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Title: Quantum Monte Carlo for the x-ray absorption spectrum of pyrrole at the nitrogen K-edge

Abstract

Fixed-node diffusion Monte Carlo (FNDMC) is used to simulate the x-ray absorption spectrum of a gas-phase pyrrole molecule at the nitrogen K-edge. Trial wave functions for core-excited states are constructed from ground-state Kohn-Sham determinants substituted with singly occupied natural orbitals from configuration interaction with single excitations calculations of the five lowest valence-excited triplet states. The FNDMC ionization potential (IP) is found to lie within 0.3 eV of the experimental value of 406.1 {+-} 0.1 eV. The transition energies to anti-bonding virtual orbitals match the experimental spectrum after alignment of IP values and agree with the existing assignments.

Authors:
;  [1];  [1]
  1. Kenneth S. Pitzer Center for Theoretical Chemistry, Department of Chemistry, University of California Berkeley, Berkeley, California 94720-1460 (United States)
Publication Date:
OSTI Identifier:
22047194
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 136; Journal Issue: 14; Other Information: (c) 2012 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTRA; CONFIGURATION INTERACTION; EXCITED STATES; GROUND STATES; MONTE CARLO METHOD; NITROGEN; PYRROLES; X RADIATION; X-RAY SPECTRA

Citation Formats

Zubarev, Dmitry Yu, Austin, Brian M, Lester, Jr, William A, and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720. Quantum Monte Carlo for the x-ray absorption spectrum of pyrrole at the nitrogen K-edge. United States: N. p., 2012. Web. doi:10.1063/1.3700803.
Zubarev, Dmitry Yu, Austin, Brian M, Lester, Jr, William A, & Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720. Quantum Monte Carlo for the x-ray absorption spectrum of pyrrole at the nitrogen K-edge. United States. https://doi.org/10.1063/1.3700803
Zubarev, Dmitry Yu, Austin, Brian M, Lester, Jr, William A, and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720. 2012. "Quantum Monte Carlo for the x-ray absorption spectrum of pyrrole at the nitrogen K-edge". United States. https://doi.org/10.1063/1.3700803.
@article{osti_22047194,
title = {Quantum Monte Carlo for the x-ray absorption spectrum of pyrrole at the nitrogen K-edge},
author = {Zubarev, Dmitry Yu and Austin, Brian M and Lester, Jr, William A and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720},
abstractNote = {Fixed-node diffusion Monte Carlo (FNDMC) is used to simulate the x-ray absorption spectrum of a gas-phase pyrrole molecule at the nitrogen K-edge. Trial wave functions for core-excited states are constructed from ground-state Kohn-Sham determinants substituted with singly occupied natural orbitals from configuration interaction with single excitations calculations of the five lowest valence-excited triplet states. The FNDMC ionization potential (IP) is found to lie within 0.3 eV of the experimental value of 406.1 {+-} 0.1 eV. The transition energies to anti-bonding virtual orbitals match the experimental spectrum after alignment of IP values and agree with the existing assignments.},
doi = {10.1063/1.3700803},
url = {https://www.osti.gov/biblio/22047194}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 14,
volume = 136,
place = {United States},
year = {Sat Apr 14 00:00:00 EDT 2012},
month = {Sat Apr 14 00:00:00 EDT 2012}
}