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  The Oscillatory Photoelectron Signal of N-Methylmorpholine as a Test Case for the Algebraic-Diagrammatic Construction Method of Second Order

Dsouza, R., Cheng, X., Li, Z., Miller, R. J. D., & Kochman, M. A. (2018). The Oscillatory Photoelectron Signal of N-Methylmorpholine as a Test Case for the Algebraic-Diagrammatic Construction Method of Second Order. The Journal of Physical Chemistry A, 122(50), 9688-9700. doi:10.1021/acs.jpca.8b10241.

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Item Permalink: https://hdl.handle.net/21.11116/0000-0002-9488-D Version Permalink: https://hdl.handle.net/21.11116/0000-0006-CF82-E
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Animations of three representative simulated trajectories in MP4 format (ZIP) Simulated trajectories in xyz format (ZIP) Analysis of basis set effects, benchmark coupled-cluster calculations, gradient difference vector structures, molecular structures, and eigenvectors, Lewis structure of morpholine, table of normal modes of morpholine, comments on the definition of parameter Δ, discussion of the raw simulated spectrum and the effect of the Gaussian blur, ground-state conformers of NMM, and Cartesian coordinates of ground- and excited-state equilibrium geometries (PDF)
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https://dx.doi.org/10.1021/acs.jpca.8b10241 (Publisher version)
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 Creators:
Dsouza, R.1, Author           
Cheng, X.1, 2, Author           
Li, Z.1, Author           
Miller, R. J. D.1, 2, 3, Author           
Kochman, M. A.4, Author
Affiliations:
1Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society, ou_1938288              
2Hamburg Centre for Ultrafast Imaging (CUI), Universität Hamburg, ou_persistent22              
3Department of Chemistry and Physics, University of Toronto, ou_persistent22              
4Department of Physics, Chemistry and Biology (IFM), Linköping University, ou_persistent22              

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 Abstract: Motivated by recent progress in the application of time-resolved photoelectron spectroscopy (TRPES) to molecular Rydberg states, we report herein a detailed assessment of the performance of the second-order algebraic diagrammatic construction (ADC(2)) method in the simulation of their TRPES spectra. As the test case, we employ the tertiary aliphatic amine N -methylmorpholine (NMM), which is notable for the fact that the signal of its 3s state exhibits long-lived oscillations along the electron binding energy axis. The relaxation process of photoexcited NMM is simulated via the Born-Oppenheimer molecular dynamics method, and the resulting TRPES spectrum is generated basing on ionization energies and approximate Dyson orbital norms calculated with the continuum orbital technique. On the whole, the simulated TRPES spectrum achieves satisfactory agreement with experiment, which suggests that the ADC(2) method provides a realistic description of the potential energy surfaces of the relevant excited and ionized states. In particular, the simulations reproduce the fine oscillatory structure of the signal of the 3s state, and provide evidence to the effect that it results from a coherent vibrational wavepacket evolving along the deformation modes of the six-membered ring. However, it is found that ADC(2) underestimates of electron binding energies by up to a few tenths of an electronvolt. The case of NMM demonstrates the usefulness of ADC(2) as a tool to aid the interpretation of the TRPES spectra of large organic molecules.

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Language(s): eng - English
 Dates: 2018-11-262018-10-212018-11-272018-12-20
 Publication Status: Issued
 Pages: 13
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 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.jpca.8b10241
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Title: The Journal of Physical Chemistry A
  Other : J. Phys. Chem. A
Source Genre: Journal
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Publ. Info: Columbus, OH : American Chemical Society
Pages: - Volume / Issue: 122 (50) Sequence Number: - Start / End Page: 9688 - 9700 Identifier: ISSN: 1089-5639
CoNE: https://pure.mpg.de/cone/journals/resource/954926947766_4