Global Potential Energy Surface, Vibrational Spectrum, and Reaction Dynamics of the First Excited (Ấ²A′) State of HO₂

Anyang Li; Daiqian Xie; Richard Dawes; Ahren W. Jasper; Jianyi Ma; Hua Guo

doi:10.1063/1.3490642

Global Potential Energy Surface, Vibrational Spectrum, and Reaction Dynamics of the First Excited (Ấ²A′) State of HO₂

Anyang Li
, Daiqian Xie
, Richard Dawes
, Ahren W. Jasper
, Jianyi Ma
, Hua Guo

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

The authors report extensive high-level ab initio studies of the first excited (Ã A2 ') state of HO ₂ . A global potential energy surface (PES) was developed by spline-fitting 17 000 ab initio points at the internal contracted multireference configuration interaction (icMRCI) level with the AVQZ basis set. To ascertain the spectroscopic accuracy of the PES, the near-equilibrium region of the molecule was also investigated using three interpolating moving least-squares-based PESs employing dynamically weighted icMRCI methods in the complete basis set limit. Vibrational energy levels on all four surfaces agree well with each other and a new assignment of some vibrational features is proposed. In addition, the dynamics of both the forward and reverse directions of the H+ O ₂ (ã Δ1 _g ) OH+O reaction (J=0) were studied using an exact wave packet method. The reactions are found to be dominated by sharp resonances.

Original language	American English
Journal	Journal of Chemical Physics
Volume	133
DOIs	https://doi.org/10.1063/1.3490642
State	Published - Oct 1 2010

Keywords

Ab initio
Ab initio study
Basis sets
Complete basis set limit
Excited states
Global potential energy surfaces
Moving least squares
Multi reference configuration interactions
Potential energy surfaces
Quantum chemistry
Reaction dynamics
Sulfur compounds
Vibrational energy levels
Vibrational features
Wave-packet method, Potential energy

Disciplines

Chemistry

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https://doi.org/10.1063/1.3490642

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@article{6135c69416ee4ebe8eef717ef5a04037,

title = "Global Potential Energy Surface, Vibrational Spectrum, and Reaction Dynamics of the First Excited (Ấ²A′) State of HO₂",

abstract = " The authors report extensive high-level ab initio studies of the first excited ({\~A} A2 ') state of HO 2 . A global potential energy surface (PES) was developed by spline-fitting 17 000 ab initio points at the internal contracted multireference configuration interaction (icMRCI) level with the AVQZ basis set. To ascertain the spectroscopic accuracy of the PES, the near-equilibrium region of the molecule was also investigated using three interpolating moving least-squares-based PESs employing dynamically weighted icMRCI methods in the complete basis set limit. Vibrational energy levels on all four surfaces agree well with each other and a new assignment of some vibrational features is proposed. In addition, the dynamics of both the forward and reverse directions of the H+ O 2 ({\~a} Δ1 g ) OH+O reaction (J=0) were studied using an exact wave packet method. The reactions are found to be dominated by sharp resonances.",

keywords = "Ab initio, Ab initio study, Basis sets, Complete basis set limit, Excited states, Global potential energy surfaces, Moving least squares, Multi reference configuration interactions, Potential energy surfaces, Quantum chemistry, Reaction dynamics, Sulfur compounds, Vibrational energy levels, Vibrational features, Wave-packet method, Potential energy",

author = "Anyang Li and Daiqian Xie and Richard Dawes and Jasper, \{Ahren W.\} and Jianyi Ma and Hua Guo",

year = "2010",

month = oct,

day = "1",

doi = "10.1063/1.3490642",

language = "American English",

volume = "133",

journal = "Journal of Chemical Physics",

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TY - JOUR

T1 - Global Potential Energy Surface, Vibrational Spectrum, and Reaction Dynamics of the First Excited (Ấ²A′) State of HO₂

AU - Li, Anyang

AU - Xie, Daiqian

AU - Dawes, Richard

AU - Jasper, Ahren W.

AU - Ma, Jianyi

AU - Guo, Hua

PY - 2010/10/1

Y1 - 2010/10/1

N2 - The authors report extensive high-level ab initio studies of the first excited (Ã A2 ') state of HO 2 . A global potential energy surface (PES) was developed by spline-fitting 17 000 ab initio points at the internal contracted multireference configuration interaction (icMRCI) level with the AVQZ basis set. To ascertain the spectroscopic accuracy of the PES, the near-equilibrium region of the molecule was also investigated using three interpolating moving least-squares-based PESs employing dynamically weighted icMRCI methods in the complete basis set limit. Vibrational energy levels on all four surfaces agree well with each other and a new assignment of some vibrational features is proposed. In addition, the dynamics of both the forward and reverse directions of the H+ O 2 (ã Δ1 g ) OH+O reaction (J=0) were studied using an exact wave packet method. The reactions are found to be dominated by sharp resonances.

AB - The authors report extensive high-level ab initio studies of the first excited (Ã A2 ') state of HO 2 . A global potential energy surface (PES) was developed by spline-fitting 17 000 ab initio points at the internal contracted multireference configuration interaction (icMRCI) level with the AVQZ basis set. To ascertain the spectroscopic accuracy of the PES, the near-equilibrium region of the molecule was also investigated using three interpolating moving least-squares-based PESs employing dynamically weighted icMRCI methods in the complete basis set limit. Vibrational energy levels on all four surfaces agree well with each other and a new assignment of some vibrational features is proposed. In addition, the dynamics of both the forward and reverse directions of the H+ O 2 (ã Δ1 g ) OH+O reaction (J=0) were studied using an exact wave packet method. The reactions are found to be dominated by sharp resonances.

KW - Ab initio

KW - Ab initio study

KW - Basis sets

KW - Complete basis set limit

KW - Excited states

KW - Global potential energy surfaces

KW - Moving least squares

KW - Multi reference configuration interactions

KW - Potential energy surfaces

KW - Quantum chemistry

KW - Reaction dynamics

KW - Sulfur compounds

KW - Vibrational energy levels

KW - Vibrational features

KW - Wave-packet method, Potential energy

UR - https://scholarsmine.mst.edu/chem_facwork/383

UR - https://doi.org/10.1063/1.3490642

U2 - 10.1063/1.3490642

DO - 10.1063/1.3490642

M3 - Article

VL - 133

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

ER -

Global Potential Energy Surface, Vibrational Spectrum, and Reaction Dynamics of the First Excited (Ấ²A′) State of HO₂

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Keywords

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