Quantum Electrodynamics Effects in Rovibrational Spectra of Molecular Hydrogen (original) (raw)
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Rovibrational energy levels of the hydrogen molecule through nonadiabatic perturbation theory
Physical Review A, 2019
We present an accurate theoretical determination of rovibrational energy levels of the hydrogen molecule and its isotopologues in its electronic ground state. We consider all significant corrections to the Born-Oppenheimer approximation, obtained within nonadiabatic perturbation theory, including the mixed nonadiabatic-relativistic effects. Quantum electrodynamic corrections in the leading α 5 m and the next-to-leading α 6 m orders, as well as finite nuclear size effect, are also taken into account but within the Born-Oppenheimer approximation only. Final results for the transition wavelength between rovibrational levels achieve accuracy of the order of 10 −3-10 −7 cm −1 , and are provided by simple to use computer code.
QED Effects in Molecules: Test on Rotational Quantum States of H_{2}
Physical Review Letters, 2011
Quantum electrodynamic effects have been systematically tested in the progression of rotational quantum states in the X 1 AE þ g , v ¼ 0 vibronic ground state of molecular hydrogen. High-precision Doppler-free spectroscopy of the EF 1 AE þ g -X 1 AE þ g (0,0) band was performed with 0:005 cm À1 accuracy on rotationally hot H 2 (with rotational quantum states J up to 16). QED and relativistic contributions to rotational level energies as high as 0:13 cm À1 are extracted, and are in perfect agreement with recent calculations of QED and high-order relativistic effects for the H 2 ground state.
Laser-stimulated electric quadrupole transitions in the molecular hydrogen ion H2+
Molecular hydrogen ions are of metrological relevance due to the possibility of precise theoretical evaluation of their spectrum and of external-field-induced shifts. We report the results of the calculations of the rate of laser-induced electric quadrupole transitions between a large set of rovibrational states of H + 2. The hyperfine and Zeeman structure of the E2 transition spectrum and the effects of the laser polarization are treated in detail. We also present the nuclear spin-electron spin coupling constants, computed with a precision 10 times higher than previously.
Quadrupole Transition Probabilities for the Excited Rovibrational States of H 2
The Astrophysical Journal Supplement Series, 1998
Accurate calculations of the quadrupole moment of carried out with a 494 term variational repre-H 2 , sentation of the electronic eigenfunction, are reported, and the quadrupole transition probabilities connecting all the bound rovibrational levels of are presented. H 2
arXiv (Cornell University), 2016
Accurate EF 1 Σ + g − X 1 Σ + g transition energies in molecular hydrogen were determined for transitions originating from levels with highly-excited vibrational quantum number, v = 11, in the ground electronic state. Doppler-free two-photon spectroscopy was applied on vibrationally excited H * 2 , produced via the photodissociation of H 2 S, yielding transition frequencies with accuracies of 45 MHz or 0.0015 cm −1. An important improvement is the enhanced detection efficiency by resonant excitation to autoionizing 7pπ electronic Rydberg states, resulting in narrow transitions due to reduced ac-Stark effects. Using known EF level energies, the level energies of X(v = 11, J = 1, 3 − 5) states are derived with accuracies of typically 0.002 cm −1. These experimental values are in excellent agreement with, and are more accurate than the results obtained from the most advanced ab initio molecular theory calculations including relativistic and QED contributions.
International Journal of Quantum Chemistry, 2011
Starting with the Hamilton-Jacobi equation, Campos et al. have applied Hylleraas' method along with the series obtained by Wind-Jaffe to several molecular ions, among which the H + 2 system, to determine their electronic energies in different states. In this work, we have fitted the potential energy curves for the 2pπ, 3dσ , 4dσ , 4f π, 4f σ , 5gσ , and 6iσ electronic states of the H + 2 ion employing the Rydberg generalized function. From these fittings, the spectroscopic constants and the rovibrational energies have been determined by two distinct methods: Dunham's and the discrete variable representation. The theoretically obtained results are in a satisfactory agreement and are expected to provide a comparison source to future works in the experimental field.
Fundamental Vibration of Molecular Hydrogen
Physical Review Letters, 2013
The fundamental ground tone vibration of H 2 , HD, and D 2 is determined to an accuracy of 2 Â 10 À4 cm À1 from Doppler-free laser spectroscopy in the collisionless environment of a molecular beam. This rotationless vibrational splitting is derived from the combination difference between electronic excitation from the X 1 AE þ g , v ¼ 0, and v ¼ 1 levels to a common EF 1 AE þ g , v ¼ 0 level. Agreement within 1 between the experimental result and a full ab initio calculation provides a stringent test of quantum electrodynamics in a chemically bound system.
Indonesian Journal of Chemistry
This study aims to apply a semi-classical approach using some analytically solvable potential functions to accurately compute the first ten pure vibrational energies of molecular hydrogen (H2) and its isotopes in their ground electronic states. This study also aims at comparing the accuracy of the potential functions within the framework of the semi-classical approximation. The performance of the approximation was investigated as a function of the molecular mass. In this approximation, the nuclei were assumed to move in a classical potential. The Bohr-Sommerfeld quantization rule was then applied to calculate the vibrational energies of the molecules numerically. The results indicated that the first vibrational transition frequencies (v1ß0) of all hydrogen isotopes were consistent with the experimental ones, with a minimum percentage error of 0.02% for ditritium (T2) molecule using the Modified-Rosen-Morse potential. It was also demonstrated that, in general, the Rosen-Morse and the...