화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.108, No.41, 8590-8598, 2004
Vector-algebra approach to obtain molecular fields from conical intersections: Numerical applications to H+H-2 and Na+H-2
In this paper is presented a theory according to which all of the elements of the nonadiabatic coupling matrix, tau(jk)(q,phi), are created at the singular points of the system. (These points are known also as points of conical intersections.) For this purpose, we consider the angular distribution of the angular components, tau(phijk)(q(j)similar to0,phi(j)), at the close vicinity of their singularities, namely, around the jth singularity points q(j) = 0. It is shown that these distributions determine the intensity of the entire field created by the nonadiabatic coupling matrix at every point in the region of interest. To support these statements, the three lower states of the H + H-2 system (which in our example form three conical intersections) and the third and fourth states of the Na + H-2 system (which in our example form four conical intersections) are considered. From ab initio treatments, we obtain the above-mentioned angular distributions and, having those, create the field at every desired point employing vector-algebra. The final results are compared with ab initio calculations.