Total molecular photoionization cross-sections by algebraic diagrammatic construction-Stieltjes-Lanczos method: Benchmark calculations
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...
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| Main Authors: | , , , , , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
10 October 2013
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| In: |
The journal of chemical physics
Year: 2013, Volume: 139, Issue: 14, Pages: 1-10 |
| ISSN: | 1089-7690 |
| DOI: | 10.1063/1.4824431 |
| Online Access: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1063/1.4824431 Verlag, lizenzpflichtig, Volltext: https://aip.scitation.org/doi/10.1063/1.4824431 
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| Author Notes: | M. Ruberti, R. Yun, K. Gokhberg, S. Kopelke, L.S. Cederbaum, F. Tarantelli, and V. Averbukh |
| Summary: | 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. |
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| Item Description: | Gesehen am 21.01.2022 |
| Physical Description: | Online Resource |
| ISSN: | 1089-7690 |
| DOI: | 10.1063/1.4824431 |