skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Ab initio multireference configuration interaction and coupled cluster studies of potential surfaces for proton transfer in (H{sub 3}N---H---OH{sub 2}){sup +}

Abstract

Proton-transfer reactions are important in chemical and biological processes, including photosynthesis and vision. The multiple reference double-excitation configuration interaction method (MRD-CI) and the coupled cluster method (CCM) were applied for the studies of the ground-state and low-lying excited states for the proton-transfer system (H{sub 3}N---H---OH{sub 2}){sup +}. The geometry optimization at the SCF level indicates the rapid change in geometry of subunits while the proton moves between N and O atoms. The significant difference was found between the structure of potential curves for the short N-O distances (2.707, 2.95, 3.2 {Angstrom}) and the long N-O distance (5.0 {Angstrom}). The complicated multireference structure of potential curves results from the strong interactions between them. The ground state is described by a single determinant wave function for short N-O distances; however, for a distance of 5.0 {Angstrom} the multireference structure becomes significant for intermediate regions of the hydrogen bond. The correlation between the protonation potential surfaces for NH{sub 3} and H{sub 2}O and the structure of surfaces for the proton-transfer system of the complex can be recognized. The simple interpretation of the gross atomic population on the transferred proton indicates that the reaction proceeds as a {open_quotes}proton transfer{close_quotes} in the ground electronic statemore » and a {open_quotes}hydrogen transfer{close_quotes} in low-lying excited states. 33 refs., 13 figs., 3 tabs.« less

Authors:
; ;  [1];  [2]
  1. Johns Hopkins Univ., Baltimore, MD (United States)
  2. Tel Aviv Univ. (Israel)
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
255256
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry
Additional Journal Information:
Journal Volume: 96; Journal Issue: 5; Other Information: PBD: 5 Mar 1992
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; 66 PHYSICS; AMMONIA; PROTON TRANSPORT; WATER; CONFIGURATION INTERACTION; MATHEMATICAL MODELS; POTENTIAL ENERGY; PROTONS; GROUND STATES; EXCITED STATES; HYDROGEN COMPLEXES

Citation Formats

Roszak, S, Chapman, D A, Kaufman, J J, and Kaldor, U. Ab initio multireference configuration interaction and coupled cluster studies of potential surfaces for proton transfer in (H{sub 3}N---H---OH{sub 2}){sup +}. United States: N. p., 1992. Web. doi:10.1021/j100184a021.
Roszak, S, Chapman, D A, Kaufman, J J, & Kaldor, U. Ab initio multireference configuration interaction and coupled cluster studies of potential surfaces for proton transfer in (H{sub 3}N---H---OH{sub 2}){sup +}. United States. https://doi.org/10.1021/j100184a021
Roszak, S, Chapman, D A, Kaufman, J J, and Kaldor, U. 1992. "Ab initio multireference configuration interaction and coupled cluster studies of potential surfaces for proton transfer in (H{sub 3}N---H---OH{sub 2}){sup +}". United States. https://doi.org/10.1021/j100184a021.
@article{osti_255256,
title = {Ab initio multireference configuration interaction and coupled cluster studies of potential surfaces for proton transfer in (H{sub 3}N---H---OH{sub 2}){sup +}},
author = {Roszak, S and Chapman, D A and Kaufman, J J and Kaldor, U},
abstractNote = {Proton-transfer reactions are important in chemical and biological processes, including photosynthesis and vision. The multiple reference double-excitation configuration interaction method (MRD-CI) and the coupled cluster method (CCM) were applied for the studies of the ground-state and low-lying excited states for the proton-transfer system (H{sub 3}N---H---OH{sub 2}){sup +}. The geometry optimization at the SCF level indicates the rapid change in geometry of subunits while the proton moves between N and O atoms. The significant difference was found between the structure of potential curves for the short N-O distances (2.707, 2.95, 3.2 {Angstrom}) and the long N-O distance (5.0 {Angstrom}). The complicated multireference structure of potential curves results from the strong interactions between them. The ground state is described by a single determinant wave function for short N-O distances; however, for a distance of 5.0 {Angstrom} the multireference structure becomes significant for intermediate regions of the hydrogen bond. The correlation between the protonation potential surfaces for NH{sub 3} and H{sub 2}O and the structure of surfaces for the proton-transfer system of the complex can be recognized. The simple interpretation of the gross atomic population on the transferred proton indicates that the reaction proceeds as a {open_quotes}proton transfer{close_quotes} in the ground electronic state and a {open_quotes}hydrogen transfer{close_quotes} in low-lying excited states. 33 refs., 13 figs., 3 tabs.},
doi = {10.1021/j100184a021},
url = {https://www.osti.gov/biblio/255256}, journal = {Journal of Physical Chemistry},
number = 5,
volume = 96,
place = {United States},
year = {Thu Mar 05 00:00:00 EST 1992},
month = {Thu Mar 05 00:00:00 EST 1992}
}