Investigation of 2P Be− Shape Resonances Using a Quadratically Convergent Complex Multiconfigurational Self-Consistent Field Method
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- 作者：Kousik Samanta ; Danny L. Yeager
- 刊名：Journal of Physical Chemistry B
- 出版年：2008
- 出版时间：December 18, 2008
- 年：2008
- 卷：112
- 期：50
- 页码：16214-16219
- 全文大小：155K
- 年卷期：v.112,no.50(December 18, 2008)
- ISSN：1520-5207
文摘
We develop, implement, and apply a quadratically convergent complex multiconfigurational self-consistent field method (CMCSCF) that uses the complex scaling theorem of Aguilar, Balslev, and Combes within the framework of the multiconfigurational self-consistent field method (MCSCF) in order to theoretically investigate the resonances originated due to scattering of a low-energy electron off of a neutral or an ionic target (atomic or molecular). The need to scale the electronic coordinates of the Hamiltonian as prescribed in the complex scaling theorem requires the use of a modified second quantization algebra suitable for biorthonormal spin orbital bases. In order to control the convergence to a stationary point in the complex energy hypersurface, a modified step-length control algorithm is incorporated. The position and width of 2P Be− shape resonances are calculated by inspecting the continuum states of Be−. To our knowledge, this is the first time that CMCSCF has been directly used to determine electron−atom/molecule scattering resonances. We demonstrate that both relaxation and nondynamical correlation are important for accurately describing shape resonances. For all of the calculations, the quadratically convergent CMCSCF was found to converge to the correct stationary point with a tolerance of 1.0 × 10−10 au for the energy gradient within 10 iterations or less.