High-Level, First-principles, Full-dimensional Quantum Calculation of the Ro-vibrational Spectrum of the Simplest Criegee Intermediate (CH₂OO)

Abstract

The ro-vibrational spectrum of the simplest Criegee intermediate (CH 2OO) has been determined quantum mechanically based on nine-dimensional potential energy and dipole surfaces for its ground electronic state. the potential energy surface is fitted to more than 50 000 high-level ab initio points with a root-mean-square error of 25 cm-1, using a recently proposed permutation invariant polynomial neural network method. the calculated rotational constants, vibrational frequencies, and spectral intensities of CH2OO are in excellent agreement with experiment. the potential energy surface provides a valuable platform for studying highly excited vibrational and unimolecular reaction dynamics of this important molecule. © 2014 American Chemical Society.

Department(s)

Chemistry

Research Center/Lab(s)

Center for High Performance Computing Research

Keywords and Phrases

Potential energy surfaces; Quantum chemistry; Vibrational spectra; Ab initio calculations; Criegee intermediates; Ground electronic state; Invariant polynomials; ro-vibrational spectrum; Root-mean square errors; Rotational constants; Unimolecular reactions; Calculations; ab initio calculations; Criegee intermediate; potential energy surface; ro-vibrational spectrum

International Standard Serial Number (ISSN)

1948-7185

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2014 American Chemical Society (ACS), All rights reserved.

Publication Date

01 Jul 2014

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