Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 139, Issue 14, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.4824431
Keywords
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Funding
- EU through the Marie Curie ITN CORINF
- Engineering and Physical Sciences Research Council (EPSRC, UK) through the Career Acceleration Fellowship [EP/H003657/1]
- Programme Grant on Attosecond Dynamics [EP/I032517]
- Research Unit 1789 of the Deutsche Forschungsgemeinschaft
- EPSRC [EP/H003657/1, EP/I032517/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/I032517/1, EP/H003657/1] Funding Source: researchfish
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we introduced a new L(2)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. (C) 2013 AIP Publishing LLC.
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