arXiv subjects

Peter F. Bernath

Publications and source records attributed to Peter F. Bernath.

12 recordsLinked to original sources

arXiv2026

Rotational spectra and de-perturbation analysis for ground state ytterbium oxide, YbO

A combination difference analysis of Fourier transform microwave spectroscopy (FTMW) measurements of $^{174}$YbO combined with earlier near-infrared chemiluminescence data have resulted in much improved YbO rotational and centrifugal distortion constants. These have been confirmed in a multi-isotopologue analysis of further FTMW measurements of $^{172}$YbO and $^{176}$YbO and an analysis of nuclear-size-dependent Born-Oppenheimer breakdown effects in the molecule. Multiple excited electronic states overlap with low-lying excited vibrational levels of the electronic ground state leading to irregularities in its vibrational spacings and other previously observed electronic manifolds. This has been modeled with a matrix of the vibrational levels of the ground and multiple interacting states assuming Morse potentials and including electronic Hamiltonian matrix elements mixing the states. Vibrational level overlaps were calculated numerically assuming Morse vibrational wavefunctions. The resulting de-perturbed potentials for the states inform continuing experimental and theoretical work on this and other ytterbium-containing molecules.

physics.chem-ph↗

arXiv2019

MARVEL analysis of the measured high-resolution spectra of $^{14}$NH

Rovibronic energy levels are determined for four low-lying electronic states (\X, \A, \Sa, and \Sc) of the imidogen free radical ($^{14}$NH) using the \Marvel\ (Measured Active Rotational-Vibrational Energy Levels) technique. Compilation of transitions from both laboratory measurements and solar spectra, found in 18 publications, yields a dataset of 3002 rovibronic transitions forming elements of a measured spectroscopic network (SN). At the end of the MARVEL procedure, the majority of the transitions form a single, self-consistent SN component of 2954 rovibronic transitions and 1058 energy levels, \NoX, \NoA, and \Noc\ for the \X, \A, and \Sc\ electronic states, respectively. The \Sa\ electronic state is characterized by \Noa\ $Λ$-doublet levels, counting each level only once. Electronic structure computations show that unusually the CCSD(T) method does not accurately predict the \Sa\ excitation energy even at the complete basis set limit.

physics.chem-ph↗

arXiv2016

Experimental energy levels and partition function of the $^{12}$C$_2$ molecule

The carbon dimer, the $^{12}$C$_2$ molecule, is ubiquitous in astronomical environments. Experimental-quality rovibronic energy levels are reported for $^{12}$C$_2$, based on rovibronic transitions measured for and among its singlet, triplet, and quintet electronic states, reported in 42 publications. The determination utilizes the Measured Active Rotational-Vibrational Energy Levels (MARVEL) technique. The 23,343 transitions measured experimentally and validated within this study determine 5,699 rovibronic energy levels, 1,325, 4,309, and 65 levels for the singlet, triplet, and quintet states investigated, respectively. The MARVEL analysis provides rovibronic energies for six singlet, six triplet, and two quintet electronic states. For example, the lowest measurable energy level of the \astate\ state, corresponding to the $J=2$ total angular momentum quantum number and the $F_1$ spin-multiplet component, is 603.817(5) \cm. This well-determined energy difference should facilitate observations of singlet--triplet intercombination lines which are thought to occur in the interstellar medium and comets. The large number of highly accurate and clearly labeled transitions that can be derived by combining MARVEL energy levels with computed temperature-dependent intensities should help a number of astrophysical observations as well as corresponding laboratory measurements. The experimental rovibronic energy levels, augmented, where needed, with {\it ab initio} variational ones based on empirically adjusted and spin-orbit coupled potential energy curves obtained using the \Duo\ code, are used to obtain a highly accurate partition function, and related thermodynamic data, for $^{12}$C$_2$ up to 4,000 K.

astro-ph.GA↗

arXiv2015

Molecular Data: Division B / Commission 14 / Working Group Molecular Data

The current report covers the period from the second half of 2011 to late 2014. It is divided into three areas covering rotational, vibrational, and electronic spectroscopy. A signifcant amount of experimental and theoretical work has been accomplished over the past three years, leading to the development and expansion of a number of databases whose links are provided below. Two notable publications have appeared recently: An issue of The Journal of Physical Chemistry A in 2013 honoring the many contributions of Takeshi Oka (J. Phys. Chem. A, 117, pp. 9305-10143); and IAU Symposium 297 on Diffuse Interstellar Bands. A number of the relevant papers from these volumes are cited. Related research on collisions, reactions on grain surfaces, and astrochemistry are not included here.

physics.atom-ph↗

arXiv2015

High-resolution absorption cross sections of C$_{2}$H$_{6}$ at elevated temperatures

Infrared absorption cross sections near 3.3 $μ$m have been obtained for ethane, C$_{2}$H$_{6}$. These were acquired at elevated temperatures (up to 773 K) using a Fourier transform infrared spectrometer and tube furnace with a resolution of 0.005 cm$^{-1}$. The integrated absorption was calibrated using composite infrared spectra taken from the Pacific Northwest National Laboratory (PNNL). These new measurements are the first high-resolution infrared C$_{2}$H$_{6}$ cross sections at elevated temperatures.

astro-ph.EP↗

arXiv2015

Empirical line lists and absorption cross sections for methane at high temperature

Hot methane is found in many "cool" sub-stellar astronomical sources including brown dwarfs and exoplanets, as well as in combustion environments on Earth. We report on the first high-resolution laboratory absorption spectra of hot methane at temperatures up to 1200 K. Our observations are compared to the latest theoretical spectral predictions and recent brown dwarf spectra. The expectation that millions of weak absorption lines combine to form a continuum, not seen at room temperature, is confirmed. Our high-resolution transmittance spectra account for both the emission and absorption of methane at elevated temperatures. From these spectra, we obtain an empirical line list and continuum that is able to account for the absorption of methane in high temperature environments at both high and low resolution. Great advances have recently been made in the theoretical prediction of hot methane, and our experimental measurements highlight the progress made and the problems that still remain.

astro-ph.SR↗

arXiv2015

Line Strengths of Rovibrational and Rotational Transitions in the X$^2Π$ Ground State of OH

A new line list including positions and absolute intensities (in the form of Einstein $A$ values and oscillator strengths) has been produced for the OH ground X\DP\ state rovibrational (Meinel system) and pure rotational transitions. All possible transitions are included with v$\primed$ and v$\Dprimed$ up to 13, and $J$ up to between 9.5 and 59.5, depending on the band. An updated fit to determine molecular constants has been performed, which includes some new rotational data and a simultaneous fitting of all molecular constants. The absolute line intensities are based on a new dipole moment function, which is a combination of two high level ab initio calculations. The calculations show good agreement with an experimental v=1 lifetime, experimental $μ_\mathrm{v}$ values, and $Δ$v=2 line intensity ratios from an observed spectrum. To achieve this good agreement, an alteration in the method of converting matrix elements from Hund's case (b) to (a) was made. Partitions sums have been calculated using the new energy levels, for the temperature range 5-6000 K, which extends the previously available (in HITRAN) 70-3000 K range. The resulting absolute intensities have been used to calculate O abundances in the Sun, Arcturus, and two red giants in the Galactic open and globular clusters M67 and M71. Literature data based mainly on [O I] lines are available for the Sun and Arcturus, and excellent agreement is found.

astro-ph.SR↗

arXiv2014

Recommended isolated-line profile for representing high-resolution spectroscopic transitions (IUPAC Technical Report)

The report of an IUPAC Task Group, formed in 2011 on "Intensities and line shapes in high-resolution spectra of water isotopologues from experiment and theory" (Project No. 2011-022-2-100), on line profiles of isolated high-resolution rotational-vibrational transitions perturbed by neutral gas-phase molecules is presented. The well-documented inadequacies of the Voigt profile (VP), used almost universally by databases and radiative-transfer codes, to represent pressure effects and Doppler broadening in isolated vibrational-rotational and pure rotational transitions of the water molecule have resulted in the development of a variety of alternative line-profile models. These models capture more of the physics of the influence of pressure on line shapes but, in general, at the price of greater complexity. The Task Group recommends that the partially Correlated quadratic-Speed-Dependent Hard-Collision profile should be adopted as the appropriate model for high-resolution spectroscopy. For simplicity this should be called the Hartmann--Tran profile (HTP). The HTP is sophisticated enough to capture the various collisional contributions to the isolated line shape, can be computed in a straightforward and rapid manner, and reduces to simpler profiles, including the Voigt profile, under certain simplifying assumptions.

physics.optics↗

arXiv2013

ExoMol line lists II: The ro-vibrational spectrum of SiO

Accurate rotation-vibration line lists are calculated for silicon monoxide. Line lists are presented for the main isotopologue, $^{28}$Si$^{16}$O, and for four monosubsituted isotopologues ($^{29}$Si$^{16}$O, $^{30}$Si$^{16}$O, $^{28}$Si$^{18}$O and $^{28}$Si$^{17}$O), in their ground electronic states. These line lists are suitable for high temperatures (up to 9000 K) including those relevant to exoplanetary atmospheres and cool stars. A combination of empirical and \textit{ab initio} methods is used: the potential energy curves are determined to high accuracy by fitting to extensive data from the analysis of both laboratory and sunspot spectra; a high quality {\it ab initio} dipole moment curve is calculated at the large basis set, multi-reference configuration interaction level. A partition function plus full line lists of rotation-vibration transitions are made available in an electronic form as supplementary data to this article and at \url{www.exomol.com}.

astro-ph.SR↗

arXiv2012

Line strengths and updated molecular constants for the C2 Swan system

New rotational line strengths for the C2 Swan system have been calculated for vibrational bands with v'=0-10 and v"=0-9, and J values up to J=34-96, based on previous observations in 30 vibrational bands. Line positions from several sources were combined with the results from recent deperturbation studies of the v'=4 and v'=6 states, and a weighted global least squares fit was performed. We report the updated molecular constants. The line strengths are based on a recent ab initio calculation of the transition dipole moment function. A line list has been made available, including observed and calculated line positions, Einstein A coefficients and oscillator strengths (f-values). The line list will be useful for astronomers and combustion scientists who utilize C2 Swan spectra. Einstein A coefficients and f-values were also calculated for the vibrational bands of the Swan system.

astro-ph.SR↗

arXiv2012

Division Xii/commission 14/WORKING Group on Molecular Data

The current report covers the period from the second half of 2003 to the first half of 2011, bringing the Working Group's efforts up to date, and is divided into three main sections covering rotational, vibrational, and electronic spectroscopy. Rather than being exhaustive, space limitations only allow us to highlight a representative sample of work on molecular spectra. Related research on collisions, reactions on grain surfaces, and astrochemistry appear in the report by another Working Group. These also recount recent conferences and workshops on molecular astrophysics.

astro-ph.SR↗

arXiv2009

Molecular astronomy of cool stars and sub-stellar objects

The optical and infrared spectra of a wide variety of `cool' astronomical objects including the Sun, sunspots, K-, M- and S-type stars, carbon stars, brown dwarfs and extrasolar planets are reviewed. The review provides the necessary astronomical background for chemical physicists to understand and appreciate the unique molecular environments found in astronomy. The calculation of molecular opacities needed to simulate the observed spectral energy distributions is discussed.

astro-ph.SR↗