Low-lying vibronic level structure of the ground state of the methoxy radical: Slow electron velocity-map imaging (SEVI) spectra and Köppel-Domcke-Cederbaum (KDC) vibronic Hamiltonian calculations

Weichman, Marissa L.; Cheng, Lan; Kim, Jongjin B.; Stanton, John F.; Neumark, Daniel M.

doi:10.1063/1.4984963

Cited by 21 publications

(30 citation statements)

References 46 publications

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“…Previous cryo-SEVI studies have uncovered myriad non-Born Oppenheimer behavior in small molecules that fail to be reproduced by FC simulations, most notably vibronic coupling. [134][135][136][137] The signatures of this phenomenon in cryo-SEVI are well established, arising due to borrowed electronic character from an excited state. 64,135,[137][138][139][140][141] Among these signatures are differing photoelectron angular distributions between transitions that are allowed only though vibronic coupling and those that are FC-allowed.…”

Section: Discussionmentioning

confidence: 99%

Unveiling the Coexistence of Cis and Trans Isomers in the Hydrolysis of ZrO2: A Coupled DFT and High-Resolution Photoelectron Spectroscopy Study

Taka¹,

Babin²,

Sheng³

et al. 2020

Preprint

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High-resolution anion photoelectron spectroscopy of the ZrO3H2- and ZrO3D2- anions and complementary electronic structure calculations are used to investigate the reaction between zirconium dioxide and a single water molecule, ZrO20/- + H2O. Experimental spectra of ZrO3H2- and ZrO3D2- were obtained using slow photoelectron velocity-map imaging (cryo-SEVI), revealing the presence of two dissociative adduct conformers and yielding insight into the vibronic structure of the corresponding neutral species. Franck-Condon simulations for both the \textit{cis}-- and \textit{trans}--dihydroxide structures are required to fully reproduce the experimental spectrum. Additionally, it was found that water-splitting is stabilized more by ZrO2 than TiO2, suggesting Zr-based catalysts are more reactive toward hydrolysis.

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Section: Discussionmentioning

confidence: 99%

Unveiling the Coexistence of Cis and Trans Isomers in the Hydrolysis of ZrO2: A Coupled DFT and High-Resolution Photoelectron Spectroscopy Study

Taka¹,

Babin²,

Sheng³

et al. 2020

Preprint

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“…Therefore, aiming to obtain accurate branching factors higher than 10 −5 , it is necessary to calculate the A 2 Π 1/2 (000) vibronic wave function using a multi-state Hamiltonian with all of these relevant perturbations taken into account. We thus adopt the KDC Hamiltonian widely used to account for spinvibronic coupling in spectrum simulation [58][59][60][61][62][63][64][65][66][67][68].…”

mentioning

confidence: 99%

Accurate prediction and measurement of vibronic branching ratios for laser cooling linear polyatomic molecules

Zhang,

Augenbraun,

Lasner

et al. 2021

Preprint

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We report a generally applicable computational and experimental approach to determine vibronic branching ratios in linear polyatomic molecules to the 10 −5 level, including for nominally symmetry-forbidden transitions. These methods are demonstrated in CaOH and YbOH, showing approximately two orders of magnitude improved sensitivity compared with the previous state of the art. Knowledge of branching ratios at this level is needed for the successful deep laser cooling of a broad range of molecular species.

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“…The Köppel–Domcke–Cederbaum (KDC) vibronic coupling method − is an often-employed approach − for determining nonadiabatic spectral intensities, producing discrete line spectra. In its time-independent form, the KDC algorithm uses a Lanczos procedure to diagonalize the molecular Hamiltonian in a direct product basis of harmonic nuclear vibrations and diabatic electronic states.…”

mentioning

confidence: 99%

Compact Bases for Vibronic Coupling in Spectral Simulations: The Photoelectron Spectrum of Cyclopentoxide in the Full 39 Internal Modes

Shen

Yarkony

2020

J. Phys. Chem. Lett.

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We report an algorithm to automatically generate compact multimode vibrational bases for the Köppel–Domcke–Cederbaum (KDC) vibronic coupling wave function used in spectral simulations of moderate-sized molecules. As a full quantum method, the size of the vibronic expansion grows exponentially with respect to the number of vibrational modes, necessitating compact bases for moderate-sized systems. The problem of generating such a basis consists of two parts: one is the choice of vibrational normal modes, and the other is the number of phonons allowed in each mode. A previously developed final-state-biased technique addresses the former part, and this work focuses on the latter part: proposing an algorithm for generating an optimal phonon distribution. By virtue of this phonon distribution, compact and affordable bases can be automatically generated for systems with on the order of 15 atoms. Our algorithm is applied to determine the nonadiabatic photoelectron spectrum of cyclopentoxide in the full 39 internal modes.

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Low-lying vibronic level structure of the ground state of the methoxy radical: Slow electron velocity-map imaging (SEVI) spectra and Köppel-Domcke-Cederbaum (KDC) vibronic Hamiltonian calculations

Abstract: A multi-plate velocity-map imaging design for high-resolution photoelectron spectroscopy

Cited by 21 publications

References 46 publications

Unveiling the Coexistence of Cis and Trans Isomers in the Hydrolysis of ZrO2: A Coupled DFT and High-Resolution Photoelectron Spectroscopy Study

Unveiling the Coexistence of Cis and Trans Isomers in the Hydrolysis of ZrO2: A Coupled DFT and High-Resolution Photoelectron Spectroscopy Study

Accurate prediction and measurement of vibronic branching ratios for laser cooling linear polyatomic molecules

Compact Bases for Vibronic Coupling in Spectral Simulations: The Photoelectron Spectrum of Cyclopentoxide in the Full 39 Internal Modes

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