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Title: Properties of reactive oxygen species by quantum Monte Carlo

Abstract

The electronic properties of the oxygen molecule, in its singlet and triplet states, and of many small oxygen-containing radicals and anions have important roles in different fields of chemistry, biology, and atmospheric science. Nevertheless, the electronic structure of such species is a challenge for ab initio computational approaches because of the difficulties to correctly describe the statical and dynamical correlation effects in presence of one or more unpaired electrons. Only the highest-level quantum chemical approaches can yield reliable characterizations of their molecular properties, such as binding energies, equilibrium structures, molecular vibrations, charge distribution, and polarizabilities. In this work we use the variational Monte Carlo (VMC) and the lattice regularized Monte Carlo (LRDMC) methods to investigate the equilibrium geometries and molecular properties of oxygen and oxygen reactive species. Quantum Monte Carlo methods are used in combination with the Jastrow Antisymmetrized Geminal Power (JAGP) wave function ansatz, which has been recently shown to effectively describe the statical and dynamical correlation of different molecular systems. In particular, we have studied the oxygen molecule, the superoxide anion, the nitric oxide radical and anion, the hydroxyl and hydroperoxyl radicals and their corresponding anions, and the hydrotrioxyl radical. Overall, the methodology was able to correctly describemore » the geometrical and electronic properties of these systems, through compact but fully-optimised basis sets and with a computational cost which scales as N{sup 3} − N{sup 4}, where N is the number of electrons. This work is therefore opening the way to the accurate study of the energetics and of the reactivity of large and complex oxygen species by first principles.« less

Authors:
 [1];  [2];  [3]
  1. Dipartimento di Fisica, La Sapienza - Università di Roma, Piazzale Aldo Moro 2, 00185 Rome (Italy)
  2. Department of Chemical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Ave, Cambridge, Massachusetts 02139 (United States)
  3. Dipartimento di Scienze Fisiche e Chimiche, Università degli studi de L'Aquila, Via Vetoio, 67100 Coppito, L'Aquila (Italy)
Publication Date:
OSTI Identifier:
22308750
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 141; Journal Issue: 1; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANIONS; BINDING ENERGY; CHARGE DISTRIBUTION; ELECTRONIC STRUCTURE; ELECTRONS; HYDROXIDES; MOLECULAR STRUCTURE; MOLECULES; MONTE CARLO METHOD; NITRIC OXIDE; OXYGEN; POLARIZABILITY; RADICALS; REACTIVITY

Citation Formats

Zen, Andrea, Trout, Bernhardt L., and Guidoni, Leonardo. Properties of reactive oxygen species by quantum Monte Carlo. United States: N. p., 2014. Web. doi:10.1063/1.4885144.
Zen, Andrea, Trout, Bernhardt L., & Guidoni, Leonardo. Properties of reactive oxygen species by quantum Monte Carlo. United States. https://doi.org/10.1063/1.4885144
Zen, Andrea, Trout, Bernhardt L., and Guidoni, Leonardo. 2014. "Properties of reactive oxygen species by quantum Monte Carlo". United States. https://doi.org/10.1063/1.4885144.
@article{osti_22308750,
title = {Properties of reactive oxygen species by quantum Monte Carlo},
author = {Zen, Andrea and Trout, Bernhardt L. and Guidoni, Leonardo},
abstractNote = {The electronic properties of the oxygen molecule, in its singlet and triplet states, and of many small oxygen-containing radicals and anions have important roles in different fields of chemistry, biology, and atmospheric science. Nevertheless, the electronic structure of such species is a challenge for ab initio computational approaches because of the difficulties to correctly describe the statical and dynamical correlation effects in presence of one or more unpaired electrons. Only the highest-level quantum chemical approaches can yield reliable characterizations of their molecular properties, such as binding energies, equilibrium structures, molecular vibrations, charge distribution, and polarizabilities. In this work we use the variational Monte Carlo (VMC) and the lattice regularized Monte Carlo (LRDMC) methods to investigate the equilibrium geometries and molecular properties of oxygen and oxygen reactive species. Quantum Monte Carlo methods are used in combination with the Jastrow Antisymmetrized Geminal Power (JAGP) wave function ansatz, which has been recently shown to effectively describe the statical and dynamical correlation of different molecular systems. In particular, we have studied the oxygen molecule, the superoxide anion, the nitric oxide radical and anion, the hydroxyl and hydroperoxyl radicals and their corresponding anions, and the hydrotrioxyl radical. Overall, the methodology was able to correctly describe the geometrical and electronic properties of these systems, through compact but fully-optimised basis sets and with a computational cost which scales as N{sup 3} − N{sup 4}, where N is the number of electrons. This work is therefore opening the way to the accurate study of the energetics and of the reactivity of large and complex oxygen species by first principles.},
doi = {10.1063/1.4885144},
url = {https://www.osti.gov/biblio/22308750}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 1,
volume = 141,
place = {United States},
year = {Mon Jul 07 00:00:00 EDT 2014},
month = {Mon Jul 07 00:00:00 EDT 2014}
}