DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Several Levels of Theory for Description of Isotope Effects in Ozone: Symmetry Effect and Mass Effect

Abstract

The essential components of theory for the description of isotope effects in recombination reaction that forms ozone are presented, including the introduction of three reaction pathways for symmetric and asymmetric isotopomers, a brief review of relevant experimental data for singly- and doubly substituted isotopologues, the definitions of ζ-effect and η-effect, and the introduction of isotopic enrichment δ. Two levels of theory are developed to elucidate the role of molecular symmetry, atomic masses, vibrational zero-point energies, and rotational excitations in the recombination process. Here, the issue of symmetry is not trivial, since the important factors, such as 1/2 and 2, appear in seven different places in the formalism. It is demonstrated that if all these effects are taken into account properly, then no anomalous isotope effects emerge. At the next level of theory, a model is considered in which one scattering resonance (sitting right at the top of centrifugal barrier) is introduced per ro-vibrational channel. It is found that this approach is equivalent to statistical treatment with partition functions at the transition state. Accurate calculations using hyper-spherical coordinates show that no isotope effects come from difference in the number of states. In contrast, differences in vibrational and rotational energies lead tomore » significant isotope effects. However, those effects appear to be local, found for the rather extreme values of rotational quantum numbers. They largely cancel when rate coefficients are computed for the thermal distribution of rotational excitations. Although large isotope effects (observed in experiments) are not reproduced here, this level of theory can be used as a foundation for more detailed computational treatment, with accurate information about resonance energies and lifetimes computed and included.« less

Authors:
 [1]; ORCiD logo [2]
  1. Marquette Univ., Milwaukee, WI (United States). Dept. of Chemistry; Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Theoretical Div. (T-1, MS B221)
  2. Marquette Univ., Milwaukee, WI (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1543638
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 122; Journal Issue: 47; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Physics

Citation Formats

Teplukhin, Alexander, and Babikov, Dmitri. Several Levels of Theory for Description of Isotope Effects in Ozone: Symmetry Effect and Mass Effect. United States: N. p., 2018. Web. doi:10.1021/acs.jpca.8b09025.
Teplukhin, Alexander, & Babikov, Dmitri. Several Levels of Theory for Description of Isotope Effects in Ozone: Symmetry Effect and Mass Effect. United States. https://doi.org/10.1021/acs.jpca.8b09025
Teplukhin, Alexander, and Babikov, Dmitri. Wed . "Several Levels of Theory for Description of Isotope Effects in Ozone: Symmetry Effect and Mass Effect". United States. https://doi.org/10.1021/acs.jpca.8b09025. https://www.osti.gov/servlets/purl/1543638.
@article{osti_1543638,
title = {Several Levels of Theory for Description of Isotope Effects in Ozone: Symmetry Effect and Mass Effect},
author = {Teplukhin, Alexander and Babikov, Dmitri},
abstractNote = {The essential components of theory for the description of isotope effects in recombination reaction that forms ozone are presented, including the introduction of three reaction pathways for symmetric and asymmetric isotopomers, a brief review of relevant experimental data for singly- and doubly substituted isotopologues, the definitions of ζ-effect and η-effect, and the introduction of isotopic enrichment δ. Two levels of theory are developed to elucidate the role of molecular symmetry, atomic masses, vibrational zero-point energies, and rotational excitations in the recombination process. Here, the issue of symmetry is not trivial, since the important factors, such as 1/2 and 2, appear in seven different places in the formalism. It is demonstrated that if all these effects are taken into account properly, then no anomalous isotope effects emerge. At the next level of theory, a model is considered in which one scattering resonance (sitting right at the top of centrifugal barrier) is introduced per ro-vibrational channel. It is found that this approach is equivalent to statistical treatment with partition functions at the transition state. Accurate calculations using hyper-spherical coordinates show that no isotope effects come from difference in the number of states. In contrast, differences in vibrational and rotational energies lead to significant isotope effects. However, those effects appear to be local, found for the rather extreme values of rotational quantum numbers. They largely cancel when rate coefficients are computed for the thermal distribution of rotational excitations. Although large isotope effects (observed in experiments) are not reproduced here, this level of theory can be used as a foundation for more detailed computational treatment, with accurate information about resonance energies and lifetimes computed and included.},
doi = {10.1021/acs.jpca.8b09025},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 47,
volume = 122,
place = {United States},
year = {2018},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 8 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Two upper frames show the side- and the front-views of the PES of O3 presented as iso-energy surface in hyper-spherical coordinates. Frame a permits one to see, in three dimensions, how the reagent channels connect to the product wells through narrow transition states, as the process of ozonemore » formation proceeds along the reaction path, described here by the hyper-radius ρ. Frame b emphasizes the symmetry of the process described by the hyper-angle $\varphi$: three channels, six transition states and three wells. Frame c correlates with frame b, but gives a “map” of possible formation pathways for the case of singly substituted isotopologue, indicating the wells for symmetric 16O18O16O and asymmetric 16O16O18O, the three types of transition states for the processes A, B, and S in eqs 4 and 5, and the two types of the reagent channels, 16O + 18O16O and 16O16O + 18O. The dashed line represents the reflection plane of symmetry.« less

Save / Share:

Works referenced in this record:

The role of the radical-complex mechanism in the ozone recombination/dissociation reaction
journal, January 2005

  • Luther, Klaus; Oum, Kawon; Troe, Jürgen
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 14
  • DOI: 10.1039/b504178c

Third-body dependence of rate coefficients for ozone formation in 16O–18O mixtures
journal, June 2000


Heavy Ozone--A Difficult Puzzle to Solve
journal, November 1996


Surprising rate coefficients for four isotopic variants of O+O2+M
journal, October 1997

  • Anderson, S. M.; Hülsebusch, Detlev; Mauersberger, Konrad
  • The Journal of Chemical Physics, Vol. 107, Issue 14
  • DOI: 10.1063/1.474247

Relative formation rates of 50O3 and 52O3 in 16O–18O mixtures
journal, October 1999

  • Janssen, Christof; Guenther, Juergen; Krankowsky, Dieter
  • The Journal of Chemical Physics, Vol. 111, Issue 16
  • DOI: 10.1063/1.480045

Ozone Isotope Enrichment: Isotopomer-Specific Rate Coefficients
journal, January 1999


Kinetic origin of the ozone isotope effect: a critical analysis of enrichments and rate coefficients
journal, October 2001

  • Janssen, Christof; Guenther, Jürgen; Mauersberger, Konrad
  • Physical Chemistry Chemical Physics, Vol. 3, Issue 21
  • DOI: 10.1039/b107171h

Mass-Independent Isotope Effects in Planetary Atmospheres and the Early Solar System
journal, January 1999


History and Applications of Mass-Independent Isotope Effects
journal, May 2006


The Physical Chemistry of Mass-Independent Isotope Effects and Their Observation in Nature
journal, May 2012


DYNAMICAL STUDIES OF THE OZONE ISOTOPE EFFECT: A Status Report
journal, May 2006


Coriolis coupling as a source of non-RRKM effects in ozone molecule: Lifetime statistics of vibrationally excited ozone molecules
journal, June 2010

  • Kryvohuz, M.; Marcus, R. A.
  • The Journal of Chemical Physics, Vol. 132, Issue 22
  • DOI: 10.1063/1.3430514

Formation of ozone: Metastable states and anomalous isotope effect
journal, August 2003

  • Babikov, Dmitri; Kendrick, Brian K.; Walker, Robert B.
  • The Journal of Chemical Physics, Vol. 119, Issue 5
  • DOI: 10.1063/1.1587113

Metastable states of ozone calculated on an accurate potential energy surface
journal, April 2003

  • Babikov, Dmitri; Kendrick, Brian K.; Walker, Robert B.
  • The Journal of Chemical Physics, Vol. 118, Issue 14
  • DOI: 10.1063/1.1557936

Quantum origin of an anomalous isotope effect in ozone formation
journal, May 2003


Towards quantum mechanical description of the unconventional mass-dependent isotope effect in ozone: Resonance recombination in the strong collision approximation
journal, November 2009

  • Grebenshchikov, S. Yu.; Schinke, R.
  • The Journal of Chemical Physics, Vol. 131, Issue 18
  • DOI: 10.1063/1.3253994

Quantum-mechanical calculations on pressure and temperature dependence of three-body recombination reactions: Application to ozone formation rates
journal, February 2004

  • Charlo, David; Clary, David C.
  • The Journal of Chemical Physics, Vol. 120, Issue 6
  • DOI: 10.1063/1.1635361

Quantum-mechanical calculations on termolecular association reactions XY+Z+M→XYZ+M: Application to ozone formation
journal, July 2002

  • Charlo, David; Clary, David C.
  • The Journal of Chemical Physics, Vol. 117, Issue 4
  • DOI: 10.1063/1.1485069

Collisional stabilization of van der Waals states of ozone
journal, May 2011

  • Ivanov, Mikhail V.; Babikov, Dmitri
  • The Journal of Chemical Physics, Vol. 134, Issue 17
  • DOI: 10.1063/1.3585690

Efficient quantum-classical method for computing thermal rate constant of recombination: Application to ozone formation
journal, May 2012

  • Ivanov, Mikhail V.; Babikov, Dmitri
  • The Journal of Chemical Physics, Vol. 136, Issue 18
  • DOI: 10.1063/1.4711760

On molecular origin of mass-independent fractionation of oxygen isotopes in the ozone forming recombination reaction
journal, February 2013

  • Ivanov, M. V.; Babikov, D.
  • Proceedings of the National Academy of Sciences, Vol. 110, Issue 44
  • DOI: 10.1073/pnas.1215464110

On stabilization of scattering resonances in recombination reaction that forms ozone
journal, April 2016

  • Ivanov, Mikhail V.; Babikov, Dmitri
  • The Journal of Chemical Physics, Vol. 144, Issue 15
  • DOI: 10.1063/1.4945779

Quantum inelastic scattering study of isotope effects in ozone stabilization dynamics
journal, August 2005


Intra- and intermolecular energy transfer in highly excited ozone complexes
journal, June 2004

  • Ivanov, Mikhail V.; Grebenshchikov, Sergy Yu.; Schinke, Reinhard
  • The Journal of Chemical Physics, Vol. 120, Issue 21
  • DOI: 10.1063/1.1712866

Temperature dependent energy transfer in Ar–O3 collisions
journal, June 2005

  • Ivanov, Mikhail V.; Schinke, Reinhard
  • The Journal of Chemical Physics, Vol. 122, Issue 23
  • DOI: 10.1063/1.1927526

An intramolecular theory of the mass-independent isotope effect for ozone. I
journal, September 1999

  • Hathorn, B. C.; Marcus, R. A.
  • The Journal of Chemical Physics, Vol. 111, Issue 9
  • DOI: 10.1063/1.480267

An intramolecular theory of the mass-independent isotope effect for ozone. II. Numerical implementation at low pressures using a loose transition state
journal, December 2000

  • Hathorn, B. C.; Marcus, R. A.
  • The Journal of Chemical Physics, Vol. 113, Issue 21
  • DOI: 10.1063/1.1321045

Strange and Unconventional Isotope Effects in Ozone Formation
journal, May 2001


On the theory of the strange and unconventional isotopic effects in ozone formation
journal, January 2002

  • Gao, Yi Qin; Marcus, R. A.
  • The Journal of Chemical Physics, Vol. 116, Issue 1
  • DOI: 10.1063/1.1415448

A theoretical study of ozone isotopic effects using a modified ab initio potential energy surface
journal, July 2002

  • Gao, Yi Qin; Chen, Wei-Chen; Marcus, R. A.
  • The Journal of Chemical Physics, Vol. 117, Issue 4
  • DOI: 10.1063/1.1488577

Communication: An accurate global potential energy surface for the ground electronic state of ozone
journal, November 2013

  • Dawes, Richard; Lolur, Phalgun; Li, Anyang
  • The Journal of Chemical Physics, Vol. 139, Issue 20
  • DOI: 10.1063/1.4837175

Calculated vibrational states of ozone up to dissociation
journal, February 2016

  • Ndengué, Steve; Dawes, Richard; Wang, Xiao-Gang
  • The Journal of Chemical Physics, Vol. 144, Issue 7
  • DOI: 10.1063/1.4941559

Efficient method for calculations of ro-vibrational states in triatomic molecules near dissociation threshold: Application to ozone
journal, September 2016

  • Teplukhin, Alexander; Babikov, Dmitri
  • The Journal of Chemical Physics, Vol. 145, Issue 11
  • DOI: 10.1063/1.4962914

Lifetimes and wave functions of ozone metastable vibrational states near the dissociation limit in a full-symmetry approach
journal, October 2016


State-to-state reaction dynamics of 18 O+ 32 O 2 studied by a time-dependent quantum wavepacket method
journal, February 2015

  • Xie, Wenbo; Liu, Lan; Sun, Zhigang
  • The Journal of Chemical Physics, Vol. 142, Issue 6
  • DOI: 10.1063/1.4907229

Differential Cross Sections and Product Rovibrational Distributions for 16 O + 32 O 2 and 18 O + 36 O 2 Collisions
journal, November 2015

  • Rao, Tammineni Rajagopala; Guillon, Grégoire; Mahapatra, Susanta
  • The Journal of Physical Chemistry A, Vol. 119, Issue 46
  • DOI: 10.1021/acs.jpca.5b08638

A full-dimensional model of ozone forming reaction: the absolute value of the recombination rate coefficient, its pressure and temperature dependencies
journal, January 2016

  • Teplukhin, Alexander; Babikov, Dmitri
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 28
  • DOI: 10.1039/C6CP02224C

Visualization of Potential Energy Function Using an Isoenergy Approach and 3D Prototyping
journal, November 2014

  • Teplukhin, Alexander; Babikov, Dmitri
  • Journal of Chemical Education, Vol. 92, Issue 2
  • DOI: 10.1021/ed500683g

Quantum reactive scattering in three dimensions using hyperspherical (APH) coordinates. Theory
journal, October 1987

  • Pack, Russell T.; Parker, Gregory A.
  • The Journal of Chemical Physics, Vol. 87, Issue 7
  • DOI: 10.1063/1.452944

Global permutationally invariant potential energy surface for ozone forming reaction
journal, April 2013

  • Ayouz, Mehdi; Babikov, Dmitri
  • The Journal of Chemical Physics, Vol. 138, Issue 16
  • DOI: 10.1063/1.4799915

One possible source of mass-independent fractionation of sulfur isotopes in the Archean atmosphere of Earth
journal, May 2017

  • Babikov, Dmitri; Semenov, Alexander; Teplukhin, Alexander
  • Geochimica et Cosmochimica Acta, Vol. 204
  • DOI: 10.1016/j.gca.2017.01.029

Several levels of theory for description of isotope effects in ozone: Effect of resonance lifetimes and channel couplings
journal, October 2018

  • Teplukhin, Alexander; Gayday, Igor; Babikov, Dmitri
  • The Journal of Chemical Physics, Vol. 149, Issue 16
  • DOI: 10.1063/1.5042590

Molecular Symmetry and Spectroscopy
journal, August 1979

  • Bunker, P. R.; Matsen, F. A.
  • Physics Today, Vol. 32, Issue 8
  • DOI: 10.1063/1.2995676

Works referencing / citing this record:

Use of Isotope Effects To Understand the Present and Past of the Atmosphere and Climate and Track the Origin of Life
journal, May 2019

  • Thiemens, Mark H.; Lin, Mang
  • Angewandte Chemie International Edition, Vol. 58, Issue 21
  • DOI: 10.1002/anie.201812322

Rotationally inelastic scattering of O 3 –Ar: state-to-state rates with the multiconfigurational time dependent Hartree method
journal, January 2020

  • Sur, Sangeeta; Ndengué, Steve A.; Quintas-Sánchez, Ernesto
  • Physical Chemistry Chemical Physics, Vol. 22, Issue 4
  • DOI: 10.1039/c9cp06501f

Use of Isotope Effects To Understand the Present and Past of the Atmosphere and Climate and Track the Origin of Life
journal, February 2019


The ratio of the number of states in asymmetric and symmetric ozone molecules deviates from the statistical value of 2
journal, March 2019

  • Gayday, Igor; Teplukhin, Alexander; Babikov, Dmitri
  • The Journal of Chemical Physics, Vol. 150, Issue 10
  • DOI: 10.1063/1.5082850

Development of a potential energy surface for the O 3 –Ar system: rovibrational states of the complex
journal, January 2019

  • Sur, Sangeeta; Quintas-Sánchez, Ernesto; Ndengué, Steve A.
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 18
  • DOI: 10.1039/c9cp01044k