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Journal of Chemical Physics / Volume 136 / Issue 6 / ARTICLES / Theoretical Methods and Algorithms

J. Chem. Phys. 136, 064107 (2012); http://dx.doi.org/10.1063/1.3682324 (15 pages)

Calculations of nonlinear response properties using the intermediate state representation and the algebraic-diagrammatic construction polarization propagator approach: Two-photon absorption spectra

S. Knippenberg1, D. R. Rehn2, M. Wormit3, J. H. Starcke1, I. L. Rusakova4, A. B. Trofimov5, and A. Dreuw2

1Institute for Physical and Theoretical Chemistry, Goethe University Frankfurt, Max-von-Laue-Str. 7, 60438 Frankfurt/Main, Germany
2Interdisciplinary Center for Scientific Computing, Ruprecht-Karls University, Im Neuenheimer Feld 368, 69120 Heidelberg, Germany
3Centre for Theoretical Chemistry and Physics, Institute for Advanced Study, Massey University, Auckland, New Zealand
4A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Street, 664033 Irkutsk, Russia
5Laboratory of Quantum Chemistry, Irkutsk State University, Karl Marx Street 1, 664003 Irkutsk, Russia

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(Received 30 November 2011; accepted 17 January 2012; published online 10 February 2012)

An earlier proposed approach to molecular response functions based on the intermediate state representation (ISR) of polarization propagator and algebraic-diagrammatic construction (ADC) approximations is for the first time employed for calculations of nonlinear response properties. The two-photon absorption (TPA) spectra are considered. The hierarchy of the first- and second-order ADC/ISR computational schemes, ADC(1), ADC(2), ADC(2)-x, and ADC(3/2), is tested in applications to H2O, HF, and C2H4 (ethylene). The calculated TPA spectra are compared with the results of coupled cluster (CC) models and time-dependent density-functional theory (TDDFT) calculations, using the results of the CC3 model as benchmarks. As a more realistic example, the TPA spectrum of C8H10 (octatetraene) is calculated using the ADC(2)-x and ADC(2) methods. The results are compared with the results of TDDFT method and earlier calculations, as well as to the available experimental data. A prominent feature of octatetraene and other polyene molecules is the existence of low-lying excited states with increased double excitation character. We demonstrate that the two-photon absorption involving such states can be adequately studied using the ADC(2)-x scheme, explicitly accounting for interaction of doubly excited configurations. Observed peaks in the experimental TPA spectrum of octatetraene are assigned based on our calculations.

© 2012 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. THEORY
    1. Algebraic diagrammatic-construction approach to polarization propagator and intermediate state representation concept
    2. Two-photon absorption cross sections in ADC/ISR formalism
    3. Block-Lanczos and sum-over-states approaches to computation of two-photon transition moments
    4. ADC/ISR approximation schemes
  3. COMPUTATIONS
  4. RESULTS AND DISCUSSION
    1. Comparison of various ADC/ISR schemes
      1. Two-photon absorption in H 2 O
      2. Two-photon absorption in HF
      3. Two-photon absorption in C 2 H 4
    2. Convergence of the Lanczos and SOS procedures
    3. Theoretical study of the two-photon absorption spectrum of octatetraene
  5. SUMMARY AND CONCLUSIONS

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KEYWORDS and PACS

Keywords

excited states, hydrogen compounds, molecule-photon collisions, organic compounds, photoexcitation, two-photon spectra, water

PACS

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.3682324

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

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