Improvement on van Vleck’s formula for diatomic nonadiabatic energy shiftsстатья
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Аннотация:A formula Delta E(ivJ) approximate to [v(J)\textbackslash[2m(E(ivJ) - U-i(J))B-ij(2) + (dB(ij)/dR(2)]/Delta U-ij/v(J)]/m(2), where m is the reduced molecular mass, B-ij = [i/partial derivative/partial derivative R/j] is the radial nonadiabatic coupling matrix element for two interactive electronic states i and j, and Delta U-ij = U-i(J)(R) - U-j(J)(R) is the difference in the corresponding effective adiabatic internuclear potentials, is offered to approximate a nonadiabatic shift of the rovibronic term E(ivJ) arising from regular homogeneous perturbations in diatomic molecules. The formula has been numerically tested for B-1 Sigma(u)(+), B’(1) Sigma(u)(+), C-1 Pi(u) and D-1 Pi(u), states of molecular hydrogen. It is demonstrated that the present approximation is more accurate than the original Van Vleck formula for high v-values and has a high efficiency for nondiagonal systems with significant continuum contribution. (C) 1997 Published by Elsevier Science B.V.