Towards an accurate representation of the continuum in calculations of electron, positron and laser field interactions with molecules

2nd International Conference on Mathematical Modeling in Physical Sciences 2013

物理学;数学

Maín, Zdenk^1 ; Gorfinkiel, Jimena D.^1

Open University, Department of Physical Sciences, Walton Hall, Milton Keynes MK7 6AA, United Kingdom^1

关键词: Ab initio calculations;    Analytical expressions;    B spline functions;    Gaussian-type orbitals;    Integral calculations;    Molecular integrals;    Overlap integrals;    Structure of molecules;   

Others  :  https://iopscience.iop.org/article/10.1088/1742-6596/490/1/012090/pdf
DOI  :  10.1088/1742-6596/490/1/012090

来源: IOP

【 摘 要 】

Gaussian-type orbitals (GTOs) are the most common choice of basis functions in calculations of electronic structure of molecules, i.e. for the description of bound electrons. The main advantage of this approach is the analytic form of the multicentre molecular integrals. For the same reason GTOs have been adopted as basis functions for the description of the unbound particle in many ab-initio calculations of electron, positron and laser fields interacting with molecules. However, the accurate description of the unbound particle using GTOs may become very difficult and in some cases numerically unstable. We describe an approach for the representation of the continuum in which the unbound particle is described using a mixed GTO and B-spline basis set in a manner which exploits the best features of these functions. Analytical expressions for the GTO-only molecular integrals allow us to accurately represent the part of the wavefunction close to the target, while the B-splines enable us to represent accurately the wavefunction's tail, corresponding to the unbound particle, over a wide range of kinetic energies. The main challenge posed by this approach is the accurate and rapid numerical evaluation of a large number of mixed BTO/GTO molecular integrals. We propose a scheme for this integral calculation in which the overlap integrals between GTOs and B-spline functions play a central role and demonstrate that they can be calculated rapidly and accurately.