scholarly journals Ionic State Relaxation Processes in VUV-Excited Polyatomic Molecules

1983 ◽  
Vol 2 (5-6) ◽  
pp. 285-307 ◽  
Author(s):  
Sydney Leach ◽  
Gérald Dujardin
Keyword(s):  
Vibrational Energy ◽  
Molecular Ions ◽  
Quantum Yields ◽  
Relaxation Processes ◽  
Relaxation Rates ◽  
Model Calculations ◽  
Relaxation Parameters ◽  
Gradual Onset ◽  
Mode Selectivity ◽  
Vibrational Levels

Advantages of molecular ions for the study of electronic radiationless transitions are discussed. Several coincidence techniques for measuring key relaxation parameters are briefly described. The different cases of radiationless transition studies of molecular ions are outlined and examples mentioned. Coincidence measurements between threshold photoelectrons and ion fluorescence photons emitted by VUV-excited hexafluorobenzene are presented. The radiative, kr, and nonradiative, knr, relaxation rates for specific vibrational levels in the B∼2A2u and C∼2B2u states of C6F6+ are derived from the measured lifetimes and quantum yields of ion fluorescence. The kr rate for excitation of the C∼, 0° level is found to be about 25% of that for the B∼2A2u state where kr = (18±3) × 106 s−1. The knr rates for the 1n and 1n21 progressions in the B∼ state increase with n but exhibit a mode selective behavior. Model calculations of knr confirm the mode selectivity. These calculations were carried out on a noncommunicating, harmonic oscillator basis. Progressive deviations between experimental and calculated results are interpreted as indicating the gradual onset of vibrational redistribution with increasing vibrational energy. The results illustrate a new method for demonstrating the growing in of intramolecular vibrational relaxation.

Vibrational dependence of electronic nonradiative processes in the state of and

1984 ◽  
Vol 62 (12) ◽  
pp. 1361-1368 ◽  
Author(s):  
D. Winkoun ◽  
D. Chapoulard ◽  
G. Dujardin ◽  
S. Leach
Keyword(s):  
Vibrational Mode ◽  
Spectroscopic Properties ◽  
Quantum Yields ◽  
Electronic Relaxation ◽  
Matrix Elements ◽  
Relaxation Rates ◽  
Fluorescence Quantum Yields ◽  
Fluorescence Photon ◽  
Mode Selectivity ◽  
Nonradiative Processes

Vibrational mode selective, radiationless transitions have been sought in the [Formula: see text] states of [Formula: see text] and [Formula: see text] by determining the radiative kr(ν′) and nonradiative knr(ν′) rates of electronic relaxation of energy selected vibronic levels of these cations. The relaxation rates were derived from measurements of ion fluorescence quantum yields and lifetimes using a photoelectron-fluorescence photon delayed coincidence apparatus, described in the text, in which the ions are formed by direct photoionization. Mode selective behavior is confirmed for the ν1 and ν2 modes of the [Formula: see text] state of [Formula: see text], previously studied by a threshold photoelectron-fluorescence photon coincidence method in which photoion formation involved auto-ionization as well as direct photoionization. In the case of the ν3 and ν4 modes of [Formula: see text], knr(ν′) was found to depend only on the excess energy Eν′ in the [Formula: see text] state and not on the particular mode optically excited. The absence of mode selectivity in this cation could be due to very rapid vibrational redistribution, but more probably results from similar-valued nonradiative coupling matrix elements of vibronic levels involving ν3 and (or) ν4 modes for a given value of Eν′. This is shown to be consistent with the known spectroscopic properties of [Formula: see text].

Electron Spin Decoherence by Nuclei

2018 ◽  
Author(s):  
M. M. Glazov
Keyword(s):  
Electron Spin ◽  
Spin Dynamics ◽  
Magnetic Moments ◽  
Host Lattice ◽  
Spin Model ◽  
Relaxation Processes ◽  
Nuclear Spins ◽  
Model Calculations ◽  
Spin Decoherence ◽  
Quantum Mechanical Approach

The discussion of the electron spin decoherence and relaxation phenomena via the hyperfine interaction with host lattice spins is presented here. The spin relaxation processes processes limit the conservation time of spin states as well as the response time of the spin system to external perturbations. The central spin model, where the spin of charge carrier interacts with the bath of nuclear spins, is formulated. We also present different methods to calculate the spin dynamics within this model. Simple but physically transparent semiclassical treatment where the nuclear spins are considered as largely static classical magnetic moments is followed by more advanced quantum mechanical approach where the feedback of electron spin dynamics on the nuclei is taken into account. The chapter concludes with an overview of experimental data and its comparison with model calculations.

Diffusion Phenomena of the Oxygen and Nitrogen in Niobium by Mechanical Spectroscopy

2010 ◽  
Vol 297-301 ◽  
pp. 1346-1353
Author(s):  
Odila Florêncio ◽  
Paulo Sergio Silva ◽  
Carlos Roberto Grandini
Keyword(s):  
Diffusion Coefficients ◽  
Short Range ◽  
Annealed Sample ◽  
Relaxation Processes ◽  
Torsion Pendulum ◽  
Mechanical Spectroscopy ◽  
Interstitial Diffusion ◽  
Relaxation Parameters ◽  
Low Concentrations ◽  
Diffusion Phenomena

The short-range diffusion phenomenon (Snoek Effect) was investigated by mechanical spectroscopy measurements between 300 K and 650 K, in a polycrystalline niobium sample, containing oxygen and nitrogen, using a torsion pendulum. Experimental spectra of anelastic relaxation were obtained under three conditions: as-received sample; annealed sample and subsequently annealed in an oxygen atmosphere for three hours at 1170 K in partial pressure of 5x10-5mbar. The experimental spectra obtained were decomposed in elementary Debye peaks and the anelastic relaxation processes were identified. With anelastic relaxation parameters and the lattice parameters, the interstitial diffusion coefficients of the oxygen and nitrogen in niobium were calculated for each kind of preferential occupation (octahedral and tetrahedral). The results were compared with the literature data, and confirmed that the best adjustment is for the preferential occupation octahedral model for low concentrations of interstitial solutes, but at higher concentration of oxygen were observed deviations of experimental data for the interstitial diffusion coefficients of oxygen in niobium when compared with the literature data, this could be related to the possible occurrence of a double occupation of interstitial sites in the niobium lattice by oxygen interstitials.

Wavelength-dependent photodissociation as a probe for vibrational energy distributions in molecular ions

1996 ◽  
Vol 29 (13) ◽  
pp. 2763-2773 ◽  
Author(s):  
J J Blangé ◽  
X Urbain ◽  
H Rudolph ◽  
H A Dijkerman ◽  
H C W Beijerinck ◽  
...  
Keyword(s):  
Vibrational Energy ◽  
Molecular Ions ◽  
Energy Distributions

scholarly journals Resolving the mesospheric nighttime 4.3 µm emission puzzle: comparison of the CO<sub>2</sub>(<i>ν</i><sub>3</sub>) and OH(<i>ν</i>) emission models

2017 ◽  
Vol 17 (16) ◽  
pp. 9751-9760 ◽  
Author(s):  
Peter A. Panka ◽  
Alexander A. Kutepov ◽  
Konstantinos S. Kalogerakis ◽  
Diego Janches ◽  
James M. Russell ◽  
...  
Keyword(s):  
Energy Transfer ◽  
Vibrational Energy ◽  
Lower Thermosphere ◽  
Vibrational Energy Relaxation ◽  
Density Distributions ◽  
Direct Mechanism ◽  
Vibrational Levels ◽  
Emission Models ◽  
The Impact ◽  
Good Agreement

Abstract. In the 1970s, the mechanism of vibrational energy transfer from chemically produced OH(ν) in the nighttime mesosphere to the CO2(ν3) vibration, OH(ν) ⇒ N2(ν) ⇒ CO2(ν3), was proposed. In later studies it was shown that this "direct" mechanism for simulated nighttime 4.3 µm emissions of the mesosphere is not sufficient to explain space observations. In order to better simulate these observations, an additional enhancement is needed that would be equivalent to the production of 2.8–3 N2(1) molecules instead of one N2(1) molecule in each quenching reaction of OH(ν) + N2(0). Recently a new "indirect" channel of the OH(ν) energy transfer to N2(ν) vibrations, OH(ν) ⇒ O(1D) ⇒ N2(ν), was suggested and then confirmed in a laboratory experiment, where its rate for OH(ν = 9) + O(3P) was measured. We studied in detail the impact of the "direct" and "indirect" mechanisms on CO2(ν3) and OH(ν) vibrational level populations and emissions. We also compared our calculations with (a) the SABER/TIMED nighttime 4.3 µm CO2 and OH 1.6 and 2.0 µm limb radiances of the mesosphere–lower thermosphere (MLT) and (b) with ground- and space-based observations of OH(ν) densities in the nighttime mesosphere. We found that the new "indirect" channel provides a strong enhancement of the 4.3 µm CO2 emission, which is comparable to that obtained with the "direct" mechanism alone but assuming an efficiency that is 3 times higher. The model based on the "indirect" channel also produces OH(ν) density distributions which are in good agreement with both SABER limb OH emission observations and ground and space measurements. This is, however, not true for the model which relies on the "direct" mechanism alone. This discrepancy is caused by the lack of an efficient redistribution of the OH(ν) energy from higher vibrational levels emitting at 2.0 µm to lower levels emitting at 1.6 µm. In contrast, the new  indirect  mechanism efficiently removes at least five quanta in each OH(ν ≥ 5) + O(3P) collision and provides the OH(ν) distributions which agree with both SABER limb OH emission observations and ground- and space-based OH(ν) density measurements. This analysis suggests that the important mechanism of the OH(ν) vibrational energy relaxation in the nighttime MLT, which was missing in the emission models of this atmospheric layer, has been finally identified.

scholarly journals Mode-Selective Vibrational Energy Transfer Dynamics in 1,3,5-Trinitroperhydro-1,3,5-Triazine (RDX) Thin Films

2021 ◽  
Author(s):  
Neil Cole-Filipiak ◽  
Robert Knepper ◽  
Mitchell A. Wood ◽  
Krupa Ramasesha
Keyword(s):  
Energy Transfer ◽  
Thermal Equilibrium ◽  
Transient Absorption ◽  
Vibrational Energy ◽  
Energetic Material ◽  
Transient Absorption Spectroscopy ◽  
Vibrational Energy Transfer ◽  
Mid Infrared ◽  
Mode Selectivity ◽  
Anharmonic Coupling

Herein, we report on the sub-picosecond to sub-nanosecond vibrational energy transfer (VET) dynamics of the solid energetic material 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) using broadband, ultrafast infrared transient absorption spectroscopy. Experiments reveal VET occurring on three distinct timescales: sub-picosecond, 5 ps, and 200 ps. The ultrafast appearance of signal at all probed modes in the mid-infrared suggests strong anharmonic coupling of all vibrations in the solid whereas the long-lived evolution demonstrates that VET is incomplete, and thus thermal equilibrium is not attained, even on the hundred picosecond timescale. Mode-selectivity of the longest dynamics suggests coupling of the N–N and axial NO<sub>2</sub> stretching modes with the long-lived, excited phonon bath.

scholarly journals Anab initiobased full-dimensional potential energy surface for OH + O2⇄ HO3and low-lying vibrational levels of HO3

2019 ◽  
Vol 21 (25) ◽  
pp. 13766-13775 ◽  
Author(s):  
Xixi Hu ◽  
Junxiang Zuo ◽  
Changjian Xie ◽  
Richard Dawes ◽  
Hua Guo ◽  
...  
Keyword(s):  
Potential Energy ◽  
Potential Energy Surface ◽  
Quantum Dynamics ◽  
Energy Surface ◽  
Vibrational Energy ◽  
Energy Levels ◽  
Vibrational Levels ◽  
Vibrational Energy Levels

A full-dimensional potential energy surface for HO3, including the HO + O2dissociation asymptote, is developed and rigorous quantum dynamics calculations based on this PES have been carried out to compute the vibrational energy levels of HO3.

scholarly journals Are the Carriers of Diffuse Interstellar Bands and Extended Red Emission the same?

2020 ◽  
Author(s):  
Thomas S-Y Lai ◽  
Adolf N Witt ◽  
Carlos Alvarez ◽  
Jan Cami
Keyword(s):  
Molecular Ions ◽  
Ionization Front ◽  
Stellar Spectrum ◽  
Red Emission ◽  
Large Molecules ◽  
Radiation Fields ◽  
Diffuse Interstellar Bands ◽  
Vibrational Levels ◽  
Extended Red Emission ◽  
Photodissociation Region

Abstract We report the first spectroscopic observations of a background star seen through the region between the ionization front and the dissociation front of the nebula IC 63. This photodissociation region (PDR) exhibits intense extended red emission (ERE) attributed to fluorescence by large molecules/ions. We detected strong diffuse interstellar bands (DIB) in the stellar spectrum, including an exceptionally strong and broad DIB at λ4428. The detection of strong DIBs in association with ERE could be consistent with the suggestion that the carriers of DIBs and ERE are identical. The likely ERE process is recurrent fluorescence, enabled by inverse internal conversions from highly excited vibrational levels of the ground state to low-lying electronic states with subsequent transitions to ground. This provides a path to rapid radiative cooling for molecules/molecular ions, greatly enhancing their ability to survive in a strongly irradiated environment. The ratio of the equivalent widths (EW) of DIBs λ5797 and λ5780 in IC 63 is the same as that observed in the low-density interstellar medium with UV interstellar radiation fields (ISRF) weaker by at least two orders of magnitude. This falsifies suggestions that the ratio of these two DIBs can serve as a measure of the UV strength of the ISRF. Observations of the nebular spectrum of the PDR of IC 63 at locations immediately adjacent to where DIBs were detected failed to reveal any presence of sharp emission features seen in the spectrum of the Red Rectangle nebula. This casts doubts upon proposals that the carriers of these features are the same as those of DIBs seen at slightly shorter wavelengths.

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