Ab Initio simulation of the photoelectron spectrum for methoxy radical

Stanton, John F.

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https://hdl.handle.net/2142/79238 Copy

Description

Title

Ab Initio simulation of the photoelectron spectrum for methoxy radical

Author(s)

Stanton, John F.

Contributor(s)

• Neumark, Daniel
• Ichino, Takatoshi
• Kim, Jongjin B.
• Weichman, Marissa L.
• Cheng, Lan

Issue Date

23-Jun-15

Keyword(s)

Radicals

Abstract

"A theoretical simulation of the photoelectron spectrum for the ground state of methoxy radical is reported based on the quasidiabatic model Hamiltonian originally proposed by K\""oppel, Domcke, and Cederbaum. The parameters in the model Hamiltonian have been obtained from ab initio coupled-cluster calculations. The linear and quadratic force constants have been calculated using equation-of-motion coupled-cluster ionization potential method with the singles, doubles, and triples (EOMIP-CCSDT) truncation scheme together with atomic natural orbital basis sets of triple-zeta quality (ANO1). The cubic and quartic force constants have been obtained from EOMIP-CCSD calculations with ANO basis sets of double-zeta quality (ANO0), and the spin-orbit coupling constant has been computed at the EOMIP-CCSD/pCVTZ level. The nuclear Schroedinger equation has been solved using the Lanzcos algorithm to obtain vibronic energy levels as well as the corresponding intensities. The simulated spectrum compares favorably with the recent high-resolution slow electron velocity-map imaging experiment for vibronic levels up to 2000 cm$^{-1}$."

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

English

Permalink

http://hdl.handle.net/2142/79238

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