Improved Potential Energy Surface of Ozone Constructed Using the Fitting by Permutationally Invariant Polynomial Function

Ayouz, Mehdi; Babikov, Dmitri

doi:10.1155/2012/951371

Title: Improved Potential Energy Surface of Ozone Constructed Using the Fitting by Permutationally Invariant Polynomial Function

Full Record
Other Related Research

Abstract

New global potential energy surface for the ground electronic state of ozone is constructed at the complete basis set level of the multireference configuration interaction theory. A method of fitting the data points by analytical permutationally invariant polynomial function is adopted. A small set of 500 points is preoptimized using the old surface of ozone. In this procedure the positions of points in the configuration space are chosen such that the RMS deviation of the fit is minimized. New ab initio calculations are carried out at these points and are used to build new surface. Additional points are added to the vicinity of the minimum energy path in order to improve accuracy of the fit, particularly in the region where the surface of ozone exhibits a shallow van der Waals well. New surface can be used to study formation of ozone at thermal energies and its spectroscopy near the dissociation threshold.

Authors:

Ayouz, Mehdi ^[1]; Babikov, Dmitri ^[1]

Chemistry Department, Marquette University, Wehr Chemistry Building, Milwaukee, WI 53201-1881, USA

Publication Date:: Sun Jan 01 00:00:00 EST 2012

Sponsoring Org.:: USDOE

OSTI Identifier:: 1198020

Grant/Contract Number:: AC02-05CH11231

Resource Type:: Published Article

Journal Name:: Advances in Physical Chemistry

Additional Journal Information:: Journal Name: Advances in Physical Chemistry Journal Volume: 2012; Journal ID: ISSN 1687-7985

Publisher:: Hindawi Publishing Corporation

Country of Publication:: United States

Language:: English

Citation Formats


                    Ayouz, Mehdi, and Babikov, Dmitri. Improved Potential Energy Surface of Ozone Constructed Using the Fitting by Permutationally Invariant Polynomial Function.  United States: N. p., 2012. 
Web.  doi:10.1155/2012/951371.

Copy to clipboard


                    Ayouz, Mehdi, & Babikov, Dmitri. Improved Potential Energy Surface of Ozone Constructed Using the Fitting by Permutationally Invariant Polynomial Function.  United States.  https://doi.org/10.1155/2012/951371

Copy to clipboard


                    Ayouz, Mehdi, and Babikov, Dmitri. Sun .  
"Improved Potential Energy Surface of Ozone Constructed Using the Fitting by Permutationally Invariant Polynomial Function".  United States.  https://doi.org/10.1155/2012/951371.

Copy to clipboard


                    
@article{osti_1198020,

  title        = {Improved Potential Energy Surface of Ozone Constructed Using the Fitting by Permutationally Invariant Polynomial Function},

  author       = {Ayouz, Mehdi and Babikov, Dmitri},

  abstractNote = {New global potential energy surface for the ground electronic state of ozone is constructed at the complete basis set level of the multireference configuration interaction theory. A method of fitting the data points by analytical permutationally invariant polynomial function is adopted. A small set of 500 points is preoptimized using the old surface of ozone. In this procedure the positions of points in the configuration space are chosen such that the RMS deviation of the fit is minimized. New ab initio calculations are carried out at these points and are used to build new surface. Additional points are added to the vicinity of the minimum energy path in order to improve accuracy of the fit, particularly in the region where the surface of ozone exhibits a shallow van der Waals well. New surface can be used to study formation of ozone at thermal energies and its spectroscopy near the dissociation threshold.},

  doi          = {10.1155/2012/951371},

  journal      = {Advances in Physical Chemistry},

  number       = ,

  volume       = 2012,

  place        = {United States},

  year         = {Sun Jan 01 00:00:00 EST 2012},

  month        = {Sun Jan 01 00:00:00 EST 2012}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Publisher's Version of Record
https://doi.org/10.1155/2012/951371

Other availability

Search WorldCat to find libraries that may hold this journal

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Permutationally Invariant Polynomial Expansions with Unrestricted Complexity

Journal Article Moberg, Daniel R. ; Jasper, Ahren W. - Journal of Chemical Theory and Computation

A general strategy is presented for constructing and validating permutationally invariant polynomial (PIP) expansions for chemical systems of any stoichiometry. Demonstrations are made for three categories of gas-phase dynamics and kinetics: collisional energy-transfer trajectories for predicting pressure-dependent kinetics, three-body collisions for describing transient van der Waals adducts relevant to atmospheric chemistry, and nonthermal reactivity via quasiclassical trajectories. In total, 30 systems are considered with up to 15 atoms and 39 degrees of freedom. Permutational invariance is enforced in PIP expansions with as many as 13 million terms and 13 permutationally distinct atom types by taking advantage of petascale computational resources.more »« less
https://doi.org/10.1021/acs.jctc.1c00352

Full Text Available
A permutationally invariant full-dimensional ab initio potential energy surface for the abstraction and exchange channels of the H + CH{sub 4} system

Journal Article Li, Jun ; Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 ; Chen, Jun ; ... - Journal of Chemical Physics

We report a permutationally invariant global potential energy surface (PES) for the H + CH{sub 4} system based on ∼63 000 data points calculated at a high ab initio level (UCCSD(T)-F12a/AVTZ) using the recently proposed permutation invariant polynomial-neural network method. The small fitting error (5.1 meV) indicates a faithful representation of the ab initio points over a large configuration space. The rate coefficients calculated on the PES using tunneling corrected transition-state theory and quasi-classical trajectory are found to agree well with the available experimental and previous quantum dynamical results. The calculated total reaction probabilities (J{sub tot} = 0) including themore »« less
https://doi.org/10.1063/1.4921412
Quantum and quasi-classical dynamics of the OH + CO → H + CO{sub 2} reaction on a new permutationally invariant neural network potential energy surface

Journal Article Li, Jun ; Guo, Hua ; Chen, Jun ; ... - Journal of Chemical Physics

A permutationally invariant global potential energy surface for the HOCO system is reported by fitting a larger number of high-level ab initio points using the newly proposed permutation invariant polynomial-neural network method. The small fitting error (∼5 meV) indicates a faithful representation of the potential energy surface over a large configuration space. Full-dimensional quantum and quasi-classical trajectory studies of the title reaction were performed on this potential energy surface. While the results suggest that the differences between this and an earlier neural network fits are small, discrepancies with state-to-state experimental data remain significant.
https://doi.org/10.1063/1.4863138
Potential energy surface fitting by a statistically localized, permutationally invariant, local interpolating moving least squares method for the many-body potential: Method and application to N{sub 4}

Journal Article Bender, Jason D. ; Doraiswamy, Sriram ; Candler, Graham V., E-mail: truhlar@umn.edu, E-mail: candler@aem.umn.edu ; ... - Journal of Chemical Physics

Fitting potential energy surfaces to analytic forms is an important first step for efficient molecular dynamics simulations. Here, we present an improved version of the local interpolating moving least squares method (L-IMLS) for such fitting. Our method has three key improvements. First, pairwise interactions are modeled separately from many-body interactions. Second, permutational invariance is incorporated in the basis functions, using permutationally invariant polynomials in Morse variables, and in the weight functions. Third, computational cost is reduced by statistical localization, in which we statistically correlate the cutoff radius with data point density. We motivate our discussion in this paper with amore »« less
https://doi.org/10.1063/1.4862157
A general method for constructing multidimensional molecular potential energy surfaces from {ital ab} {ital initio} calculations

Journal Article Ho, T ; Rabitz, H - Journal of Chemical Physics

A general interpolation method for constructing smooth molecular potential energy surfaces (PES{close_quote}s) from {ital ab} {ital initio} data are proposed within the framework of the reproducing kernel Hilbert space and the inverse problem theory. The general expression for an {ital a} {ital posteriori} error bound of the constructed PES is derived. It is shown that the method yields globally smooth potential energy surfaces that are continuous and possess derivatives up to second order or higher. Moreover, the method is amenable to correct symmetry properties and asymptotic behavior of the molecular system. Finally, the method is generic and can be easilymore »« less
https://doi.org/10.1063/1.470984

Similar Records