Total molecular photoionization cross-sections by algebraic diagrammatic construction-Stieltjes-Lanczos method

• Verfasst von: Ruberti, Marco [VerfasserIn]
• Verfasst von: Yun, R. [VerfasserIn]
• Verfasst von: Gokhberg, Kirill [VerfasserIn]
• Verfasst von: Kopelke, Sören [VerfasserIn]
• Verfasst von: Cederbaum, Lorenz S. [VerfasserIn]
• Verfasst von: Tarantelli, F. [VerfasserIn]
• Verfasst von: Averbukh, V. [VerfasserIn]
• Titel: Total molecular photoionization cross-sections by algebraic diagrammatic construction-Stieltjes-Lanczos method
• Titelzusatz: Benchmark calculations
• Verf.angabe: M. Ruberti, R. Yun, K. Gokhberg, S. Kopelke, L.S. Cederbaum, F. Tarantelli, and V. Averbukh
• E-Jahr: 2013
• Jahr: 10 October 2013
• Umfang: 10 S.
• Fussnoten: Gesehen am 21.01.2022
• Titel Quelle: Enthalten in: The journal of chemical physics
• Ort Quelle: Melville, NY : American Institute of Physics, 1933
• Jahr Quelle: 2013
• Band/Heft Quelle: 139(2013), 14, Artikel-ID 144107, Seite 1-10
• ISSN Quelle: 1089-7690
• DOI: doi:10.1063/1.4824431
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1786757834

Abstract

In [K. Gokhberg, V. Vysotskiy, L. S. Cederbaum, L. Storchi, F. Tarantelli, and V. Averbukh, J. Chem. Phys. 130, 064104 (2009)] we introduced a new - ℒ - 2 - L2 - ab initio method for the calculation of total molecular photoionization cross-sections. The method is based on the ab initio description of discretized photoionized molecular states within the many-electron Green's function approach, known as algebraic diagrammatic construction (ADC), and on the application of Stieltjes-Chebyshev moment theory to Lanczos pseudospectra of the ADC electronic Hamiltonian. Here we establish the accuracy of the new technique by comparing the ADC-Lanczos-Stieltjes cross-sections in the valence ionization region to the experimental ones for a series of eight molecules of first row elements: HF, NH3, H2O, CO2, H2CO, CH4, C2H2, and C2H4. We find that the use of the second-order ADC technique [ADC(2)] that includes double electronic excitations leads to a substantial systematic improvement over the first-order method [ADC(1)] and to a good agreement with experiment for photon energies below 80 eV. The use of extended second-order ADC theory [ADC(2)x] leads to a smaller further improvement. Above 80 eV photon energy all three methods lead to significant deviations from the experimental values which we attribute to the use of Gaussian single-electron bases. Our calculations show that the ADC(2)-Lanczos-Stieltjes technique is a reliable and efficient ab initio tool for theoretical prediction of total molecular photo-ionization cross-sections in the valence region.