Obtaining positions and widths of scattering resonances from a complex multiconfigurational self‐consistent field state using the M1 method

Abstract

AbstractWe present a complex multiconfigurational self‐consistent field (CMCSCF)‐based approach to investigate electron‐atom scattering resonances. It is made possible by the use of second quantization algebra adapted for biorthogonal spin orbitals, which has been applied to develop a quadratically convergent CMCSCF method. To control the convergence to the correct CMCSCF stationary point, a modified step‐length control algorithm is introduced. Convergence to a tolerance of 1.0 × 10−10 a.u. for the energy gradient is found to be typically within 10 iterations or less. A method involving the first block of the M matrix defined in the multiconfigurational spin tensor electron propagator method (MCSTEP) based on the CMCSCF reference state has been implemented to investigate 2P Be− shape resonances. The position and width of these resonances have been calculated for different complete active space choices. The wide distribution of the position and width of the resonance reported in the literature is explained by the existence of two distinct resonances which are close in energy. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010