Theoretical studies of atmospheric triatomic molecules (original) (raw)
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Regardless of the theory used for understanding atomic construction, equations that define atomic spectra must include as a derivative the Rydberg equation describing hydrogen and other single-electron ions. The following work product is evidence that defining all elemental spectra is achievable by merely changing some assumptions. The first assumption is that using integers in calculating spectra is incorrect. The second is that spin values for electrons in atoms begin at a ground state level and increase in spin-1 increments due to adding photons of spin-1. The third assumption is that photons are dual spin-1/2 composites. Using spin-1/2 as a basis produces a set of Rydberg-style equations providing spectra for all elements and their many ionic forms. The presented examples, hydrogen through neon, plus phosphorus, a spin-1/2 nucleus, reveal the equation behavior for elements of varying character. Unfortunately, determining which spectral lines dominate in multiple electron atoms is not straightforward without a solid theoretical underpinning. Current theory is lacking or it would be able to provide a similar solution. The term ‘preliminary’ in the title indicates that more than one equation solution exists for multi-electron ions. The equation sets provided represent the most logical and reasonable solutions. Although dominant line prediction is not yet forthcoming, an explanation for photon production using a combination of equation components is proffered. The enclosed information should lead to a full explanation once solutions for all elements are determined and examined in detail and theory further develops.
The Journal of Chemical Physics, 2004
Rotationally cold absorption and two-photon ionization spectra of CO in the 90–100 nm region have been recorded at a resolution of 0.3–1.0 cm−1. The analyses of up to four isotopomers seek to clarify the observations in regions where the Rydberg levels built on the ground state X 2Σ+ of the ion interact with valence states of 1Σ+ and 1Π symmetry. Previous observations of the 3sσ, B 1Σ+ Rydberg state, reviewed by Tchang-Brillet et al. [J. Chem. Phys. 96, 6735 (1992)], have been extended to energies above its avoided crossing with the repulsive part of the D′ 1Σ+ valence state where resonances of varying intensities and widths have been attributed to the fully coupled 3sσ or 4sσ and D′ potentials, and where the B state approaches a second avoided crossing with the C′ 1Σ+ valence state [Cooper and Kirby, J. Chem. Phys. 87, 424 (1987); 90, 4895 (1989); Chem. Phys. Lett. 152, 393 (1988)]. Fragments of a progression of weak and mostly diffuse bands, observed for all four isotopomers, have...
The Journal of Chemical Physics, 2004
Rotationally cold absorption and two-photon ionization spectra of CO in the 90-100 nm region have been recorded at a resolution of 0.3-1.0 cm Ϫ1 . The analyses of up to four isotopomers seek to clarify the observations in regions where the Rydberg levels built on the ground state X 2 ⌺ ϩ of the ion interact with valence states of 1 ⌺ ϩ and 1 ⌸ symmetry. Previous observations of the 3s, B 1 ⌺ ϩ Rydberg state, reviewed by Tchang-Brillet et al. ͓J. Chem. Phys. 96, 6735 ͑1992͔͒, have been extended to energies above its avoided crossing with the repulsive part of the DЈ 1 ⌺ ϩ valence state where resonances of varying intensities and widths have been attributed to the fully coupled 3s or 4s and DЈ potentials, and where the B state approaches a second avoided crossing with the CЈ 1 ⌺ ϩ valence state ͓Cooper and Kirby, J. Chem. Phys. 87, 424 ͑1987͒; 90, 4895 ͑1989͒; Chem. Phys. Lett. 152, 393 ͑1988͔͒. Fragments of a progression of weak and mostly diffuse bands, observed for all four isotopomers, have been assigned to the CЈ←X transition. The least-squares modeling of the 4p and 5p complexes reveals the 3p, E 1 ⌸ Rydberg state to be one of the perturbers, violating the ⌬vϭ0 selection rule for Rydberg-Rydberg interactions on account of its rapid transition with increasing v from Rydberg to valence state. A second 1 ⌸ perturber, very loosely bound and clearly of valence type, contributes to the confusion in the published literature surrounding the 5p, vϭ0 complex.
Predissociation of the 4pπL1Π Rydberg state of carbon monoxide
Chemical Physics, 2002
Time-domain and frequency-domain spectroscopic experiments have been performed on the ð4ppÞL 1 P, v ¼ 0 Rydberg state in three isotopomers of carbon monoxide. Accurate values for the excited state lifetimes of the f-parity components have been determined: sð 12 C 16 OÞ ¼ 1:08 AE 0:05 ns, sð 13 C 16 OÞ ¼ 72 AE 10 ps and sð 13 C 18 OÞ ¼ 29 AE 6 ps. The spectral resolution in the frequency-domain experiment goes as far as the limit imposed by the natural lifetime; Qbranch lines, or f-parity components of the heavier isotopes, are resolved for the first time. Highly accurate transition frequencies are determined in a molecular beam experiment using comparison and interpolation with a saturated iodine reference standard. The results reveal a number of perturbations and predissociation mechanisms, displaying a high degree of complexity in the energetic region of the 4p Rydberg states of CO with strong isotopic effects.
The E2Σ+ → C2Π Transition of NO and Term Values for the A, D, E, and C Lowest Rydberg Levels
Journal of Molecular Spectroscopy, 2000
The E 2 ⌺ ϩ 3 C 2 ⌸ Rydberg-Rydberg transition of 14 N 16 O near 8492 cm Ϫ1 has been studied by Fourier transform spectrometry in the emission from a dc excited supersonic jet expansion and from a dc discharge under equilibrium conditions. The same transition has also been observed in laser-induced stimulated emission. Line wavenumbers of the 0 -0, 1-1, and 2-2 bands, together with data for previously published near-infrared transitions, have been reduced to consistent sets of rovibronic term values for v ϭ 0, 1, and 2 of the A 2 ⌺ ϩ , D 2 ⌺ ϩ , E 2 ⌺ ϩ , and C 2 ⌸ states which frequently serve as intermediates in the multiphoton excitation of higher Rydberg levels of NO.
Addition to and revision of the HI Rydberg states energy region
Journal of Molecular Spectroscopy, 2020
Mass resolved REMPI data was recorded for jet cooled HI(g) for two-photon excitation in the region of 74 200-80 300 cm À1. REMPI spectra of the ions (HI + , I + and H +) were derived from the data. The spectra revealed dense and overlapping rotational peak structure due to two-photon resonant transitions to number of Rydberg and ion-pair molecular vibrational states as well as iodine atom (2 + 1) REMPI peaks. A total of 16 Rydberg state spectra and 9 ion-pair state spectra were identified and simulated to derive spectroscopic constants (band origin (m 0) and 1st and 2nd order rotational constants (B 0 , D 0)) for the excited states. Further analysis of the results for the Rydberg states and inspection of the spectral structure allowed more thorough characterization of the states as well as reassignment of some previously reported spectra. Detailed quantum defect analyses were particularly useful in that respect. The states could be specified by term symbols, ion core symmetries, Rydberg electron principal quantum numbers and configurations as well as vibrational quantum numbers. An attempt was made to assign the ion-pair spectra to vibrational quantum numbers. Relevant results on Rydberg and ion-pair states of HI, from the literature are summarized in the paper.
Predissociation of the 4ppLP Rydberg state of carbon monoxide
2002
Time-domain and frequency-domain spectroscopic experiments have been performed on the ð4ppÞLP, v 1⁄4 0 Rydberg state in three isotopomers of carbon monoxide. Accurate values for the excited state lifetimes of the f-parity components have been determined: sðCOÞ 1⁄4 1:08 0:05 ns, sðCOÞ 1⁄4 72 10 ps and sðCOÞ 1⁄4 29 6 ps. The spectral resolution in the frequency-domain experiment goes as far as the limit imposed by the natural lifetime; Qbranch lines, or f-parity components of the heavier isotopes, are resolved for the first time. Highly accurate transition frequencies are determined in a molecular beam experiment using comparison and interpolation with a saturated iodine reference standard. The results reveal a number of perturbations and predissociation mechanisms, displaying a high degree of complexity in the energetic region of the 4p Rydberg states of CO with strong isotopic effects. 2002 Elsevier Science B.V. All rights reserved.
Separation of Long-Range and Short-Range Interactions in Rydberg States of Diatomic Molecules
Journal of Chemical Physics, 128, 194301 (2008)
Observation and analysis of the f͑ᐉ =3͒, g͑ᐉ =4͒, and h͑ᐉ =5͒ Rydberg series of CaF in the range 13ഛ n ഛ 17 is presented. Simultaneous analysis of the f, g, and h Rydberg series of CaF, combined with significant improvements to the long-range model for nonpenetrating Rydberg states, provides a generally applicable scheme for separating the effects of the long-range ͑electric multipole and polarization͒ and short-range ͑core penetration͒ interactions between the Rydberg electron and ion core in diatomic molecules. Techniques for rigorous assignment of nonpenetrating states, as well as extensions of the long-range model, are discussed. Explicit formulas for the first-and second-order matrix elements of the first four anisotropic electric multipole interactions ͑electric dipole, quadrupole, octupole, and hexadecapole͒ are given. The discrepancies between the observed behavior and that predicted by the long-range model, which are particularly significant for the f series, are shown to be due to penetration of the Rydberg electron wavefunction within the ion core. We show that these penetration effects can be understood within the framework of ligand field theory and conclude with a discussion of the relative contributions of the long-and short-range interactions to the quantum defects of the core-penetrating "s," "p," and "d" series of CaF.
The Astrophysical Journal, 2006
One of the processes controlling the interstellar CO abundance and the ratio of its isotopologues is photodissociation. Accurate oscillator strengths and predissociation rates for Rydberg transitions are needed for modeling this process. We present results on absorption from the E 1 Π − X 1 Σ + (1-0) and B 1 Σ + − X 1 Σ + (6-0) bands at 1051 and 1002Å, respectively, and the vibrational progression W 1 Π − X 1 Σ + (v ′ -0) bands with v ′ = 0 to 3 at 972, 956, 941, and 925Å, respectively. The corresponding spectra were acquired at the high resolution (R ≈ 30,000) SU5 beam line at the Super ACO Synchrotron in Orsay, France. Spectra were obtained for the 12 C 16 O, 13 C 16 O, and 13 C 18 O isotopologues. These represent the most complete set of measurements available. Comparison is made with earlier results, both empirical and theoretical. While earlier determinations of oscillator strengths based on absorption from synchrotron radiation tend to be somewhat smaller than ours, the suite of measurements from a variety of techniques agree for the most part considering the mutual uncertainties. For the bands studied here, their relative weakness, or their significant line widths arising from predissociation, minimizes potential problems from large optical depths at line center in absorption measurements. Predissociating line widths could generally be extracted from the spectra thanks to the profile simulations used in the analysis. In many cases, these simulations allowed us to consider e and f parity levels separately and to determine the dependence of the width on rotational quantum number, J. Our results are consistent with earlier determinations, especially the widths inferred from laser experiments.