Marcy E. Rosenkrantz

The molecular electronic structure of the lowest 1Σ+g, 3Σ+u, 1Σ+u, 3Σ+g, 1Πu, 1Πg, 3Πu, and 3Πg states of Na2

The multiconfiguration self‐consistent field wave functions and potential energy curves for the lowest lying 1Σ+g, 1Σ+u, 3Σ+g, 3Σ+u, 1Πg, 1Πu, 3Πg, and 3Πu states of Na2 are reported. We find good agreement with recent experimental estimates of the dissociation energies for the 1Σ+g and 1Σ+u states. We find the long range hump in the B 1Πu curve to have its maximum height of 520 cm−1 above the separated atom asymptote at R=6.45±0.1 A; recent experimental estimates of the height are 474 and 554±120 cm−1.

Electronic transition dipole moment functions and difference potentials for transitions among low-lying states of Li2 and Na2

Abstract Electronic transition dipole moment functions based on ab initio multiconfiguration self-consistent field wavefunctions are computed for the transitions 1Σu+-1Σg+, 3Σg+-3Σu+, 1Πu-1Σg+, 3Πg-3Σu+, 1Σu+-1Πg, 3Σg+-3Πu, 1Πu-1Πg, and 3Πg-3Πu in Li2 and Na2. (In each case the states are the lowest lying of their symmetry.) We also calculate the matrix element 〈3Σu+|i(Lx - iLy)|3Πu〉 for the predissociation of the 3Πu state by the 3Σu+ state. Several unobserved spectral features are predicted.

The MTXαR method: Applications to the ground state Na2 and NaLi molecules

Abstract Our recently proposed MTXαR version of the multiple scattering Xα scheme is applied to the Na2 and NaLi molecules. We find that the potential curves obtained with our “molecular” αR values (αR(Li) = 0.8390; αR(Na) = 0.8939) are in substantially better agreement with experiment than the curves based on “atomic” α values now in common use.

The ‘‘most likely’’ potential energy curve for the lowest 3Σ+u state of Li2

A most likely potential curve for the 1 3Σ+u state of Li2 with constants De=340.6±15 cm−1, ωe=65.6±0.9 cm−1, ωexe=3.16±0.04 cm−1, Re=7.77±0.22a0 is obtained by a judicious combination of three disparate ab initio computations.

Semi-empirical determination of the long-range molecular states dissociating to C(3PJ)+O(3PJ′)

Abstract We estimate values for the long-range interaction coefficients C 5 , C 6 and C 8 , and the resulting approximate potential energy curves for molecular states of CO which correspond asymptotically to ground state atoms according to the semi-empirical scheme of Bussery and Aubert-Frecon. Our calculated potential curves are in good qualitative agreement with the recent ab initio computations of Rosenkrantz, Bohr and Konowalow for the quintet states.

The canonical exchange energy modulation parameters in molecular MTXα calculations. Some first row homonuclear diatomic molecules

Abstract The canonical MTXα scheme which uses the parameters α I = 2 3 for all atoms , and α II = 1 for all molecules is developed and applied to the calculation of the potential energy curves and ionization potentials for the ground electronic states of B 2 , C 2 , N 2 , O 2 and F 2 .