ISSN:
0020-7608
Schlagwort(e):
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
Methods will be developed for variational calculations of steady-state wave functions and the corresponding quasienergies. These functions appear as solutions to the time-dependent Schrödinger equation for a molecule interacting with an oscillating electromagnetic field. A variation principle is used to obtain coupled equations for each Fourier component (FC) of the steady-state wave function. The FCs are expanded in configuration state functions using the structure of the complete active space (CAS) SCF approach. Two methods are outlined, one which is based on a common set of molecular orbitals for all FCs and one based on an individual optimization of both CI coefficients and molecular orbitals for each FC. The latter method leads to molecular orbital sets for the different FCs which are mutually nonorthogonal. Formulas are derived for the calculation of higher-order dynamic susceptibilities for steady states. An application is made to the H2 molecule, and results are presented for the frequency-dependent polarizability and hyperpolarizability along the molecular axis. The static values obtained are α = 6.413 (6.387) and γ = 676 (674) atomic units, with exact numbers within parentheses.
Zusätzliches Material:
1 Ill.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/qua.560260105
