Tiresia: A code for molecular electronic continuum states and photoionization

Abstract

The Tiresia program [1] provides access to numerically accurate solutions of the one-particle Schrödinger equation for highly excited states of complex polyatomic molecules, both bound and continuum, that cannot be described by conventional Quantum Chemistry approaches. It is based on an expansion of the required solution in a local multicentric basis set, with primitive functions built as products of a radial B-spline times a real spherical harmonic. In conjunction with Density Functional Theory (DFT), it has been extensively employed in a large variety of photoionization studies, also for rather large systems. Highly excited bound states as well as wavepacket propagation can also be accurately described. In fact, the flexibility of the basis essentially allows accurate solutions of linear operator equations, like Poisson or inhomogeneous perturbative equations, which are employed in the code. The program is parallelized with standard MPI-I instructions and makes extensive use of the Scalapack linear algebra library. Ancillary programs are available for the evaluation of photoionization cross sections and angular distributions from randomly to fully oriented molecules. Program summaryProgram Title: TiresiaCPC Library link to program files:https://doi.org/10.17632/fcrjxwgjxh.1Licensing provisions: GPLv3Programming language: Fortran77, Fortran90, MPISupplementary material: Program manual documentNature of problem: Accurate solutions for highly excited and continuum electronic states in complex polyatomic molecules. Molecular photoionization cross sections and angular distributions under high energy, high-intensity radiation pulses from Synchrotron radiation and laser sources, photoelectron imaging in pump-probe experiments, basis for electronic wavepackets under ultrafast or nonperturbative excitation.Solution method: Solution of the Schrödinger and similar linear operator equations in a finite domain is obtained via basis set expansion. Flexible basis set, that may approach practical completeness within the domain, is obtained as a multicenter set of B-spline radial functions times spherical harmonics. Accurate numerical integration is employed for the evaluation of matrix elements, and conventional diagonalization for bound states, or Galerkin approach for the full multichannel solution in the continuum. Full hamiltonian and dipole matrices in the spectral basis are available for time propagation. DFT many-body description is available, and strong correlations in the bound states may be incorporated via Dyson orbitals.Additional comments including restrictions and unusual features: The code is noted for computational efficiency, which allows fast yet reasonably accurate photoionization calculations for medium-sized molecules, allowing, e.g., calculations at many molecular geometries as required to describe time-resolved photoelectron spectra in pump-probe experiments.