arXiv subjects

E. J. Salumbides

Publications and source records attributed to E. J. Salumbides.

At least 19 recordsLinked to original sources

arXiv2022

Rotational level spacings in HD from vibrational saturation spectroscopy

The R(1), R(3) and P(3) ro-vibrational transitions in the (2-0) overtone band of the HD molecule are measured in Doppler-free saturation using the technique of NICE-OHMS spectroscopy. For the P(3) line, hitherto not observed in saturation, we report a frequency of $203\,821\,936\,805\,(60)$ kHz. The dispersive line shapes observed in the three spectra show strong correlations, allowing for extraction of accurate information on rotational level spacings. This leads to level spacings of $Δ_{(J=3)-(J=1)}= 13\,283\,245\,098\,(30)$ kHz in the $v=0$ ground state, and $Δ_{(J=4)-(J=2)}= 16\,882\,368\,179\,(20)$ kHz in the $v=2$ excited vibration in HD. These results show that experimental values for the rotational spacings are consistently larger than those obtained with advanced ab initio theoretical calculations at 1.5$σ$, where the uncertainty is determined by theory. The same holds for the vibrational transitions where systematic deviations of 1.7-1.9$σ$ are consistently found for the five lines accurately measured in the (2-0) band.

physics.atom-ph↗

arXiv2022

Fourier-transform spectroscopy of $^{13}$C$^{17}$O and deperturbation analysis of the A$^1Π$ ($ν$ = 0 - 3) levels

The high-resolution B$^1Σ^+$ - A$^1Π$ (0, 0) and (0, 3) emission bands of the less-abundant $^{13}$C$^{17}$O isotopologue have been investigated by Fourier-transform spectroscopy in the visible region using a Bruker IFS 125HR spectrometer at an accuracy 0.003 cm$^{-1}$. These spectra are combined with high-resolution photoabsorption measurements of the $^{13}$C$^{17}$O B$^1Σ^+$ $\leftarrow$ X$^1Σ^+$ (0, 0), B$^1Σ^+$ $\leftarrow$ X$^1Σ^+$ (1, 0) and C$^1Σ^+$ $\leftarrow$ X$^1Σ^+$ (0, 0) bands recorded with an accuracy of 0.01 cm$^{-1}$ using the vacuum ultraviolet Fourier-transform spectrometer, installed on the DESIRS beamline at the SOLEIL synchrotron. In the studied 17,950 - 22,500 cm$^{-1}$ and 86,800 - 92,100 cm$^{-1}$ regions, 480 transitions have been measured. These new experimental data were combined with data from the C $\to$ A and B $\to$ A systems, previously analyzed in 13C17O. The frequencies of 1003 transitions derived from 12 bands were used to analyze the perturbations between the A$^1Π$ ($ν$ = 0 - 3) levels and rovibrational levels of the d$^3Δ_i$, e$^3Σ^-$, a$'{}^3Σ^+$, I$^1Σ^-$ and D$^1Δ$ states as well as to a preliminary investigation of weak irregularities that appear in the B$^1Σ^+$ ($ν$ = 0) level. Deperturbed molecular constants and term values of the A$^1Π$ state were obtained. The spin-orbit and L-uncoupling interaction parameters as well as isotopologue-independent spin-orbit and rotation-electronic perturbation parameters were derived.

physics.chem-ph↗

arXiv2022

Improved Ionization and Dissociation Energies of the Deuterium Molecule

The ionization energy of D$_2$ has been determined experimentally from measurements involving two-photon Doppler-free vacuum-ultraviolet pulsed laser excitation and near-infrared continuous-wave laser excitation to yield $E_\mathrm{I}(\mathrm{D}_2)=124\,745.393\,739(26)$ \wn. From this value, the dissociation energy of D$_2$ is deduced to be $D_0$(D$_2$) = 36\,748.362\,282(26) \wn, representing a 25-fold improvement over previous values, and found in good agreement (at $1.6σ$) with recent ab initio calculations of the 4-particle nonadiabatic relativistic energy and of quantum-electrodynamic corrections up to order $mα^6$. This result constitutes a test of quantum electrodynamics in the molecular domain, while a perspective is opened to determine nuclear charge radii from molecules.

physics.atom-ph↗

arXiv2021

Chirp-compensated pulsed titanium-sapphire laser system for precision spectroscopy

Active frequency-chirp compensation for a narrowband pulsed Titanium-Sapphire laser system is demonstrated using an intra-cavity electro-optic modulator resulting in improved spectral resolution and stability. With referencing to an optical frequency comb and further residual frequency chirp detection from shot-to-shot measurements, the resulting laser pulses are frequency up-converted for high-precision spectroscopy measurements in the VUV regime, where the relative uncertainty contribution due to frequency chirp is pushed to the $5 \times 10^{-11}$ level.

physics.optics↗

arXiv2021

Precision measurement of quasi-bound resonances in H$_2$ and the H + H scattering length

Quasi-bound resonances of H$_2$ are produced via two-photon photolysis of H$_2$S molecules as reactive intermediates or transition states, and detected before decay of the parent molecule into three separate atoms. As was previously reported [K.F. Lai et al., Phys. Rev. Lett. 127, 183001 (2021)] four centrifugally bound quantum resonances with lifetimes of multiple $μ$s, lying energetically above the dissociation limit of the electronic ground state X$^1Σ_g^+$ of H$_2$, were observed as X($v,J$) = (7,21)$^*$, (8,19)$^*$, (9,17)$^*$, and (10,15)$^*$, while also the short-lived ($\sim 1.5$ ns) quasi-bound resonance X(11,13)$^*$ was probed. The present paper gives a detailed account on the identification of the quasi-bound or shape resonances, based on laser detection via F-X two-photon transitions, and their strongly enhanced Franck-Condon factors due to the shifting of the wave function density to large internuclear separation. In addition, the assignment of the rotational quantum number is verified by subsequent multi-step laser excitation into autoionization continuum resonances. Existing frameworks of full-fledged ab initio computations for the bound region in H$_2$, including Born-Oppenheimer, adiabatic, non-adiabatic, relativistic and quantum-electrodynamic contributions, are extended into the energetic range above the dissociation energy. These comprehensive calculations are compared to the accurate measurements of energies of quasi-bound resonances, finding excellent agreement. Etc.

physics.atom-ph↗

arXiv2021

Shape resonances in H$_2$ as photolysis reaction intermediates

Shape resonances in H$_2$, produced as reaction intermediates in the photolysis of H$_2$S precursor molecules, are measured in a half-collision approach. Before desintegrating into two ground state H atoms, the reaction is quenched by two-photon Doppler-free excitation to the F electronically excited state of H$_2$. For $J=13,15,17,19$ and 21, resonances with lifetimes in the range of nano to milliseconds were observed with an accuracy of 30~MHz (1.4~mK). The experimental resonance positions are found to be in excellent agreement with theoretical predictions when nonadiabatic and quantum electrodynamical corrections are included. This is the first time such effects are observed in collisions between neutral atoms. From the potential energy curve of the H$_2$ molecule, now tested at high accuracy over a wide range of internuclear separations, the s-wave scattering length for singlet H(1s)+H(1s) scattering is determined at $a = 0.2735^{39}_{31}~a_0$.

physics.atom-ph↗

arXiv2021

Photolysis production and spectroscopic investigation of the highest vibrational states in H$_2$ (X$^1Σ_g^+$ $v=13,14$)

Rovibrational quantum states in the $X^1Σ_g^+$ electronic ground state of H$_2$ are prepared in the $v=13$ vibrational level up to its highest bound rotational level $J=7$, and in the highest bound vibrational level $v=14$ (for $J=1$) by two-photon photolysis of H$_2$S. These states are laser-excited in a subsequent two-photon scheme into $F^1Σ_g^+$ outer well states, where the assignment of the highest ($v,J$) states is derived from a comparison of experimentally known levels in \F, combined with \emph{ab initio} calculations of \X\ levels. The assignments are further verified by excitation of $F^1Σ_g^+$ population into autoionizing continuum resonances which are compared with multi-channel quantum defect calculations. Precision spectroscopic measurements of the $F-X$ intervals form a test for the \emph{ab initio} calculations of ground state levels at high vibrational quantum numbers and large internuclear separations, for which agreement is found.

physics.chem-ph↗

arXiv2020

Fourier-transform VUV spectroscopy of $^{14,15}$N and $^{12,13}$C

Accurate Fourier-transform spectroscopic absorption measurements of vacuum ultraviolet transitions in atomic nitrogen and carbon were performed at the Soleil synchrotron. For $^{14}$N transitions from the $2s^22p^3\,^4$S$_{3/2}$ ground state and from the $2s^22p^3\,^2$P and $^2$D metastable states were determined in the $95 - 124$ nm range at an accuracy of $0.025\,\mathrm{cm}^{-1}$. Combination of these results with data from previous precision laser experiments in the vacuum ultraviolet range reveal an overall and consistent offset of -0.04 \wn\ from values reported in the NIST database. %The splitting of the $2s^22p^3\,^4$S$_{3/2}$ -- %$2s2p^4\,^4$P$_{5/2,3/2,1/2}$ The splittings of the $2s^22p^3\,^4$S$_{3/2}$ -- $2s2p^4\,^4$P$_{J}$ transitions are well-resolved for $^{14}$N and $^{15}$N and isotope shifts determined. While excitation of a $2p$ valence electron yields very small isotope shifts, excitation of a $2s$ core electron results in large isotope shifts, in agreement with theoretical predictions. For carbon six transitions from the ground $2s^22p^2\,^3$P$_{J}$ and $2s^22p3s\, ^3$P$_{J}$ excited states at $165$ nm are measured for both $^{12}$C and $^{13}$C isotopes.

physics.atom-ph↗

arXiv2020

Two-photon Doppler-free ultraviolet laser spectroscopy on sulphur atoms

The $3p^{4}$ $^{3}$P$_{J}$ - $3p^{3}4p$ $^{3}$P$_{J}$ transition in the sulphur atom is investigated in a precision two-photon excitation scheme under Doppler-free and collision-free circumstances yielding an absolute accuracy of 0.0009 cm$^{-1}$, using a narrowband pulsed laser. This verifies and improves the level separations between amply studied odd parity levels with even parity levels in S I. An improved value for the $^{3}$P$_{2}$ - $^{3}$P$_{1}$ ground state fine structure splitting is determined at $396.0564$ (7) cm$^{-1}$. A $^{34}$S - $^{32}$S atomic isotope shift was measured from combining time-of-flight mass spectrometry with laser spectroscopy.

physics.atom-ph↗

arXiv2020

Lamb-peak spectrum of the HD (2-0) P(1) line

A saturation spectroscopy measurement of the P(1) line of the ($2-0$) band in HD is performed in a sensitive cavity-enhanced optical setup involving frequency comb calibration. The spectral signature is that of a Lamb-peak, in agreement with a density-matrix model description involving 9 hyperfine components and 16 crossover resonances of $Λ$-type. Comparison of the experimental spectra with the simulations yields a rovibrational transition frequency at 209,784,242,007 (20) kHz. Agreement is found with a first principles calculation in the framework of non-adiabatic quantum electrodynamics within 2$σ$, where the combined uncertainty is fully determined by theory.

physics.atom-ph↗

arXiv2020

Precision measurement of the fundamental vibrational frequencies of tritium-bearing hydrogen molecules: T$_2$, DT, HT

High-resolution coherent Raman spectroscopic measurements of all three tritium-containing molecular hydrogen isotopologues T$_2$, DT and HT were performed to determine the ground electronic state fundamental Q-branch ($v=0 \rightarrow 1, ΔJ = 0$) transition frequencies at accuracies of $0.0005$ cm$^{-1}$. An over hundred-fold improvement in accuracy over previous experiments allows the comparison with the latest ab initio calculations in the framework of Non-Adiabatic Perturbation Theory including nonrelativisitic, relativisitic and QED contributions. Excellent agreement is found between experiment and theory, thus providing a verification of the validity of the NAPT-framework for these tritiated species. While the transition frequencies were corrected for ac-Stark shifts, the contributions of non-resonant background as well as quantum interference effects between resonant features in the nonlinear spectroscopy were quantitatively investigated, also leading to corrections to the transition frequencies. Methods of saturated CARS with the observation of Lamb dips, as well as the use of continuous-wave radiation for the Stokes frequency were explored, that might pave the way for future higher-accuracy CARS measurements.

physics.chem-ph↗

arXiv2019

Lamb-dips and Lamb-peaks in the saturation spectrum of HD

The saturation spectrum of the R(1) transition in the (2-0) band in HD is found to exhibit a composite line shape, involving a Lamb-dip and a Lamb-peak. We propose an explanation for such behavior based on the effects of cross-over resonances in the hyperfine substructure, which is made quantitative in a density-matrix calculation. This resolves an outstanding discrepancy on the rovibrational R(1) transition frequency, which is now determined at 217 105 181 901 (50) kHz and in agreement with current theoretical calculations.

physics.atom-ph↗

arXiv2019

H$_2$/HD molecular data for analysis of quasar spectra in search of varying constants

Absorption lines of H$_2$ and HD molecules observed at high redshift in the line of sight towards quasars are a test ground to search for variation of the proton-to-electron mass ratio $μ$. For this purpose, results from astronomical observations are compared with a compilation of molecular data of the highest accuracy, obtained in laboratory studies as well as in first-principles calculations. Aims: A comprehensive line list is compiled for H$_2$ and HD absorption lines in the Lyman ($B^1Σ_u^+$ - $X^1Σ_g^+$) and Werner ($C^1Π_u$ - $X^1Σ_g^+$) band systems up to the Lyman cutoff at 912 Angstroms. Molecular parameters listed for each line $i$ are the transition wavelength $λ_i$, the line oscillator strength $f_i$, the radiative damping parameter of the excited state $Γ_i$, and the sensitivity coefficient $K_i$ for a variation of the proton-to-electron mass ratio. Methods: The transition wavelengths $λ_i$ for the H$_2$ and HD molecules are determined by a variety of advanced high-precision spectroscopic experiments involving narrowband vacuum ultraviolet lasers, Fourier-transform spectrometers, and synchrotron radiation sources. Results for the line oscillator strengths $f_i$, damping parameters $Γ_i$, and sensitivity coefficients $K_i$ are obtained in theoretical quantum chemical calculations. Results: A new list of molecular data is compiled for future analyses of cold clouds of hydrogen absorbers, specifically for studies of $μ$-variation from quasar data. The list is applied in a refit of quasar absorption spectra of B0642$-$5038 and J1237$+$0647 yielding constraints on a variation of the proton-to-electron mass ratio $Δμ/μ$ consistent with previous analyses.

astro-ph.CO↗

arXiv2018

Precision spectroscopy and comprehensive analysis of perturbations in the $A\,{}^1Π(v=0$) state of ${}^{\rm 13}$C${}^{\rm 18}$O

We have reinvestigated the A$^1Π$$(v=0)$ level of $^{13}$C$^{18}$O\ using new high-resolution spectra obtained via multi-photon laser excitation as well as with synchrotron-based Fourier-transform absorption spectroscopy of the A$^1Π-\textrm{X}^1Σ^+$$(0, 0)$, e$^3Σ^--\textrm{X}^1Σ^+$$(1, 0)$, d$^3Δ-\textrm{X}^1Σ^+$$(4, 0)$, a$'^3Σ^+-\textrm{X}^1Σ^+$$(9, 0)$, and \atX$(11, 0)$ bands. In addition, Fourier-transform emission spectroscopy in the visible range is performed on the ${\rm B}^1Σ^+-{\rm A}^1Π$$(0, 0)$ band. Spectra of the \BX$(0, 0)$ band are measured in order to tie information from the latter emission data to the level structure of A$^1Π$$(v=0)$. The high pressures in the absorption cell at the synchrotron and the high temperatures in the emission discharge permitted monitoring of high rotational quantum levels in A$^1Π$$(v=0)$ up to $J=43$. All information, in total over 900 spectral lines, was included in an effective-Hamiltonian analysis of the A$^1Π(v=0, J)$ levels that are directly perturbed by the e$\,^3Σ^-$$(v=1)$, d$^3\!Δ$$(v=4)$, a$'^3Σ^+$$(v=9)$, d$^3\!Δ$$(v=0)$, I$\,^1Σ^-$$(v=0, 1)$ close-lying levels and the e$\,^3Σ^-$$(v=0,2)$, d$^3\!Δ$$(v=3,5)$, a$'^3Σ^+$$(v=8,10)$ remote levels, as well being indirectly influenced by the a$^3Π$$(v=10, 11)$ state. The influence of nine further perturber levels and their interactions was investigated and are not significant for reproducing the present experimental data. This analysis leads to a much improved description in terms of molecular constants and interaction parameters, compared to previous studies of the same energy region for other CO isotopologues.

physics.atom-ph↗

arXiv2018

Dissociation energy of the hydrogen molecule at 10$^{-9}$ accuracy

The ionization energy of ortho-H$_2$ has been determined to be $E^\mathrm{o}_\mathrm{I}(\mathrm{H}_2)/(hc)=124\,357.238\,062(25)$ cm$^{-1}$ from measurements of the GK(1,1)--X(0,1) interval by Doppler-free two-photon spectroscopy using a narrow band 179-nm laser source and the ionization energy of the GK(1,1) state by continuous-wave near-infrared laser spectroscopy. $E^\mathrm{o}_\mathrm{I}$(H$_2$) was used to derive the dissociation energy of H$_2$, $D^{N=1}_{0}$(H$_2$), at $35\,999.582\,894(25)$ cm$^{-1}$ with a precision that is more than one order of magnitude better than all previous results. The new result challenges calculations of this quantity and represents a benchmark value for future relativistic and QED calculations of molecular energies.

physics.chem-ph↗

arXiv2018

Relativistic and QED effects in the fundamental vibration of T$_2$

The hydrogen molecule has become a test ground for quantum electrodynamical calculations in molecules. Expanding beyond studies on stable hydrogenic species to the heavier radioactive tritium-bearing molecules, we report on a measurement of the fundamental T$_2$ vibrational splitting $(v= 0 \rightarrow 1)$ for $J=0-5$ rotational levels. Precision frequency metrology is performed with high-resolution coherent anti-Stokes Raman spectroscopy at an experimental uncertainty of $10-12$~MHz, where sub-Doppler saturation features are exploited for the strongest transition. The achieved accuracy corresponds to a fifty-fold improvement over a previous measurement, and allows for the extraction of relativistic and QED contributions to T$_2$ transition energies.

physics.chem-ph↗

arXiv2017

Sub-Doppler frequency metrology in HD for test of fundamental physics

Weak transitions in the (2,0) overtone band of the HD molecule at $λ= 1.38 \, μ$m were measured in saturated absorption using the technique of noise-immune cavity-enhanced optical heterodyne molecular spectroscopy. Narrow Doppler-free lines were interrogated with a spectroscopy laser locked to a frequency comb laser referenced to an atomic clock to yield transition frequencies [R(1) = $217\,105\,181\,895\,(20)$ kHz; R(2) = $219\,042\,856\,621\,(28)$ kHz; R(3) = $220\,704\,304\,951\,(28)$ kHz] at three orders of magnitude improved accuracy. These benchmark values provide a test of QED in the smallest neutral molecule, and open up an avenue to resolve the proton radius puzzle, as well as constrain putative fifth forces and extra dimensions.

physics.atom-ph↗

arXiv2017

CARS spectroscopy of the ($v=0\to1$) band in $\rm{T_2}$

Molecular hydrogen is a benchmark system for bound state quantum calculation and tests of quantum electrodynamical effects. While spectroscopic measurements on the stable species have progressively improved over the years, high resolution studies on the radioactive isotopologues $\rm{T_2}$, $\rm{HT}$ and $\rm{DT}$ have been limited. Here we present an accurate determination of $\rm{T_2}$ $Q(J = 0 - 5)$ transition energies in the fundamental vibrational band of the ground electronic state, by means of high resolution Coherent Anti-Stokes Raman Spectroscopy. With the present experimental uncertainty of $0.02\,\rm{cm^{-1}}$, which is a fivefold improvement over previous measurements, agreement with the latest theoretical calculations is demonstrated.

physics.atom-ph↗