Population Of Vibrational Levels Research Articles

Regulating the redshift of the charge transfer band edge and antithermal quenching by ion substitution strategy in YP1-xVxO4:Eu3+ phosphor

The redshift of the charge transfer band (CTB) edge of phosphor induced by temperature rise is pervasively accompanied by antithermal quenching. Accordingly, exploring the mechanism of the CTB redshift is thus not only propitious for optimizing the sensitivity of optical thermometry but also tenders a new idea for the design of antithermal quenching phosphors. Herein, a family of YP1-xVxO4:Eu3+ phosphors were designed via the V5+/P5+ ion substitution strategy. With the increase of the V5+ ratio, the relative integral intensity of the 5D0→7F2 transition multiplies from 1.25 to 28.67 times under CTB edge excitation. Moreover, by Gaussian fitting, the reduction degree of vanadate band gap energy 1E (1T1)→1B2 (1T2), 1A2 (1T1)→1B2 (1T2) increased from 0.122 eV and 0.065 eV to0.162 eV and 0.083 eV, respectively, in the range of 303–523 K. Both reveal an enhance in redshift of the excitation spectra. The decrease of charge transfer state (CTS) energy level and the alteration of photoelectron thermal population are two mechanisms that induce CTB redshift. Specifically, the decrease of the CTS level is dominant in the YPO4:Eu3+ sample, and the thermal population of the higher vibrational levels of the VO43−ground state is dominant in the presence of a tiny amount of V5+ doping. In addition, according to the experimental phenomenon, a dual-mode temperature sensing scheme based on excitation intensity ratio (EIR) and single band ratiometric (SBR) is proposed. Y0.9P0.1V0.9O4:0.1Eu3+ achieves a maximum sensitivity of Sr-max = 4.040 % K−1 and a minimum temperature determination uncertainty of δT = 0.124 K at 323 K, which excellent performance indicates that this is a promising non-contact optical thermometer.

Time-dependent electron Boltzmann equation for hypersonic plasmas

The electron kinetics in hypersonic plasmas is modeled by solving the time-dependent electron Boltzmann equation for the electron energy distribution function (EEDF). This plasma is created by strong shock compression of the gas in front of a vehicle moving with hypersonic speed. The main source of energy for the electrons is gas heating due to elastic collisions and second-kind collisions (de-excitation) from vibrationally excited states of N2. We established that the electron energy distribution function is most sensitive to vibrational level populations. At mid-altitudes (tens of kilometers), the electron temperature equilibrates with the vibrational temperature on a microsecond timescale. The electron distribution function reaches steady state on a comparable timescale. Numerical simulations of air plasma showed that the electron energy distribution function is far from Maxwellian and the collision rates differ by orders of magnitude from those computed with a Maxwellian distribution. The two most important parameters for the electron kinetics and the electron energy distribution function are the vibrational temperature and ionization degree.

Electronic, spectroscopic, dynamic and thermodynamic properties of systems formed by noble gases and oxygen

Using accurate methodologies, an extensive study was conducted to investigate the electronic, spectroscopic, dynamic, and thermodynamic properties of systems comprising noble gases (Ng) and oxygen atoms in low-lying electronic states derived from the Ng (1S) + O (3P) separated atom limits. Our target has been to obtain information complementary to that provided by previous important studies performed on such systems. The analysis of electronic energy decomposition indicates that Ng–O systems exhibit a significant non-covalent nature in the resulting bond. In terms of thermodynamics, the Ar–O and He–O systems demonstrate the highest and lowest propensity, respectively, for formation within 50–500 K. The populations of vibrational levels in the Ne–O, Ar–O, Kr–O, and Xe–O systems exhibit an inverted distribution as the temperature is increased from 50 K to room temperature and 500 K. This fact may serve as motivation for future experimental-theoretical studies, as they suggest that these systems may have possible technological applications in lasers.

Vibrational kinetics in repetitively pulsed atmospheric pressure nitrogen discharges: average-power-dependent switching behaviour

Characterisation of the vibrational kinetics in nitrogen-based plasmas at atmospheric pressure is crucial for understanding the wider plasma chemistry, which is important for a variety of biomedical, agricultural and chemical processing applications. In this study, a 0-dimensional plasma chemical-kinetics model has been used to investigate vibrational kinetics in repetitively pulsed, atmospheric pressure plasmas operating in pure nitrogen, under application-relevant conditions (average plasma powers of 0.23–4.50 W, frequencies of 1–10 kHz, and peak pulse powers of 23–450 W). Simulations predict that vibrationally excited state production is dominated by electron-impact processes at lower average plasma powers. When the average plasma power increases beyond a certain limit, due to increased pulse frequency or peak pulse power, there is a switch in behaviour, and production of vibrationally excited states becomes dominated by vibrational energy transfer processes (vibration–vibration (V–V) and vibration–translation (V–T) reactions). At this point, the population of vibrational levels up to increases significantly, as a result of V–V reactions causing vibrational up-pumping. At average plasma powers close to where the switching behaviour occurs, there is potential to control the energy efficiency of vibrational state production, as small increases in energy deposition result in large increases in vibrational state densities. Subsequent pathways analysis reveals that energy in the vibrational states can also influence the wider reaction chemistry through vibrational–electronic (V–E) linking reactions (N + N N + N and N + N N + N), which result in increased Penning ionisation and an increased average electron density. Overall, this study investigates the potential for delineating the processes by which electronically and vibrationally excited species are produced in nitrogen plasmas. Therefore, potential routes by which nitrogen-containing plasma sources could be tailored, both in terms of chemical composition and energy efficiency, are highlighted.

Nuclear quantum dynamics on the ground electronic state of neutral silver dimer 107Ag109Ag probed by femtosecond NeNePo spectroscopy.

The nuclear quantum dynamics on the ground electronic state of the neutral silver dimer 107Ag109Ag are studied by femtosecond (fs) pump-probe spectroscopy using the 'negative ion - to neutral - to positive ion' (NeNePo) excitation scheme. A vibrational wave packet is prepared on the X1Σ+g state of Ag2via photodetachment of mass-selected, cryogenically cooled Ag2- using a first ultrafast pump laser pulse. The temporal evolution of the wave packet is then probed by an ultrafast probe pulse via resonant multiphoton ionization to Ag2+. Frequency analysis of the fs-NeNePo spectra obtained for a single isotopologue and pump-probe delay times up to 60 ps yields the harmonic (ωe = 192.2 cm-1), quadratic anharmonic (ωexe = 0.637 cm-1) and cubic anharmonic (ωeye = 3 × 10-4 cm-1) constants for the X1Σ+g state of neutral Ag2. The fs-NeNePo spectra obtained at different pump wavelengths provide insight into the excitation mechanism. At a pump wavelength of 510 nm instead of 1010 nm, resonant excitation of a short-lived electronically excited state of the anion followed by autodetachment results in population of higher-energy vibrational levels of the neutral ground state. In contrast, at 1140 nm dynamics with a slightly shorter beating period and different relative phase are observed. The present study demonstrates that isotopologue-specific fs-NeNePo spectroscopy provides accurate vibrational constants of mass-selected neutral clusters in their electronic ground state in the terahertz spectral region, which remains difficult to obtain directly in the frequency domain with any other type of spectroscopy of comparable sensitivity.

Explaining the temperature-induced shift of the V-O charge transfer band experimentally and design of single-excitation ratiometric optical thermometry.

Temperature-induced redshift of the V-O charge transfer band (CTB) is promising for designing high performance optical thermometry. The shift mechanism is considered as the thermal populations of high vibrational energy levels of the VO4 3- ground state. Direct experimental evidence for this, however, is still lacking. In this work, Tm3+-doped YVO4 with various doping concentrations was studied to achieve strong 1D2 emission of Tm3+. The temperature dependent CTB was studied at low temperatures to give direct evidence experimentally for the shift mechanism of the CTB using YVO4:20% Tm3+. It was found that the V-O CTB does not shift when the temperature is lower than a certain temperature (60 K), verifying the proposed shift mechanism experimentally. In addition, based on the temperature quenching of 1D2 emission of Tm3+ and the redshift of the CTB, single-excitation ratiometric thermometry was carried out using YVO4:30% Tm3+,6% Sm3+. High relative sensitivity was achieved with a maximal value reaching up to 3.86% K-1 at approximately 355 K.

Kinetic and Continuum Modeling of High-Temperature Oxygen and Nitrogen Binary Mixtures

The present paper provides a comprehensive comparative analysis of thermochemistry models of various fidelity levels developed in leading research groups around the world. Fully kinetic, hybrid kinetic–continuum, and fully continuum approaches are applied to analyze parameters of hypersonic flows starting from the revision of single-temperature rate constants up to the application in 1-D postshock conditions. Comparison of state-specific and two-temperature approaches shows there are very significant and often qualitative differences in the time-dependent nonequilibrium reaction rates and their ratio to the corresponding single-temperature rates. A major impact of the vibration–dissociation coupling on the temporal relaxation of gas properties is shown. For instance, the legacy Park’s model has a strongly nonlinear behavior of nonequilibrium reaction rate with vibrational temperature, while a nearly linear shape exists for all state-specific approaches. Analysis of vibrational level populations in the nonequilibrium region shows a profound impact of the numerical approach and the model on the population ratios, and thus vibrational temperatures inferred from such ratios. The difference in the ultraviolet absorption coefficients, calculated by a temperature-based spectral code using vibrational populations from state-specific and kinetic approaches, is found to exceed an order of magnitude.

Electron transport properties of molecular junctions with anharmonic double-well potentials

In the present paper, we investigated the electron transport properties of molecular junctions with anharmonic vibrations described by double-well potentials in the sequential tunneling regime. It was found that the suppression of the low-bias current caused by strong electron-vibration couplings under harmonic approximation, i.e., the Franck-Condon blockade effect, could be lifted in the case of symmetric double-well potentials. The removal of the Franck-Condon blockade effect is a result of the distribution of the ground vibrational wave function in the two wells. Such a feature also enables the Franck-Condon blockade effect to be restored by breaking the symmetry of the double-well potential. We further demonstrated that the special vibrational transition properties of asymmetric double-well potentials could enable the effective modulation of the charge transport properties of such molecular junctions in the Franck-Condon blockade region by inducing population in excited vibrational levels with external fields such as infrared excitation.

Effect of Freezing out Vibrational Modes on Gas-Phase Fluorescence Spectra of Small Ionic Dyes.

While action spectroscopy of cold molecular ions is a well-established technique to provide vibrationally resolved absorption features, fluorescence experiments are still challenging. Here we report the fluorescence spectra of pyronin-Y and resorufin ions at 100 K using a newly constructed setup. Spectra narrow upon cooling, and the emission maxima blueshift. Temperature effects are attributed to the population of vibrational excited levels in S1, and that frequencies are lower in S1 than in S0. This picture is supported by calculated spectra based on a Franck-Condon model that not only predicts the observed change in maximum, but also assigns Franck-Condon active vibrations. In-plane vibrational modes that preserve the mirror plane present in both S0 and S1 of resorufin and pyronin Y account for most of the observed vibrational bands. Finally, at low temperatures, it is important to pick an excitation wavelength as far to the red as possible to not reheat the ions.

Vibrationally Induced Photophysical Response of Sr2NaMg2V3O12:Eu3+ for Dual‐Mode Temperature Sensing and Safety Signs

In the dual‐emitting Eu3+‐activated Sr2NaMg2V3O12 garnet, vibrationally induced thermometric response and thermochromic luminescence are investigated for the first time. Based on the diverse thermal quenching of VO43− and Eu3+ along with the advantage of variation in the fluorescence intensity ratio, a potential phosphor for sensitive dual‐mode ratiometric and colorimetric temperature sensors is proposed in which maximum absolute and relative sensitivity of 0.0135 K−1 and 1.61% K−1 are obtained at 420 K with a temperature resolution <0.2 K. Efficient thermochromic luminescence in which colorific shift from white (300 K) to red (500 K) is observed such that the requirement of larger number of phonons weakens the nonradiative relaxation of Eu3+, resulting in slow quenching, substantiated by estimating radiative and nonradiative decay rates by the 4f–4f intensity method. In contrast, a strong vibrational coupling of excited electrons of the VO43− complex is identified and verified by means of temperature‐dependent Raman and photoluminescence excitation spectra for the first time. Consequently, an increased thermal population of vibrational levels favors rapid thermal quenching of luminescence of VO43− via crossover mechanism. Hence dual‐centered Sr2NaMg2V3O12:Eu is an efficient thermometric and thermochromic luminescent material for optical thermometry and safety sign applications in a high‐temperature environment.

Численное моделирование течения термически и химически неравновесного воздуха за фронтом ударной волны

We used the model of a five-component air mixture flow behind the front of a one-dimensional shock wave to compute the flow parameters for shock front temperatures of up to 7000 K, taking into account the variable composition, translational and vibrational temperatures and pressure in the relaxation zone. Vibrational level population in oxygen and nitrogen obeys the Boltzmann distribution with one common vibrational temperature. We consider the effect that temperature nonequilibrium has on the chemical reaction rate by introducing a nonequilibrium factor to the reaction rate constant, said factor depending on the vibrational and translational temperatures. We compared our calculation results for dissociation behind the shock front to the published data concerning temperature nonequilibrium in a pure oxygen flow behind a shock wave front for two different intensities of the latter. The comparison shows a good agreement between the vibrational temperature, experimental data and calculations based on the experimental values of vibrational temperature and molality. We computed the parameters of thermodynamically nonequilibrium dissociation in the air behind the shock wave front, comparing them to those of equilibrium dissociation and calculation results previously published by others. The study demonstrates that the molality values computed converge gradually with those found in published data as the distance from the shock front increases. We list the reasons for the discrepancy between our calculation results and previously published data

Effect of Reagent Vibration and Rotation on the State-to-State Dynamics of the Hydrogen Exchange Reaction, H + H2 → H2 + H.

State-to-state dynamics of the benchmark hydrogen exchange reaction H + H2 (v = 0-4, j = 0-3) → H2 (v', j') + H is investigated with the aid of the real wave packet approach of Gray and Balint-Kurti (J. Chem. Phys. 1998, 108, 950-962) and electronic ground BKMP2 potential energy surface of Boothroyd et al. (J. Chem. Phys. 1996, 104, 7139-7152). Initial state-selected and product state-resolved reaction probabilities, integral cross section, and product diatom vibrational and rotational level populations at a few collision energies are reported to elucidate the energy disposal mechanism. State-specific thermal rate constants are also calculated and compared with the available literature results. Coriolis coupling terms of the nuclear Hamiltonian are included, and calculations are parallelized over the helicity quantum number, Ω'. Attempts are made, in particular, to study the effect of reagent vibrational and rotational excitations on the dynamical attributes. It is found that the calculations become computationally expensive with reagent vibrational and rotational excitation. Reagent vibrational excitation is found to enhance the reactivity and has significant impact on the energy disposal to the vibrational and rotational degrees of freedom of the product. The interplay of reagent translational and vibrational energy on the product vibrational distribution unfolds an important aspect of the energy disposal mechanism. The effect of reagent rotation on the state-to-state dynamics is found not to be very significant, and the weak effect turns out to be specific to v'.

Formation of ultracold ground-state CsYb molecules via Feshbach-optimized photoassociation

We investigate theoretically the formation of ultracold ground-state CsYb molecules on the lowest vibrational level via the Feshbach-optimized photoassociation process. Three s-wave Feshbach resonances of CsYb are found. The probability density of the scattering state in the short-range internuclear distance is significantly enhanced near the resonance positions. The population transfer efficiency reaches its maximum when the pulse duration equals half a period of the Rabi oscillation. By using the optimized laser parameters including the peak intensity and detuning, the final population of the lowest vibrational level of the ground electronic state reaches order of 10−1 in the four-laser scheme.

Modelling of vibrational nonequilibrium effects on the H2–air mixture ignition under shock wave conditions in the state-to-state and mode approximations

Kinetics of physicochemical processes occurring during combustion of a hydrogen–air mixture initiated by a shock wave was studied using state-to-state and mode models that take into account nonequilibrium vibrational excitation of N2, O2, H2, and OH molecules. The effect of vibrational–translational relaxation on the induction time was considered: it was shown that the delay in establishing thermodynamic equilibrium between vibrational and translational degrees of freedom slows down the initiation of combustion, while the intensity of this effect depends on the temperature and pressure of the gas behind the shock front. An analysis of the peculiarities of vibrational distributions showed that populations of the lower vibrational levels of molecules in the course of chain reactions of combustion behind the shock wave are close to the Boltzmann ones. Therefore, it is sufficient to use the mode approximation. Calculations of the induction time using models of mode approximation showed a significant dependence of the results on the choice of the nonequilibrium factor model. If the nonequilibrium factors are calculated based on the summation of level rate constants of physicochemical processes, the accuracy of the mode model is not inferior to the accuracy of the state-to-state approximation.

Improved Analysis of Ultraviolet Absorption Spectra Under Nonequilibrium Shock Conditions

A landmark set of measurements of high-temperature relaxation under strong shock heating conditions, conducted in 2013 by Ibraguimova et al. (“Investigation of Oxygen Dissociation and Vibrational Relaxation at Temperatures 4000–10800 K,” Journal of Chemical Physics, Vol. 139, No. 3, 2013, Paper 034317) using ultraviolet (UV) absorption converted to time-dependent vibrational temperature profiles, have been receiving considerable attention in the literature as a test of nonequilibrium thermochemical models. A number of attempts by computational fluid dynamics modelers to reproduce the published results were unsuccessful in predicting the peak vibrational temperature, the downstream slope, or both. Our recent analysis has shown that some of the assumptions used in spectra-to-temperature conversions, such as the two-temperature approximation, are violated in the early region of the shock, and a more detailed analysis and direct comparison of UV absorption, and not temperatures, is necessary. This work presents such an analysis where a gas number density, translational temperature, and distribution of rotational and vibrational level populations, obtained using a kinetic gas dynamic approach, are converted into UV in-band absorption for each temporal or spatial location in the shock using a detailed spectroscopic model. The computed UV absorption is then directly compared with the raw measured time-dependent UV absorption curves at several wavelengths. Such a comparison is shown to have more validity than the previous ones.

Dissociation dynamics of carbon dioxide cation (CO2 +) in the C2Σg + state via [1+1] two-photon excitation.

The dissociation dynamics of CO2 + in the C2Σg + state has been studied in the 8.14-8.68 eV region by [1+1] two-photon excitation via vibronically selected intermediate A2Πu and B2Σu + states using a cryogenic ion trap velocity map imaging spectrometer. The cryogenic ion trap produces an internally cold mass selected ion sample of CO2 +. Total translational energy release (TER) and two-dimensional recoiling velocity distributions of fragmented CO+ ions are measured by time-sliced velocity map imaging. High resolution TER spectra allow us to identify and assign three dissociation channels of CO2 + (C2Σg +) in the studied energy region: (1) production of CO+(X2Σ+) + O(3P) by predissociation via spin-orbit coupling with the repulsive 14Πu state; (2) production of CO+(X2Σ+) + O(1D) by predissociation via bending and/or anti-symmetric stretching mediated conical intersection crossing with A2Πu or B2Σu +, where the C2Σg +/A2Πu crossing is considered to be more likely; (3) direct dissociation to CO+(A2Π) + O(3P) on the C2Σg + state surface, which exhibits a competitive intensity above its dissociation limit (8.20 eV). For the first dissociation channel, the fragmented CO+(X2Σ+) ions are found to have widely spread populations of both rotational and vibrational levels, indicating that bending of the parent CO2 + over a broad range is involved upon dissociation, while for the latter two channels, the produced CO+(X2Σ+) and CO+(A2Π) ions have relatively narrow rotational populations. The anisotropy parameters β are also measured for all three channels and are found to be nearly independent of the vibronically selected intermediate states, likely due to complicated intramolecular interactions in the studied energy region.

Vibrational and rotational cooling dynamics of the triatomic molecular ion N2O+ stored in RICE

SynopsisWe studied radiative cooling dynamics of the triatomic molecular ion N2O+ stored in RICE. We observed the evolution of the populations at vibrational and rotational levels up to several 100 s by measuring neutral fragments from the laser-induced predissociation process. We found clear evidence of radiative cooling of the vibrational level populations with a time constant of several seconds. In contrast, absence of significant changes in the rotational levels revealed that the time scale of the rotational cooling is far longer, which is consistent to our simulation.

Photodissociation transition states characterized by chirped pulse millimeter wave spectroscopy

The 193-nm photolysis of CH2CHCN illustrates the capability of chirped-pulse Fourier transform millimeter-wave spectroscopy to characterize transition states. We investigate the HCN, HNC photofragments in highly excited vibrational states using both frequency and intensity information. Measured relative intensities of J = 1-0 rotational transition lines yield vibrational-level population distributions (VPD). These VPDs encode the properties of the parent molecule transition state at which the fragment molecule was born. A Poisson distribution formalism, based on the generalized Franck-Condon principle, is proposed as a framework for extracting information about the transition-state structure from the observed VPD. We employ the isotopologue CH2CDCN to disentangle the unimolecular 3-center DCN elimination mechanism from other pathways to HCN. Our experimental results reveal a previously unknown transition state that we tentatively associate with the HCN eliminated via a secondary, bimolecular reaction.

Ro-vibrational cooling of diatomic molecules Cd2 and Yb2: rotational energy structure included

Method of ro-vibrational cooling of Cd and Yb molecules occupying initially their excited ro-vibrational levels in the ground electronic state is proposed. The method employs the and electronic transitions in Cd and Yb, respectively. The cooling relies on a successive decrease of population of the ground-state vibrational and rotational levels using a series of laser-induced excitations from a selected ground-state (, ) to the excited-state (, ) ro-vibrational levels, followed by spontaneous de-excitations to the ground state. The proposal is an extension of the vibrational cooling method recently proposed by Urbańczyk et al. [Mol. Phys. 116, 3475–3486 (2018)].

The Boltzmann Vibrational Temperature of N2 (B3Πg) Derived From ISUAL Imager Multiband Measurements of Transient Luminous Events

AbstractOne of the main challenges for the observation of a transient luminous event (TLE) is to observe TLEs in different emission bands. Here, we show TLEs recorded using the ISUAL 427.8 nm, 630 nm, N2 1P (623–750 nm) and 762‐nm‐filtered imager, and we analyze the 630‐nm‐filtered, N2 1P‐filtered, and 762‐nm‐filtered images of TLEs for estimating the N2 (B3Πg) Boltzmann vibrational temperature in comparison with the theoretical N2 1P spectrum. For ISUAL recorded sprites, the average brightness of N2 1P (I1p), 762 nm (I762), and 630 nm (I630) emission was 2.3, 0.6, and 0.02 MR. The N2 (B3Πg) vibrational temperatures (Tv) was estimated to be 2800 K, 3200 K, and 4300 K for multiband emission ratios of I630/I1p, I630/I762, and I762/I1p. For observed elves, the average brightness I1p, I762, and I630 were 170, 50, and 3 kR. The estimated Tv values were 3700 K, 3700 K, and 3800 K for ratios I630/I1p, I630/I762, and I762/I1p. For observed gigantic jets, the derived Tv values were 3000–5000 K for a ratio I762/I1p. Through N2 (B3Πg) Tv analyses from emission ratios of ISUAL multiband observation, we derived the N2 (B3Πg) vibrational temperature that ranges between 3000 and 5000 K or higher in TLEs. Accuracy and variations of derived N2 (B3Πg) Tv are also discussed while relative population of vibrational levels in the Boltzmann equilibrium are also compared with past spectra observation.