Computing photoionization spectra in Gaussian basis sets

We present a method to compute the photoionization spectra of atoms and molecules in linear response time-dependent density functional theory. The electronic orbital variations corresponding to ionized electrons are expanded on a basis set of delocalized functions obtained as the solution of the inhomogeneous Helmholtz equation with gaussian basis set functions as right-hand side. The resulting scheme is able to reproduce photoionization spectra without any need for artificial regularization or localization. We demonstrate that it is able to produce accurate spectra for semilocal exchange-correlation functionals even using relatively small standard gaussian basis sets.

[1]  L. Greengard,et al.  Eliminating artificial boundary conditions in time-dependent density functional theory using Fourier contour deformation , 2022, Journal of chemical theory and computation.

[2]  I. Duchemin,et al.  Efficient extraction of resonant states in systems with defects , 2022, J. Comput. Phys..

[3]  J. Toulouse,et al.  Photoionization and core resonances from range-separated density-functional theory: General formalism and example of the beryllium atom. , 2022, The Journal of chemical physics.

[4]  Antoine Levitt,et al.  Finite-size effects in response functions of molecular systems , 2021, The SMAI Journal of computational mathematics.

[5]  Mohammad Al Azah,et al.  Computation of the Complex Error Function using Modified Trapezoidal Rules , 2020, SIAM J. Numer. Anal..

[6]  B. N. C. Tenorio,et al.  Molecular Photoionization and Photodetachment Cross Sections Based on L$$^2$$ Basis Sets: Theory and Selected Examples , 2021, Advances in Methods and Applications of Quantum Systems in Chemistry, Physics, and Biology.

[7]  Timothy C. Berkelbach,et al.  Recent developments in the PySCF program package. , 2020, The Journal of chemical physics.

[8]  Benjamin P Pritchard,et al.  New Basis Set Exchange: An Open, Up-to-Date Resource for the Molecular Sciences Community , 2019, J. Chem. Inf. Model..

[9]  J. Toulouse,et al.  Ab initio lifetime correction to scattering states for time-dependent electronic-structure calculations with incomplete basis sets. , 2017, The Journal of chemical physics.

[10]  Alan Edelman,et al.  Julia: A Fresh Approach to Numerical Computing , 2014, SIAM Rev..

[11]  Thierry Deutsch,et al.  Accurate complex scaling of three dimensional numerical potentials. , 2013, The Journal of chemical physics.

[12]  Pascal Molin.  Multi-precision computation of the complex error function , 2011 .

[13]  S. Ten-no,et al.  Range-separation by the Yukawa potential in long-range corrected density functional theory with Gaussian-type basis functions , 2008 .

[14]  Seiichiro Ten-no,et al.  New implementation of second-order Møller-Plesset perturbation theory with an analytic Slater-type geminal. , 2007, The Journal of chemical physics.

[15]  Seiichiro Ten-no,et al.  Initiation of explicitly correlated Slater-type geminal theory , 2004 .

[16]  J. G. Muga,et al.  Complex absorbing potentials , 2004 .

[17]  M. E. Casida.  Time-Dependent Density Functional Response Theory for Molecules , 1995 .

[18]  T. Dunning,et al.  Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions , 1992 .

[19]  T. H. Dunning.  Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen , 1989 .