born-Oppenheimer approximation.
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References
Thorsheim HR, Weiner J, Julienne PS (1987) Phys Rev Lett 58:2420
Fioretti A, Comparat D, Crubellier A, Dulieu O, Masnou-Seeuw F, Pillet P (1998) Phys Rev Lett 80:4402
Weiner J, Bagnato VC, Zilio S, Julienne PS (1999) Rev Mod Phys 71:1
Masnou-Seeuws F, Pillet P (2001) Adv Atom Mol Opt Phys 47:53
Bahns JT, Stwalley WC, Gould PL (2000) Adv Atom Mol Opt Phys 42:171
Rosker MJ, Rose TS, Zewail AH (1988) Chem Phys Lett 146:175
Engel V, Metiu H, Almeida R, Zewail AH (1988) Chem Phys Lett 152:1
Choi SE, Light JC (1989) J Chem Phys 90:2593
Grønager M, Henriksen NE (1998) J Chem Phys 109:4335
Balakrishnan N, Esry BD, Sadeghpour HR, Cornett ST, Cavagnero MJ (1999) Phys Rev A 60:1407
Igel-Mann G, Wedig U, Fuentealba P, Stoll H (1986) J Chem Phys 84:5007
Urban M, Sadlej AJ (1995) J Chem Phys 103:9692
Korek M, Allouche AR, Kobeissi M, Chaalan A, Dagher M, Fakherddin F, Aubert-Frecon M (2000) Chem Phys 256:1
Korek M, Younes G, AL-Shawa S. (2009) J Mol Struct (Theochem) 899:25
Jendoubi I, Berriche H, Ben Ouada H, Gadea FX (2011) J. Phys. Chem. A (submitted)
Jendoubi I, Berriche H, Ben Ouada H (2010) Unpublished work Conf Proc (in press)
Jensen JO, Yarkony DR (1988) J Chem Phys 89:975
Bishop DM, Cheung LM (1977) Phys Rev A 16:640
Kolos W, Wolniewicz L (1964) J Chem Phys 41:3663; (1965) 43:2429; 45 (1966) 509; 48 (1968) 3672; 49 (1968) 404; 50 (1969) 3228
Kolos W, Wolniewicz L (1963) Rev Mod Phys 35:473
Bishop DM, Cheung LM (1979) J Mol Spectrosc 75:462
Price RI (1978) Chem Phys 31:309
Koxos W, Wolniewicz L (1964) J Chem Phys 41:3663
Vidal CR, Stwalley WC (1982) J Chem Phys 77:883
Chan YC, Harding DR, Stwalley WC, Vidal CR (1986) J Chem Phys 85:2437
Berriche H (1995) Thèse Doctorat de l’Université Paul Sabatier, Toulouse
Gadea FX, Berriche H, Romero O, Villarreal P, Delgado Barrio G (1997) J Chem Phys 107:24
Gemperle F, Gadea FX (1999) J Chem Phys 110:11197
Gemperle F, Gadea FX (1999) EuroPhys Lett 48:513
Bishop DM, Cheung LM (1983) Chem Phys 78:1396
Bishop DM, Cheung LM (1983) Chem Phys 78:7265
Boutalib A, Gadéa FX (1992) J Chem Phys 97:1144
Gadéa FX, Boutalib A (1993) J Phys Atom Mol Opt Phys 26:61
Khelifi N, Oujia B, Gadéa FX (2001) J Chem Phys 117:879
Khelifi N, Zrafi W, Oujia B, Gadéa FX (2002) Phys Rev A 65:042513
Zrafi W, Oujia B, Berriche H, Gadéa FX (2006) J Mol Struct (Theochem) 777:87
Zrafi W, Oujia B, Gadéa FX (2006) J Phys B Atom Mol Opt Phys 39:1
Gadéa FX (1987) Tèse d’Etat, Université Paul Sabatier, Toulouse
Gadéa FX, Kuntz PJ (1988) Mol Phys 63:27
Gadéa FX (1987) Phys Rev A 36:2557
Gadéa FX (1991) Phys Rev A 43:1160
Gadéa FX, Pélissier M (1990) J Chem Phys 93:545
Mabrouk N, Berriche H, Gadea FX (2007) AIP Conf Proc 963:23
Mabrouk N, Berriche H (2009) AIP Conf Proc 1148:326
Johnson VA (1941) Phys Rev 60:373
Acknowledgements
We acknowledge support of this work by King Abdul Aziz City for Science and Technology (KACST) through the Long-Term Comprehensive National Plan for Science, Technology and Innovation program under Project No. 08-NAN148-7.
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Jendoubi, I., Berriche, H., Ouada, H.B., Gadea, F.X. (2012). Radial Coupling and Adiabatic Correction for the LiRb Molecule. In: Hoggan, P., Brändas, E., Maruani, J., Piecuch, P., Delgado-Barrio, G. (eds) Advances in the Theory of Quantum Systems in Chemistry and Physics. Progress in Theoretical Chemistry and Physics, vol 22. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-2076-3_24
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