Jacobi vectors motion

Consider a polyatomic system consisting of N nuclei (where > 3) and elecbons. In the absence of any external fields, we can rigorously separate the motion of the center of mass G of the whole system as its potential energy function V is independent of the position vector of G (rg) in a laboratory-fixed frame with origin O. This separation introduces, besides rg, the Jacobi vectors R = (R , , R , .. , Rxk -1) = (fi I "21 I fvji) fot nuclei and electrons,... 

Banachiewicz method, 67 characteristic roots, 67 characteristic vectors, 67 Cholesky method, 67 Danilevskii method, 74 deflation, 71 derogatory form, 73 "equations of motion, 418 Givens method, 75 Hessenberg form, 73 Hessenberg method, 75 Householder method, 75 Jacobi method, 71 Krylov method, 73 Lanczos form, 78 method of modification, 67 method of relaxation, 62 method of successive displacements,... 

In order to illustrate electronic transitions we discuss the simple two-dimensional model of a linear triatomic molecule ABC as depicted in Figure 2.1. R and r are the appropriate Jacobi coordinates to describe the nuclear motion and the vector q comprises all electronic coordinates. The total molecular Hamiltonian Hmoi, including all nuclear and electronic degrees of freedom, is given by Equation (2.28) with Hei and Tnu being the electronic Hamiltonian and the kinetic energy of the nuclei, respectively. 

Mass-scaled Jacobi coordinates associated to a generic arrangement X — a for A -I- BC, /I for B + CA and ) for C + AB) cU c denoted by r (diatom vector) and R (atom-molecule vector). They are used in the definition of hyperspherical coordinates which parametrize the nuclear motion of the system, namely the principal axis body frame hyperspherical coordinates [3, 4, 5]. These coordinates are ... 

In addition to the electronically adiabatic representation described by (4) and (5) or, equivalently (57) and (58), other representations can be defined in which the adiabatic electronic wave function basis set used in expansions (4) or (58) is replaced by some other set of functions of the electronic coordinates rel or r. Let us in what follows assume that we have separated the motion of the center of mass G of the system and adopted the Jacobi mass-scaled vectors R and r defined after (52), and in terms of which the adiabatic electronic wave functions are i] l,ad(r q) and the corresponding nuclear wave function coefficients are Xnd (R). The symbol q(R) refers to the set of scalar nuclear position coordinates defined after (56). Let iKil d(r q) label that alternate electronic basis set, which is allowed to be parametrically dependent on q, and for which we will use the designation diabatic. We now proceed to define such a set. LetXn(R) be the nuclear wave function coefficients associated with those diabatic electronic wave functions. As a result, we may rewrite (58) as... 

Let A, B, and C be the three atoms or particles of interest with mr r = A, J , C) being their masses and being the column vectors of their coordinates relative to an origin hxed in the laboratory. Then, after separation of the center of mass motion, the well-known Jacobi coordinates for relative motion are... 

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