Spin controlled surface chemistry: alkyl desorption from Si(100)-2×1 by nonadiabatic hydrogen elimination

Pohlman, Andrew; Kaliakin, Danil S.; Varganov, Sergey A.; Casey, Sean M.

doi:10.1039/d0cp01913e

Cited by 3 publications

(2 citation statements)

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“…These kinetics calculations were carried out in part using the master equation program MESMER . Note that RRKM theory is microcanonical transition state theory , applied to a unimolecular reaction, and μNA-TST is the extension of this theory to electronically nonadiabatic processes. − …”

Section: Methodsmentioning

confidence: 99%

Role of Triplet States in the Photodynamics of Aniline

2021

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The dynamics of excited heteroaromatic molecules is a key to understanding the photoprotective properties of many biologically relevant chromophores that dissipate their excitation energy nonreactively and thereby prevent the detrimental effects of ultraviolet radiation. Despite their structural variability, most heteroaromatic compounds share a common feature of a repulsive 1 πσ* potential energy surface. This surface can lead to photoproducts, and it can also facilitate the population transfer back to the ground electronic state by means of a 1 πσ*/S 0 conical intersection. Here, we explore a hidden relaxation route involving the triplet electronic state of aniline, which has recently been discovered by means of time-selected photofragment translational spectroscopy [J. Chem. Phys. 2019, 151, 141101]. By using the recently available analytical gradients for multiconfiguration pair-density functional theory, it is now possible to locate the minimum energy crossing points between states of different spin and therefore compute the intersystem crossing rates with a multireference method, rather than with the less reliable single-reference methods. Using such calculations, we demonstrate that the population loss of aniline in the T 1 ( 3 ππ * ) state is dominated by C 6 H 5 NH 2 →C 6 H 5 NH⸱ + H⸱ dissociation, and we explain the long nonradiative lifetimes of the T 1 ( 3 ππ * ) state at the excitation wavelengths of 294-264 nm.

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Section: Methodsmentioning

confidence: 99%

Role of Triplet States in the Photodynamics of Aniline

2021

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“…68 Note that RRKM theory is microcanonical transition state theory 69,70 applied to a unimolecular reaction, and μNA-TST is the extension of this theory to electronically nonadiabatic processes. [71][72][73][74][75][76][77] The ISC rate constant, kISC, and unimolecular dissociation rate constant, kDis, were computed using…”

Section: Dynamicsmentioning

confidence: 99%

Role of Triplet States in the Photodynamics of Aniline

Lykhin

Truhlar²,

Gagliardi³

2021

Preprint

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The dynamics of excited heteroaromatic molecules is a key to understanding the photoprotective properties of many biologically relevant chromophores that dissipate their excitation energy nonreactively and thereby prevent the detrimental effects of ultraviolet radiation. Despite their structural variability, most heteroaromatic compounds share a common feature of a repulsive 1πσ* potential energy surface. This surface can lead to photoproducts, and it can also facilitate the population transfer back to the ground electronic state by means of a 1πσ*/S0 conical intersection. Here, we explore a hidden relaxation route involving the triplet electronic state of aniline, which has recently been discovered by means of time-selected photofragment translational spectroscopy [J. Chem. Phys. 2019, 151, 141101]. By using the recently available analytical gradients for multiconfiguration pair-density functional theory, it is now possible to locate the minimum energy crossing points between states of different spin and therefore compute the intersystem crossing rates with a multireference method, rather than with the less reliable single-reference methods. Using such calculations, we demonstrate that the population loss of aniline in the T1(3ππ*) state is dominated by C6H5NH2→C6H5NH⸱ + H⸱ dissociation, and we explain the long nonradiative lifetimes of the T1(3ππ*) state at the excitation wavelengths of 294‑264 nm.

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NAST: Nonadiabatic Statistical Theory Package for Predicting Kinetics of Spin-Dependent Processes

et al. 2022

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Spin controlled surface chemistry: alkyl desorption from Si(100)-2×1 by nonadiabatic hydrogen elimination

Abstract:
An understanding of the role that spin states play in semiconductor surface chemical reactions is currently limited. Herein, we provide evidence of a nonadiabatic reaction involving a localized singlet to...

Cited by 3 publications

References 60 publications

Role of Triplet States in the Photodynamics of Aniline

Role of Triplet States in the Photodynamics of Aniline

Role of Triplet States in the Photodynamics of Aniline

NAST: Nonadiabatic Statistical Theory Package for Predicting Kinetics of Spin-Dependent Processes

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Spin controlled surface chemistry: alkyl desorption from Si(100)-2×1 by nonadiabatic hydrogen elimination

Abstract: An understanding of the role that spin states play in semiconductor surface chemical reactions is currently limited. Herein, we provide evidence of a nonadiabatic reaction involving a localized singlet to...

Cited by 3 publications

References 60 publications

Role of Triplet States in the Photodynamics of Aniline

Role of Triplet States in the Photodynamics of Aniline

Role of Triplet States in the Photodynamics of Aniline

NAST: Nonadiabatic Statistical Theory Package for Predicting Kinetics of Spin-Dependent Processes

Contact Info

Product

Resources

About

Abstract:
An understanding of the role that spin states play in semiconductor surface chemical reactions is currently limited. Herein, we provide evidence of a nonadiabatic reaction involving a localized singlet to...