Vibration mediated photodissociation dynamics of CH<sub>3</sub>SH: manipulation of the dynamic energy disposal into products

Lee, Heesung; Kim, Sang Kyu

doi:10.1039/d0cp03575k

Cited by 2 publications

(1 citation statement)

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“…1e ), referred to as vibration-mediated photodissociation (VMP) in physical chemistry 34 – 36 . VMPs of small molecules such as water, acetylene, ammonia, nitric acid, hydrogen peroxide, pyrrole, and methanethiol have been detected by laser-based double-resonance techniques 34 – 39 . VMP has also been used to investigate intramolecular vibrational redistribution dynamics 40 – 42 , but not for organic synthesis.…”

Section: Introductionmentioning

confidence: 99%

Vibration-mediated long-wavelength photolysis of electronegative bonds beyond S0–S1 and S0–T1 transitions

Araujo Dias,

Muranaka,

Uchiyama

et al. 2024

Commun Chem

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Photolysis is an attractive method in organic synthesis to produce free radicals through direct bond cleavage. However, in this method, specific irradiation wavelengths of light have been considered indispensable for excitation through S0–Sn or S0–Tn transitions. Here we report the photoinduced homolysis of electronegative interelement bonds using light at wavelengths much longer than theoretically and spectroscopically predicted for the S0–Sn or S0–Tn transitions. This long-wavelength photolysis proceeds in N–Cl, N–F, and O–Cl bonds at room temperature under blue, green, and red LED irradiation, initiating diverse radical reactions. Through experimental, spectroscopic, and computational studies, we propose that this “hidden” absorption is accessible via electronic excitations from naturally occurring vibrationally excited ground states to unbonded excited states and is due to the electron-pair repulsion between electronegative atoms.

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Section: Introductionmentioning

confidence: 99%

Vibration-mediated long-wavelength photolysis of electronegative bonds beyond S0–S1 and S0–T1 transitions

Araujo Dias,

Muranaka,

Uchiyama

et al. 2024

Commun Chem

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Coupling of torsion and OH-stretching in tert-butyl hydroperoxide. I. The cold and warm first OH-stretching overtone spectrum

Hansen

Huchmala

Vogt

et al. 2021

The Journal of Chemical Physics

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The infrared (IR) spectrum of tert-butyl hydroperoxide (TBHP) in the region of the first OH-stretching overtone has been observed under jet-cooled and thermal (300 K, 3 Torr) conditions at ∼7017 cm−1. The jet-cooled spectrum is recorded by IR multiphoton excitation with UV laser-induced fluorescence detection of OH radical products, while direct IR absorption is utilized under thermal conditions. Prior spectroscopic studies of TBHP and other hydroperoxides have shown that the OH-stretch and XOOH (X = H or C) torsion vibrations are strongly coupled, resulting in a double well potential associated with the torsional motion about the OO bond that is different for each of the OH-stretching vibrational states. A low barrier between the wells on the torsional potential results in tunneling split energy levels, which leads to four distinct transitions associated with excitation of the coupled OH-stretch-torsion states. In order to interpret the experimental results, two theoretical models are used that include the OH-stretch-torsion coupling in TBHP. Both methods are utilized to compute the vibrational transitions associated with the coupled OH-stretch-torsion states of TBHP, revealing the underlying transitions that compose the experimentally observed features. A comparison between theory and experiment illustrates the necessity for treatments that include OH-stretch and COOH torsion in order to unravel the spectral features observed in the first OH-stretching overtone region of TBHP.

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Vibration mediated photodissociation dynamics of CH₃SH: manipulation of the dynamic energy disposal into products

Abstract: The S-H bond dissociation dynamics of CH3SH have been investigated for the S1-S0 transition mediated by either the S-H stretching (2608 cm-1) or CH3 symmetric stretching (2951 cm-1) mode excitation...

Cited by 2 publications

References 42 publications

Vibration-mediated long-wavelength photolysis of electronegative bonds beyond S0–S1 and S0–T1 transitions

Vibration-mediated long-wavelength photolysis of electronegative bonds beyond S0–S1 and S0–T1 transitions

Coupling of torsion and OH-stretching in tert-butyl hydroperoxide. I. The cold and warm first OH-stretching overtone spectrum

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Vibration mediated photodissociation dynamics of CH3SH: manipulation of the dynamic energy disposal into products

Abstract: The S-H bond dissociation dynamics of CH3SH have been investigated for the S1-S0 transition mediated by either the S-H stretching (2608 cm-1) or CH3 symmetric stretching (2951 cm-1) mode excitation...

Cited by 2 publications

References 42 publications

Vibration-mediated long-wavelength photolysis of electronegative bonds beyond S0–S1 and S0–T1 transitions

Vibration-mediated long-wavelength photolysis of electronegative bonds beyond S0–S1 and S0–T1 transitions

Coupling of torsion and OH-stretching in tert-butyl hydroperoxide. I. The cold and warm first OH-stretching overtone spectrum

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Vibration mediated photodissociation dynamics of CH₃SH: manipulation of the dynamic energy disposal into products