Formulation explicite de l'effet de rotation de la fonction d'onde de vibration-rotation d'une molecule diatomique : les fonctions harmoniques de rotation

SIGLECNRS T Bordereau / INIST-CNRS - Institut de l'Information Scientifique et TechniqueFRFranc

Theoretical electronic structure of the cadmium monohalide molecules CdX (X = F, Cl, Br, I)

The potential energy and dipole moment curves for the lowest electronic states in the representation 2s+1Λ(±) of CdX (X = F, Cl, Br, I) molecules are investigated via complete active space self-consistent field (CASSCF) and multi-reference configuration interaction MRCI (single and double excitation with Davidson correction). For the bound states of CdX diatomic molecules the bond distances Re, the vibrational harmonic frequencies ωe, the rotational constants Be, the electronic energies relative to the ground state Te, and the permanent and transition dipole moments have been computed. The dissociation energy limits of the atomic levels of CdX compounds are also calculated. The transition dipole moment between the ground state X2Σ+ and (2)2Σ+ is investigated. Consequently, the transition dipole moment values of the upper state at its equilibrium position μ21, the emission angular frequency ω21, the Einstein coefficients of spontaneous and induced emissions (A21 and B21ω), the spontaneous radiative lifetime τspon, the emission cross section σ0, the line strength and the emission oscillator strength f21 are calculated along with the ionicity of the X2Σ+ and (2)2Σ+ states. The eigenvalues Ev, the rotational constants Bv, the centrifugal distortion constants Dv and the abscissas of the turning points Rmin and Rmax of X2Σ+ states of the CdX diatomics are computed. The comparison of the results with those available in literature shows a very good agreement

Approches théoriques de quelques molécules diatomiques composées d'alcalins

Nous avons calculé l'énergie potentielle sur un large domaine de la distance internucléaire allant de 5a0 à 60 a0, pour les 30 premiers états moléculaires 2s+1[Lambda(+)] les plus bas des molécules RbCs et KCs, les 28 premiers états de LiRb, NaRb et LiCs, et les 32 premiers états de la molécules NaCs. Nous présentons des tables complètes des énergies potentielles vs la distance internucléaire sur notre site à l'adresse : http://hplasim2.univ-lyon1.fr/allouche. Les courbes représentatives sont présentées, elles montrent des croisements évités pour la plupart des états excités. Nous avons déterminé aussi les constantes spectroscopiques moléculaires pour les états liés des 6 molécules, montrant une forme régulière. Une comparaison avec les résultats expérimentaux disponibles est faite. Les calculs effectués sont basés essentiellement sur les méthods ab initio dont les algorithmes sont développés au Laboratoire de Physique Quantique de Toulouse. Ces calculs utilisent des pseudopotentiels non empiriques pour représenter les cœurs ioniques, des potentiels de polarisation dépendant de l, des procédures SCF (Self Consistent Field), et des calculs d'interaction de configurations (CI) à valence complète.LYON1-BU.Sciences (692662101) / SudocSudocFranceF

Electronic structure with dipole moment and ionicity calculations of the low-lying electronic states of ZnF molecule

Adiabatic potential energy curves of the 28 low-lying doublet and quartet electronic states in the representation 2s+1Λ(±) of the zinc monofluoride molecule are investigated using the complete active space self consistent field (CASSCF) with multi-reference configuration interaction MRCI method including single and double excitations with Davidson correction (+Q). The internuclear distance Re, the harmonic frequency e, the static and transition dipole moment µ, the rotational constant Be and the electronic transition energy with respect to the ground state Te are calculated for the bound states. The transition dipole moment between some doublet states are used to determine the Einstein spontaneous and induced emission coefficients as well as the spontaneous radiative lifetime, emission wavelength and oscillator strength. The ionicity and the equilibrium dissociation energy DE,e of the ground state are also computed. The comparison between the values of the present work and those available in the literature for several electronic states shows very good agreement. Twenty-three new electronic states have been studied in the present work for the first time.The accepted manuscript in pdf format is listed with the files at the bottom of this page. The presentation of the authors' names and (or) special characters in the title of the manuscript may differ slightly between what is listed on this page and what is listed in the pdf file of the accepted manuscript; that in the pdf file of the accepted manuscript is what was submitted by the author

Electronic structure with dipole moment and rovibrational calculations of the MgLi and MgNa Molecules

We investigate an orderly study of the adiabatic potential energy curves for 29 and 30 low-lying 2s+1Λ+/- electronic states of the molecules MgLi and MgNa respectively. The calculation has been done by using the Complete Active Space Self Consistent Field (CASSCF) followed by Multi-Reference Configuration Interaction with Davidson correction (MRCI+Q). For the investigated electronic states, the static and transition dipole moment curves are calculated along with the Einstein coefficients, the emission oscillator strength, the spontaneous radiative life time, the line strength, the classical radiative decay rate of the single-electron oscillator, the spectroscopic constants Te, ωe, ωeXe, Be, Re, and the equilibrium dissociation energy De. By means of the canonical functions approach, the ro-vibrational constants Ev, Bv, Dv and the abscissas of the turning points R_min and R_max, have been calculated for the considered electronic states up to the vibrational level v = 79. The Franck-Condon factors have been calculated and plotted for the transition between the low-lying electronic states of the two considered molecules. A good agreement is revealed between our calculated values and those available in literature. Fifty new electronic states are investigated in the present work for the first time.The accepted manuscript in pdf format is listed with the files at the bottom of this page. The presentation of the authors' names and (or) special characters in the title of the manuscript may differ slightly between what is listed on this page and what is listed in the pdf file of the accepted manuscript; that in the pdf file of the accepted manuscript is what was submitted by the author

Rotation effect in the vibration-rotation wave function of a diatomic molecule

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