High-Level, First-Principles, Full-Dimensional Quantum Calculation of the Ro-vibrational Spectrum of the Simplest Criegee Intermediate (CH2OO).
The ro-vibrational spectrum of the simplest Criegee intermediate (CH2OO) 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.
†Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, United States.
Jun
J
Li
‡Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States.
Stuart
S
Carter
‡Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States.
Joel M
JM
Bowman
§Department of Chemistry, Missouri University of Science and Technology, Rolla, Missouri 65409, United States.
Richard
R
Dawes
∥Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China.
Daiqian
D
Xie
†Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, United States.
Hua
H
Guo
Criegee intermediate; ab initio calculations; potential energy surface; ro-vibrational spectrum