Neglected Importance of Anharmonicity in Quantifying the Renner–Teller Effect

Lu, Q.

doi:10.1021/acsomega.2c05494

Cited by 1 publication

(2 citation statements)

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“…Using Eq. 5 this gives RT parameters |ε| of 0.48 and 0.41 respectively, indicating a somewhat intermediate coupling strength compared to other RT systems 61 .…”

Section: A Equilibrium Geometry and Harmonic Frequenciesmentioning

confidence: 88%

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Photoelectron spectroscopy and dissociative photoionization of fulminic acid, HCNO

Gerlach

Mant

Preitschopf

et al. 2023

The Journal of Chemical Physics

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We report a joint experimental and computational study of the photoelectron spectroscopy and the dissociative photoionization of fulminic acid, HCNO. The molecule is of interest to astrochemistry and astrobiology as a potential precursor of prebiotic molecules. Synchrotron radiation was used as the photon source. Dispersive photoelectron spectra were recorded from 10~eV to 22~eV, covering four band systems in the HCNO cation and an ionization energy of 10.83~eV was determined. Transitions into the Renner-Teller distorted $X^+{}^2\Pi$ state of the cation were simulated using wavepacket dynamics based on a vibronic coupling Hamiltonian. Very good agreement between experiment and theory is obtained. While the first excited state of the cation shows only a broad and unstructured spectrum, the next two higher states exhibit a well-resolved vibrational progression. Transitions into the excited electronic states of \cation{HCNO}{+} were not simulated, due to the large number of electronic states that contribute to these transitions. Nevertheless, a qualitative assignment is given, based on the character of the orbitals involved in the transitions. The dissociative photoionization was investigated by photoelectron-photoion coincidence spectroscopy. The breakdown diagram shows evidence for isomerization from \cation{HCNO}{+} to \cation{HNCO}{+} on the cationic potential energy surface. Zero Kelvin appearance energies for the daughter ions \cation{HCO}{+} and \cation{NCO}{+} have been derived.

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“…Using Eq. 5 this gives RT parameters |ε| of 0.48 and 0.41 respectively, indicating a somewhat intermediate coupling strength compared to other RT systems 61 .…”

Section: A Equilibrium Geometry and Harmonic Frequenciesmentioning

confidence: 88%

“…where V m is the mean potential of the split surfaces V + and V − . 61 The RT parameter can be calculated as…”

Section: B Computationalmentioning

confidence: 99%