Vibrational-rotational Levels Research Articles

The far infrared absorption spectrum of D216O, D217O, and D218O: Experimental line positions, empirical energy levels and recommended line lists

The far infrared absorption spectra of D216O, D217O, and D218O are analyzed with improved accuracy and sensitivity in the 50–720 cm−1 range corresponding to the rotational band. Four room-temperature absorption spectra of highly deuterated water vapor were recorded at the SOLEIL synchrotron by high-resolution Fourier transform spectroscopy. Line centers are reported with a typical accuracy of 5 × 10−5 cm−1 for well isolated lines. The combined line list of about 9700 water lines was assigned to about 10 400 transitions of the nine stable water isotopologues (H2XO, HDXO, D2XO, with X = 16, 17, and 18). A total of 2885 transitions of eight bands involving the first five vibrational states were assigned to D216O. Among them, 2057 are newly reported. The obtained set of transition frequencies was merged with literature data to generate a new set of empirical energy levels for the first five vibrational states of D216O. A total of 1089 transitions of the (000)–(000) and (010)–(010) bands were measured for D217O. They were merged with literature sources to derive 724 empirical term values of seven vibrational states, up to 8088 cm−1. 348 D217O levels are newly determined. A set of 1150 transitions belonging to the (000)–(000) and (010)–(010) bands was measured for D218O. 3451 empirical energies of rotation–vibration levels up to 9222 cm−1 were retrieved using our observations and literature sources. The extension and accuracy of the derived empirical energy levels allow us to recommend new line lists with empirically corrected line positions for D216O, D217O, and D218O.

Analysis of experimental spectra of phosphine in the Tetradecad range near 2.3 μm using ab initio calculations

Due to its major interest for the chemistry of planetary atmospheres and exobiology, accurate spectroscopy data of phosphine are required for the search of signatures of this molecule in astronomical observations. In this work, high resolution infrared laboratory spectra of phosphine were analyzed for the first time in the full Tetradecad region (3769–4763 cm−1) involving 26 rotationally resolved bands. Overall, 3242 lines were assigned in spectra previously recorded by Fourier transform spectroscopy at temperatures 200 K and 296 K, using a combined theoretical model based on ab initio calculations. The total nuclear motion Hamiltonian of PH3 including ab initio potential energy surface, was reduced to an effective Hamiltonian using the high-order contact transformation method adapted to vibrational polyads of the AB3 symmetric top molecules, followed by empirical optimization of the parameters. At this step, the experimental line positions were reproduced with a standard deviation of 0.0026 cm−1 that provided unambiguous identification of observed transitions. The effective dipole transition moments of the bands were obtained by fitting to the intensities obtained from variational calculations using the ab initio dipole moment surface. The assigned lines were used to newly determine 1609 experimental vibration-rotational levels up to Jmax = 18 with energy in the range 3896–6037 cm−1 that represents significant extension towards higher energies compared to previous works. Transitions for all 26 sublevels of the Tetradecad were identified but with noticeably fewer transitions for fourfold excited bands because of their weaker intensity. At the final step, pressure-broadened half widths were attached to each transition and a composite line list adopting ab initio intensities and empirical line positions corrected to the accuracy of about 0.001 cm−1 for strong and medium transitions was validated against experimental spectra available in the literature.

The fine and hyperfine structures of the low-n 3Π u Rydberg states of H2 revisited

The experimental fine and hyperfine structures of low Rydberg states with 2–4 measured in the 1970's for various vibration-rotation levels by Lichten and collaborators, and by Miller and Freund, are reanalysed in the framework of molecular frame-transformation multichannel quantum defect theory MQDT. Instead of the level by level treatment in terms of an effective Hamiltonian as was carried out at the time, a global theory is applied to all levels at once. It is found that the essence of the observed level patterns is well represented by MQDT in terms of a substantially reduced number of dynamical parameters – quantum defects – although the experimental accuracy of the experiments is not yet quite reached. Possible reasons for the remaining discrepancies are given. Since quantum defect theory MQDT, a formalism derived from scattering theory, is still rather little used in the domain of modern ultra-high precision spectroscopy, the occasion is taken here to review some of its key elements.

Molecule opacity study on low-lying states of CS

CS molecule, which plays a key role in atmospheric and astrophysical circumstances, has drawn great attention for long time. Owing to its large state density, the detailed information of the electronic structure of CS is still lacking. In this work, the high-level MRCI+Q method is used to compute the potential energy curves, dipole moments and transition dipole moments of singlet and triplet states correlated with the lowest dissociation limit of CS, based on which high accurate vibration–rotation levels and spectroscopic constants of bound states are evaluated. The opacity of CS relevant to atmospheric circumstance is computed at a pressure of 100 atms for different temperatures. With the increase of temperature, band systems from different transitions mingle with each other, and band boundaries become blurred, which are originated from the increased population on vibrational excited states and electronic excited states at high temperature.

Classification of Amino Acids Using Hybrid Terahertz Spectrum and an Efficient Channel Attention Convolutional Neural Network.

Terahertz (THz) spectroscopy is the de facto method to study the vibration modes and rotational energy levels of molecules and is a widely used molecular sensor for non-destructive inspection. Here, based on the THz spectra of 20 amino acids, a method that extracts high-dimensional features from a hybrid spectrum combined with absorption rate and refractive index is proposed. A convolutional neural network (CNN) calibrated by efficient channel attention (ECA) is designed to learn from the high-dimensional features and make classifications. The proposed method achieves an accuracy of and on two testing datasets, which are and higher than the method solely classifying the absorption spectrum. The proposed method also realizes a processing speed of 3782.46 frames per second (fps), which is the highest among all the methods in comparison. Due to the compact size, high accuracy, and high speed, the proposed method is viable for future applications in THz chemical sensors.

The absorption spectrum of short-lived isotopic variant of water, H215O: Tentative detection at the Earth's atmosphere

A calculated infrared vibration–rotation spectrum of isotopically modified water, H215O, is presented. Oxygen-15 has a half-life of about 2 minutes and H215O may be formed in the atmosphere during thunderstorms as a result of photonuclear processes or when the atmosphere is irradiated by cosmic γ-rays. Variational nuclear motion calculations of vibrational and vibrational-rotational levels up to 25000 cm−1 and up to J = 10 in angular momentum are performed within the framework of the Born-Oppenheimer approximation using an accurate water potential function. The line shape parameters for H215O are estimated. Spectral ranges that are promising for the detection of H215O in the atmosphere are identified and a search for spectral signatures conducted. A spectral feature is tentatively assigned to the 752 (0 1 0) - 643 (0 0 0) line of H215O.

A Near-infrared Survey of UV-excited Molecular Hydrogen in Photodissociation Regions

Abstract We present a comparative study of the near-infrared (NIR) H2 line emission from five regions near hot young stars: Sharpless 140, NGC 2023, IC 63, the Horsehead Nebula, and the Orion Bar. This emission originates in photodissociation or photon-dominated regions (PDRs), interfaces between photoionized and molecular gas near hot (O) stars or reflection nebulae illuminated by somewhat cooler (B) stars. In these environments, the dominant excitation mechanism for NIR emission lines originating from excited rotational-vibrational (rovibrational) levels of the ground electronic state is radiative or UV excitation (fluorescence), wherein absorption of far-UV photons pumps H2 molecules into excited electronic states from which they decay into the upper levels of the NIR lines. Our sources span a range of UV radiation fields (G 0 = 102−105) and gas densities (n H = 104−106 cm−3), enabling examination of how these properties affect the emergent spectrum. We obtained high-resolution (R ≈ 45,000) spectra spanning 1.45–2.45 μm on the 2.7 m Harlan J. Smith Telescope at McDonald Observatory with the Immersion Grating INfrared Spectrometer (IGRINS), detecting up to over 170 transitions per source from excited vibrational states (v = 1–14). The populations of individual rovibrational levels derived from these data clearly confirm UV excitation. Among the five PDRs in our survey, the Orion Bar shows the greatest deviation of the populations and spectrum from pure UV excitation, while Sharpless 140 shows the least deviation. However, we find that all five PDRs exhibit at least some modification of the level populations relative to their values under pure UV excitation, a result we attribute to collisional effects.

An improved collision - radiation model of the OH spectrum in the ultraviolet band

In order to calculate the spectral radiation characteristics of OH(A2∑) molecules more accurately, an improved collision-radiation (C-R) model is proposed to determine the excited states OH(A) number density. The six-components air model (CO, CO2, H2, H2O, N2, and O2) instead of the two-components air model (N2 and O2) are used as other plume products in the excitation/de-excitation radiation reaction, and the rate of the four reactions are modified to improve the accuracy and applicability of the number density. Effects of temperature and other plume products on the number density of excited states are analyzed in the experiment, and the spectral radiation characteristics of OH(A) can be obtained by using this improved C-R model. Results of these calculations are then compared with other series of experimental data of exhaust plume and shock layer, the results show that both the original model and the improved model can be used to calculate the radiation characteristics in shock layer, however, due to the great error, the original model not apply to calculation of the OH(A) number density in exhaust plume, and the result of the improved model is in good agreement with the Atlas experimental data. As the vibrational-rotational level distribution number density has a close relationship with radiative spectral characteristics, a more focused OH(A) particle number density model will be more helpful to the hypersonic target detection and recognition.

Study on potential energy curves and ro-vibrational energies of DT, HT and T2 molecules

Accurately monitoring and effectively controlling the tritium compounds based on their ro-vibrational energy structure are important issues in various nuclear systems. Because of their radioactivity, it is difficult to obtain the corresponding energies directly through experiments. In this paper, the potential energy curves and the corresponding ro-vibrational full spectrum of DT, HT and T2 systems are derived by ab initio methods. However, it is difficult to verify the reliability of the calculated results due to the lack of direct experimental support. Therefore, a data-driven reliability analysis method is proposed, which can confirm the reliability by extracting information from the relevant calculations and multiple experimental data (the vibrational level, rotational level, and molar heat capacity) of similar systems (HD, H2, D2). The results show that: 1) The potential energy curves obtained by the ab initio method can provide the full ro-vibrational energy spectrum with an accuracy of approximately 10 cm−1; 2) Macroscopic heat capacity information can be used to distinguish and calibrate the overall reliability of microscopic ro-vibrational energies; 3) For the isotopic energy level structure of hydrogen, the influence of isotopes is mainly mass effect.

Direct Dissociative Excitation of Heteronuclear and Homonuclear Ions of Inert Gases by Electron Impact

Abstract—A theoretical description of the process of dissociative excitation of a molecular ion by an electron impact under the condition of effective population of a large number of its vibrational–rotational levels has been given. The approach is based on the quantum version of the theory of non-adiabatic transitions between electronic terms of a molecular ion and on the replacement of the summation with respect to $${v}J$$ -levels with the integration with respect to $${v}$$ and $$J$$ . Semi-analytical formulas for the integral contribution of the entire vibrational–rotational quasicontinuum to the cross sections $$\sigma _{T}^{{{\text{de}}}}(\varepsilon )$$ and rate constants $${{\alpha }^{{{\text{de}}}}}(T,{{T}_{e}})$$ of the process under study in a plasma with the $${{T}_{e}}$$ and $$T$$ temperatures of its electronic and ionic components have been obtained. The developed theory has been used to study the processes of dissociative excitation of heteronuclear (HeXe+ and ArXe+) and homonuclear (Ar $$_{2}^{ + }$$ and Xe $$_{2}^{ + }$$ ) ions of inert gases. A strong dependence of the results on the ion dissociation energy and large differences in the behavior and characteristic values of $$\sigma _{T}^{{{\text{de}}}}(\varepsilon )$$ and $${{\alpha }^{{{\text{de}}}}}(T,{{T}_{e}})$$ for these systems in different energy, $$\varepsilon $$ , and temperatures, $${{T}_{e}}$$ and $$T$$ , has been established. The regions of dominance of the contributions of two competing channels: direct dissociative excitation and dissociative recombination to the total cross sections and the rate of destruction of molecular ions of inert gases by electron impact have been determined. The analysis of the behavior of the differential rate constants of dissociative excitation in a unit electron energy interval in the final reaction channel has demonstrated qualitative differences in the dynamics of this process in the cases of weakly and moderately bound molecular ions.

GSRB rotation and rovibration intensities for: The bent HOCl molecule, and for: Quantum monodromy in NCNCS

Considerable work has gone into identifying and delineating the effects of quantum monodromy on molecules. Recently this included consideration of transition intensities of the NCNCS molecule using ab initio electric dipole moment functions in the Generalised SemiRigid Bender (GSRB) model [M. Winnewisser et al. PCCP 16, 17373-17407 (2014)]. In that work a discrepancy between the observed and calculated spectra was discovered. The purpose of the present work is to identify the source of that discrepancy - is it due to the physics of monodromy itself or are other issues involved? To investigate this we use the same theoretical approach for the simpler molecule HOCl. This allows us to identify a programming error affecting the b-type rovibrational transitions. We show that the NCNCS spectrum calculated with the corrected GSRB model does reproduce the experimental spectrum for pure rotational transitions within the ν7 large amplitude bending vibrational states, starting from the ground state and progressing through levels at the monodromy energy and beyond, while also reproducing the a-type υ:1←0rovibrational spectrum. However, the discrepancy with regard to the b-type rovibrational transitions remains. We discuss possible reasons for this discrepancy. In the course of this work we obtain a good GSRB model for the bending vibration-rotation levels of the atmospherically important HOCl molecule and its isotopologues. With ab initio calculations of the electric dipole moment function the GSRB calculates the rotation and bending rovibrational spectrum of HOCl in agreement with other determinations and with experiment. Using the physically constrained GSRB model, errors in tabulated transitions (including in the HITRAN database) were easily identified.

Photoswitchable Photon Upconversion from Turn-on Mode Fluorescent Diarylethenes

Photon upconversion (UC) is one kind of anti-Stokes shift process, which generally requires a combination of two or more low-energy photons to produce one high-energy photon. However, another inter...

Precise test of quantum electrodynamics and determination of fundamental constants with HD+ ions.

Bound three-body quantum systems are important for fundamental physics1,2 because they enable tests of quantum electrodynamics theory and provide access to the fundamental constants of atomic physics and to nuclear properties. Molecular hydrogen ions, the simplest molecules, are representative of this class3. The metastability of the vibration-rotation levels in their ground electronic states offers the potential for extremely high spectroscopic resolution. Consequently, these systems provide independent access to the Rydberg constant (R∞), the ratios of the electron mass to the proton mass (me/mp) and of the electron mass to the deuteron mass (me/md), the proton and deuteron nuclear radii, and high-level tests of quantum electrodynamics4. Conventional spectroscopy techniques for molecular ions5-14 have long been unable to provide precision competitive with that of ab initio theory, which has greatly improved in recent years15. Here we improve our rotational spectroscopy technique for a sympathetically cooled cluster of molecular ions stored in a linear radiofrequency trap16 by nearly two orders in accuracy. We measured a set of hyperfine components of the fundamental rotational transition. An evaluation resulted in the most accurate test of a quantum-three-body prediction so far, at the level of 5×10-11, limited by the current uncertainties of the fundamental constants. We determined the value of the fundamental constants combinations [Formula: see text] and mp/me with a fractional uncertainty of 2×10-11, in agreement with, but more precise than, current Committee on Data for Science and Technology values. These results also provide strong evidence of the correctness of previous key high-precision measurements and a more than 20-fold stronger bound for a hypothetical fifth force between a proton and a deuteron.

Прямое диссоциативное возбуждение гетероядерных и гомоядерных ионов инертных газов электронным ударом

A theoretical description of the process of dissociative excitation of a molecular ion by electron impact in the case of effective population of a huge number of its vibrational-rotational levels is presented. Our consideration is based on the quantal version of the theory of non-adiabatic transitions between the electronic terms of a molecular ion combined with replacing the summation over vJ-levels by integration over v and J. Semianalytical formulas are derived for the integral contribution of the entire vibrational-rotational quasicontinuum to the cross sections, $\sigma_T^{\mathrm{de}}(\varepsilon)$, and the rate constants, $\alpha^{\mathrm{de}}(T, T_e)$ of the process under study in a plasma with temperatures $T_e$ and $T$ of its electronic and ionic components. The developed theory is used to study the processes of dissociative excitation of heteronuclear (HeXe$^{+}$ and ArXe$^{+}$) and homonuclear (Ar$_2^{+}$ and Xe$_2^{+}$) ions of inert gases. We demonstrate a strong dependence of the results on the ion dissociation energy and large differences in the behavior and characteristic values of $\sigma_T^{\mathrm{de}}(\varepsilon)$ and $\alpha^{\mathrm{de}}(T, T_e)$ for these systems in different ranges of electron energy, $\varepsilon$, and temperatures $T_e$ and $T$. The regions of dominance of the contributions of two competing channels are determined: direct dissociative excitation and dissociative recombination into total cross sections and the rate constants of destruction of rare gas molecular ions by electron impact. Analyzing behavior of the differential rate constants of dissociative excitation per unit range of electron energy in the final channel of reaction we demonstrate qualitative differences in the dynamics of this process for weakly bound and moderately bound molecular ions.

Accurate all-electron calculation on the vibrational and rotational spectra of ground states for O2 and its ions**Project supported by the National Key Research and Development Program of China (Grant No. 2017YFA0403300), the National Natural Science Foundation of China (Grant Nos. 91750104, 11574114, and 11874177), and the Natural Science Foundation of Jilin Province, China (Grant No. 20160101332JC).

The potential energy curves, spectroscopic constants, and low-lying vibration–rotation levels of ground-state O2 and its cation and anion were calculated with the explicitly correlated multireference configuration interaction method. The zeroth-order reference wavefunction was treated with the complete active space multiconfigurational self-consistent field method, in which the active space was carefully selected, and an additional molecular orbital was added into the full valence active space. The electron correlation of the 1s core in the oxygen atom was considered in the computations. The Davidson correction on molecular energy was considered to account for higher electron excitation. The relativistic effects, including the scalar relativistic effect and spin–orbit coupling, were considered in the computation of potential energy curves. These physical effects on the spectroscopic constants were examined. The low-lying levels of vibration–rotation spectra of O2 and its ions were determined based on the computed potential energy curves. Comparisons with available experiments were made and excellent agreement was obtained for the vibrational and rotational parameters. The spectroscopic constants and vibration–rotation spectrum of , which is sparse in experiments, were provided. Our study will shed some light on further theoretical and experimental studies on these simple but important molecular systems.

CO laser line wavenumbers and absorption of their radiation by gaseous nitrogen oxides

In the article, new Dunham coefficients of the CO molecule in the X1Σ+ state are determined on the basis of the energy data for high vibrational–rotational levels. A comparison of the predicted values of the vibrational terms and the centers of vibrational–rotational transitions with experimental data for different sets of Dunham coefficients showed the reliability of the coefficients found. The centers of CO laser lines formed by transitions from high-energy vibrational–rotational levels are calculated. Modeling of the absorption spectral characteristics of NO, N2O, and NO2 is carried out. It is confirmed that the emission spectrum of a CO laser within a wide spectral region significantly depends on a number of factors (for example, characteristics of laser optical elements, mechanisms of broadening, and shifts of the working levels of laser transitions), which leads to variations in the values of the centers and widths of the laser lines and, as a consequence, to different values of transmission of CO laser radiation by gaseous compounds on the same laser lines.

The infrared spectrum of PF3 and analysis of rotational energy clustering effect

The first variational calculations of the rotational-vibrational levels of PF are performed and intensities for dipole transitions between them computed. This is accomplished using new state of the art potential energy and dipole moment surfaces. This allows the infrared spectrum of PF to be simulated, providing a complete overview of the ro-vibrational spectrum up to J=100 in the wavenumber range 0–3100 cm−1. The behaviour of PF at high rotational excitations is also investigated. The formation of quasi-degenerate 6-fold rotational energy clusters at high rotational excitation are investigated up to J=270 and are found to occur around J=200. The clustering effect is analysed in terms of semi-classical rotational energy surfaces.

Electronic and Vibrational Absorption Spectra of NH2 in Solid Ne.

Irradiation of ammonia dispersed in solid neon near 4 K with tunable far-ultraviolet light from a synchrotron yielded amidogen, NH2, and imidogen, NH, radicals as products. The electronic absorption spectra of amidogen radicals in isotopic variants NH2, NHD, and ND2 were recorded in the visible and near-ultraviolet regions after photolysis of NH3 and ND3. The infrared absorption lines of NH2 associated with vibration-rotational levels of vibrational modes ν1 at 3234.3 (00,0–10,1), 3244.9 (00,0–11,1), and 3249.3 cm–1 (00,0–11,0), and ν2 at 1498.7 (10,1–11,1), 1509.5 (11,0–10,1), 1516.5 (00,0–10,1), 1528.6 (00,0–11,1), and 1533.7 cm–1 (00,0–11,0) were unambiguously identified according to the results of experiments with deuterium isotopes. The 00,0–00,0 lines of ν1 and ν2 for NH2 were derived to be at 3213.5 and 1494.6 cm–1 in solid neon.

Theoretical study of infrared spectra for the Ar–N2O complex: Fundamental and combination bands

In this work, we performed a theoretical study of fundamental and combination bands for the infrared spectra of the Ar–N2O complex based on high-precision potential energy surfaces and bound state calculations. We constructed three two-dimensional potential energy surfaces (PESs) for the ground and excited states of the Ar–N2O complex. The bound state calculations were performed to determine the energies of rotational and intermolecular vibrational levels for this complex. Based on the results of the bound state calculations, we provide predictions for the infrared spectra of the Ar–N2O complex, including the fundamental and combination bands in the ν1 and ν3 regions of the N2O monomer. The theoretical results are in excellent agreement with experimental data, so our predicted results could be helpful to further investigate the infrared spectrum of van der Waals complex Ar–N2O.

Controlling tunneling in ammonia isotopomers.

We report results of full-dimensional variational rovibrational quantum-dynamical computations for several ammonia isotopomers, based on selected potential energy and electric dipole moment hypersurfaces. The variational rovibrational eigenstates have been used as a basis for the solution of the time-dependent Schrödinger equation for nuclear motion including coherent infrared multiphoton excitation. The theoretical and computational framework developed during this study enables the investigation of the coherent inhibition or enhancement of tunneling in ammonia isotopomers by appropriately chosen laser fields. Our quantum-dynamical computations include all vibrational and rotational degrees of freedom and assume neither the alignment nor the orientation of the molecules under investigation. Specific results include accurate rotational-vibrational levels for NH2D, NHD2, NHDMu, and NHDT, probability densities for structural parameters as a function of time from the full-dimensional wavepacket results, time-dependent chirality for the isotopically chiral molecule NHDT, and detailed analyses of the enhancement and inhibition of stereomutation dynamics.