Mechanism of Chemiluminescence in the Air Afterglow Reaction DOI
Mahesh Gudem,

Anand Kumar Yadav,

Anjana Vijayan

и другие.

The Journal of Physical Chemistry A, Год журнала: 2025, Номер unknown

Опубликована: Май 8, 2025

Chemiluminescent emission resulting from the thermal reaction between nitric oxide and atomic oxygen to yield NO2 is known as an air afterglow. The product forms in both ground (2A1) excited (2B2) states, with latter being responsible for chemiluminescence. Despite recognized several decades, underlying mechanism, particularly formation of 2B2 state NO2, remains unclear. ground- excited-state PESs describing NO-O have been explored using multireference electronic structure methods (CASSCF combined XMS-CASPT2 energy corrections). Our results suggest that two distinct states involves a ridge-mediated bifurcation ground-state pathway. Additionally, thermally accessible channel has identified on PES. Molecular orbital analysis along bifurcated pathways performed elucidate how single reactant transforms into natures. Surface-hopping-based nonadiabatic dynamics simulations reveal pathway plays significant role generating state. Energetic computed MEPs indicates vibronic associated 2A1 which undergo dipole-allowed radiative emission. frequencies are good agreement observed broad chemiluminescent spectrum. mechanism afterglow strikingly different cycloperoxides, sole class systems studied depth date. This study provides new fundamental insights chemiluminescence phenomenon.

Язык: Английский

Mechanism of Chemiluminescence in the Air Afterglow Reaction DOI
Mahesh Gudem,

Anand Kumar Yadav,

Anjana Vijayan

и другие.

The Journal of Physical Chemistry A, Год журнала: 2025, Номер unknown

Опубликована: Май 8, 2025

Chemiluminescent emission resulting from the thermal reaction between nitric oxide and atomic oxygen to yield NO2 is known as an air afterglow. The product forms in both ground (2A1) excited (2B2) states, with latter being responsible for chemiluminescence. Despite recognized several decades, underlying mechanism, particularly formation of 2B2 state NO2, remains unclear. ground- excited-state PESs describing NO-O have been explored using multireference electronic structure methods (CASSCF combined XMS-CASPT2 energy corrections). Our results suggest that two distinct states involves a ridge-mediated bifurcation ground-state pathway. Additionally, thermally accessible channel has identified on PES. Molecular orbital analysis along bifurcated pathways performed elucidate how single reactant transforms into natures. Surface-hopping-based nonadiabatic dynamics simulations reveal pathway plays significant role generating state. Energetic computed MEPs indicates vibronic associated 2A1 which undergo dipole-allowed radiative emission. frequencies are good agreement observed broad chemiluminescent spectrum. mechanism afterglow strikingly different cycloperoxides, sole class systems studied depth date. This study provides new fundamental insights chemiluminescence phenomenon.

Язык: Английский

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