Physical Sciences and Mathematics Commons^™

State-To-State Rate Coefficients For Hcs+In Rotationally Inelastic Collisions With H2at Low Temperatures, Otoniel Denis-Alpizar, Ernesto Quintas-Sánchez, Richard Dawes

Chemistry Faculty Research & Creative Works

HCS⁺ ions have been detected in several regions of the interstellar medium (ISM), but an accurate determination of the chemical-physical conditions in the molecular clouds where this molecule is observed requires detailed knowledge of the collisional rate coefficients with the most common colliders in those environments. In this work, we study the dynamics of rotationally inelastic collisions of HCS⁺ + H₂ at low temperature, and report, for the first time, a set of rate coefficients for this system. We used a recently developed potential energy surface for the HCS⁺-H₂ van der Waals complex and …

Inelastic, Exchange, And Reactive Processes In Rovibrationally Excited Collisions Of Hd With H, Boyi Zhou, Benhui Yang, Balakrishnan Naduvalath, B. K. Kendrick, Maodu Chen, P. C. Stancil

Chemistry and Biochemistry Faculty Research

The HD molecule is an important coolant in early universe chemistry models and a tracer of H2 in star-forming regions. Rate coefficients for collisional excitation and de-excitation of HD rotational and vibrational levels form important ingredients in astrophysical models. While collisions with He, H2, and H are the most important, available data for H + HD collisions are largely limited to temperatures less than 1000 K for the vibrational ground state, low-lying rotational levels of the v = 1 HD vibrational level, or computed without reactive contributions. Here, through explicit quantum scattering calculations, we report extensive data for rovibrational transitions …

Cf⁺ Excitation In The Interstellar Medium, Benjamin Desrousseaux, François Lique, Javier R. Goicoechea, Ernesto Quintas-Sánchez, Richard Dawes

Chemistry Faculty Research & Creative Works

The detection of CF⁺ in interstellar clouds potentially allows astronomers to infer the elemental fluorine abundance and the ionization fraction in ultraviolet-illuminated molecular gas. Because local thermodynamic equilibrium (LTE) conditions are hardly fulfilled in the interstellar medium (ISM), the accurate determination of the CF⁺ abundance requires one to model its non-LTE excitation via both radiative and collisional processes. Here, we report quantum calculations of rate coefficients for the rotational excitation of CF⁺ in collisions with para- and ortho-H₂ (for temperatures up to 150 K). As an application, we present non-LTE excitation models that reveal population inversion …

Rotational Quenching Of Hd Induced By Collisions With H2 Molecules, Yier Wan, Nadulvalath Balakrishnan, B. H. Yang, R. C. Forrey, P. C. Stancil

Chemistry and Biochemistry Faculty Research

Rate coefficients for rotational transitions in HD induced by H2 impact for rotational levels of HD j ≤ 8 and temperatures 10 K ≤ T ≤ 5000 K are reported. The quantum mechanical close-coupling (CC) method and the coupled-states (CS) decoupling approximation are used to obtain the cross-sections employing the most recent highly accurate H2–H2 potential energy surface (PES). Our results are in good agreement with previous calculations for low-lying rotational transitions The cooling efficiency of HD compared with H2 and astrophysical applications are briefly discussed.

Exomol Line List - Xxxiv. A Rovibrational Line List For Phosphinidene (Ph) In Its X³Σ¯ And A¹Δ Electronic States, Jonathan Langleben, Jonathan Tennyson, Sergei N. Yurchenko, Peter Bernath

Chemistry & Biochemistry Faculty Publications

A rovibronic line list for the ground (X³Σ⁻) and first excited (a¹Δ) states of phosphinidene, ³¹PH, is computed. The line list is designed for studies of exoplanetary and cool stellar atmospheres with temperatures up to 4000 K. A combination of empirical and ab initio data is used to produce the line list: potential energy curves (PECs) are fitted using experimental transition frequencies; these transitions are reproduced with a root mean square error of 0.01 cm⁻¹. The nuclear Schrödinger equation is solved using these PECs plus Born–Oppenheimer and spin splitting correction terms. …

Fourier Transform Spectroscopy Of The C³Δ-X³Δ Transition Of Tio In Support Of Exoplanet Spectroscopy, James N. Hodges, Peter Bernath

Chemistry & Biochemistry Faculty Publications

Recent limitations in the TiO line list used in cross-correlation detection schemes have made the detection and quantification of TiO in exoplanetary atmospheres challenging. The quality of the line list appears to degrade at wavelengths shorter than 630 nm. The C³Δ-X³Δ electronic transition has strong rovibronic bands near 500 nm. In an effort to improve the line list, a spectrum of TiO in a furnace at 1950 K is analyzed, and the assigned lines of the C³Δ-X³Δ transition are fit with the N² Hamiltonian in the molecular spectrum fitting software, _{PGOPHER …}

Collisional Quenching Of Highly Excited H2 Due To H2 Collisions, Yier Wan, B. H. Yang, P. C. Stancil, Balakrishnan Naduvalath, Nikhil J. Parekh, R. C. Forrey

Chemistry and Biochemistry Faculty Research

Rate coefficients for pure rotational quenching in H2(ν 1 = 0, j 1) + H2(ν 2 = 0, j 2) collisions from initial levels of j 1 = 2–31 (j 2 = 0 or 1) to all lower rotational levels are presented. We carried out extensive quantum mechanical close-coupling calculations based on a recently published H2–H2 potential energy surface (PES) developed by Patkowski et al. that has been demonstrated to be more reliable than previous work. Rotational transition cross sections with initial levels of j 1 = 2–14, 18, 19, 24, and 25 were computed for energies ranging from 10−6 …

Spectroscopic Constants And Line Positions For Tio Singlet States, Dror M. Bittner, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

consistent set of spectroscopic constants for the a¹Δ,d¹Σ⁺,b¹Π,c¹Φ, and f¹Δ states of ⁴⁸Ti¹⁶O has been determined from analysis of the b¹Π–a¹Δ,b¹Π–d¹Σ⁺,c¹Φ–a¹Δ, and f¹Δ–a¹Δ systems. Three Fourier transform emission spectra have been used for the analysis. New bands of the b¹Π–a¹Δ and c¹Φ–a¹Δ systems have been fitted. The first analysis of the c¹Φ–a¹Δ system using Fourier …

Improved Ultraviolet And Infrared Oscillator Strengths For Oh+, James N. Hodges, Dror M. Bittner, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

Molecular ions are key reaction intermediates in the interstellar medium. OH⁺ plays a central role in the formation of more complex chemical species and for estimating the cosmic ray ionization rate in astrophysical environments. Here, we use a recent analysis of a laboratory spectrum in conjunction with ab initio methods to calculate infrared and ultraviolet oscillator strengths. These new oscillator strengths include branch dependent intensity corrections, arising from the Herman–Wallis effect, that have not been included before. We estimate 10% total uncertainty in the UV and 6% total uncertainty in the IR for the oscillator strengths.

Line Lists For Lif And Licl In The X1Σ+ Ground State, Dror M. Bittner, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

Vibration–rotation line lists for ⁶LiF, ⁷LiF, ⁶Li³⁵Cl, ⁶Li³⁷Cl, ⁷Li³⁵Cl, and ⁷Li³⁷Cl in the X¹Σ⁺ ground states have been prepared. The rovibrational energy levels have been calculated using potential energy surfaces determined by direct potential-fitting employing the rotational and rovibrational transition frequencies of all isotopologues, and required the inclusion of Born–Oppenheimer breakdown terms. Dipole moment functions calculated ab initio at the MRCI/aug-cc-pwCV5Z level have been used for line strength calculations. Partition functions for temperatures up to 5000 K have been calculated. LiF and LiCl …

Fourier Transform Spectroscopy Of The A3Π–X3Σ− Transition Of Oh+, James N. Hodges, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

The OH⁺ ion is of critical importance to the chemistry in the interstellar medium and is a prerequisite for the generation of more complex chemical species. Submillimeter and ultraviolet observations rely on high quality laboratory spectra. Recent measurements of the fundamental vibrational band and previously unanalyzed Fourier transform spectra of the near-ultraviolet A³Π-X 3Σ^- electronic spectrum, acquired at the National Solar Observatory at Kitt Peak in 1989, provide an excellent opportunity to perform a global fit of the available data. These new optical data are approximately four times more precise as compared to the previous values. …

Experimental Energy Levels And Partition Function Of The 12c2 Molecule, Tibor Furtenbacher, István Szabó, Attila G. Császár, Peter F. Bernath, Sergei N. Yurchenko, Jonathan Tennyson

Chemistry & Biochemistry Faculty Publications

The carbon dimer, the ¹²C₂ molecule, is ubiquitous in astronomical environments. Experimental-quality rovibronic energy levels are reported for ¹²C₂, 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 5699 rovibronic energy levels, 1325, 4309, 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 …

Stout: Cloudy's Atomic And Molecular Database, Matt L. Lykins, Gary J. Ferland, R. Kisielius, Marios Chatzikos, R. L. Porter, P. A. M. Van Hoof, R. J. R. Williams, F. P. Keenan, P. C. Stancil

Physics and Astronomy Faculty Publications

We describe a new atomic and molecular database we developed for use in the spectral synthesis code Cloudy. The design of Stout is driven by the data needs of Cloudy, which simulates molecular, atomic, and ionized gas with kinetic temperatures 2.8 K < T <10¹⁰ K and densities spanning the low-to high-density limits. The radiation field between photon energies 10⁻⁸ Ry and 100 MeV is considered, along with all atoms and ions of the lightest 30 elements, and ~10² molecules. For ease of maintenance, the data are stored in a format as close as possible to the original data …

Small Carbon Chains In Circumstellar Envelopes, R. J. Hargreaves, K. Hinkle, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

Observations of carbon-rich circumstellar envelopes were made using the Phoenix spectrograph on the Gemini South telescope to determine the abundance of small carbon chain molecules. Vibration-rotation lines of the ν3 antisymmetric stretch of C₃ near 2040 cm^-1 (4.902 μm) have been used to determine the column density for four carbon-rich circumstellar envelopes: CRL 865, CRL 1922, CRL 2023 and IRC +10216. We additionally calculate the column density of C₅ for IRC +10216, and provide an upper limit for five more objects. An upper limit estimate for the C₇ column density is also provided for IRC+10216. A …

Line Lists For The A2Π-X 2Σ+ (Red) And B2Σ+-X 2Σ+ (Violet) Systems Of Cn, 13c14n, And 12c15n, And Application To Astronomicalspectra, Christopher Sneden, Sara Lucatello, Ram S. Ram, James S. A. Brooke, Peter Bernath

Chemistry & Biochemistry Faculty Publications

New red and violet system line lists for the CN isotopologues ¹³C¹⁴N and ¹²C¹⁵N have been generated. These new transition data are combined with those previously derived for ¹²C¹⁴N, and applied to the determination of CNO abundances in the solar photosphere and in four red giant stars: Arcturus, the bright, very low-metallicity star HD 122563, and the carbon-enhanced metal-poor stars HD 196944 and HD 201626. When both red and violet system lines are detectable in a star, their derived N abundances are in good agreement. The mean N abundances determined in …

Improved Line Data For The Swan System 12c13c Isotopologue, Ram S. Ram, James S. A. Brooke, Peter F. Bernath, Christopher Sneden, Sara Lucatello

Chemistry & Biochemistry Faculty Publications

We present new, accurate predictions for rotational line positions, excitation energies, and transition probabilities of the ¹²C ¹³C isotopologue Swan d³Π-a³Π system 0-0, 0-1, 0-2, 1-0, 1-1, 1-2, 2-0, 2-1, and 2-2 vibrational bands. The line positions and energy levels were predicted through new analyses of published laboratory data for the ¹²C¹³C lines. Transition probabilities were derived from recent computations of transition dipole moments and related quantities. The ¹²C¹³C line data were combined with similar data for ¹²C₂, reported in a companion paper, and applied …

Einstein A Coefficients And Oscillator Strengths For The A 2Π-X2Σ+ (Red) And B 2Σ+-X2Σ+ (Violet) Systems And Rovibrational Transitions In The X2Σ+ State Of Cn, James S. A. Brooke, Ram S. Ram, Colin M. Western, Gang Li, David W. Schwenke, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

Line strengths have been calculated in the form of Einstein A coefficients and f-values for a large number of bands of the A ²Π-X ²Σ⁺ and B ²Σ⁺-X ²Σ⁺ systems and rovibrational transitions within the X ²Σ⁺ state of CN using Western's PGOPHER program. The J dependence of the transition dipole moment matrix elements (the Herman-Wallis effect) has been taken into account. Rydberg-Klein-Rees potential energy functions for the A ²Π, B ²Σ⁺ , and X ²Σ⁺ states were computed using spectroscopic constants from the …

Exomol Molecular Line Lists V: The Ro-Vibrational Spectra Of Nacl And Kcl, Emma J. Barton, Christopher Chiu, Shirin Golpayegani, Sergei N. Yurchenko, Jonathan Tennyson, Daniel J. Frohman, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

Accurate rotation-vibration line lists for two molecules, NaCl and KCl, in their ground electronic states are presented. These line lists are suitable for temperatures relevant to exoplanetary atmospheres and cool stars (up to 3000 K). Isotopologues ²³Na³⁵Cl, ²³Na³⁷Cl, ³⁹K³⁵Cl, ³⁹K³⁷Cl, ⁴¹K³⁵Cl and ⁴¹K³⁷Cl are considered. Laboratory data were used to refine ab initio potential energy curves in order to compute accurate ro-vibrational energy levels. Einstein A coefficients are generated using newly determined ab initio dipole moment curves calculated using the CCSD(T) method. …

The Magnesium Isotopologues Of Mgh In The A2Π-X 2Σ+ System, Kenneth H. Hinkle, Lloyd Wallace, Ram S. Ram, Peter F. Bernath, Christopher Sneden, Sara Lucatello

Chemistry & Biochemistry Faculty Publications

Using laboratory hollow cathode spectra we have identified lines of the less common magnesium isotopologues of MgH, ²⁵MgH and ²⁶MgH, in the A²Π-X²Σ⁺ system. Based on the previous analysis of ²⁴MgH, molecular lines have been measured and molecular constants derived for ²⁵MgH and ²⁶MgH. Term values and linelists, in both wavenumber and wavelength units, are presented. The A²Π-X²Σ⁺ system of MgH is important for measuring the magnesium isotope ratios in stars. Examples of analysis using the new linelists to derive the Mg isotope ratio in …

Basecol2012: A Collisional Database Repository And Web Service Within The Virtual Atomic And Molecular Data Centre (Vamdc), M.-L Duberne, M. H. Alexander, Y. A. Ba, N. Balakrishnan, C. Balança, C. Ceccarelli, J. Cernicharo, F. Daniel, F. Dayou, M. Doronin, F. Dumouchel, A. Faure, N. Feautrier, D. R. Flower, A. Grosjean, P. Halvick, J. Kłos, F. Lique, G. C. Mcbane, S. Marinakis, N. Moreau, R. Moszynsk, D. A. Neufeld, E. Roueff, P Schilke, A. Spielfiedel, P. C. Stancil, T. Stoecklin, J. Tennyson, B. Yang, A.-M. Vasserot, L. Wiesenfeld

Peer Reviewed Articles

The BASECOL2012 database is a repository of collisional data and a web service within the Virtual Atomic and Molecular Data Centre (VAMDC, http://www.vamdc.eu). It contains rate coefficients for the collisional excitation of rotational, ro-vibrational, vibrational, fine, and hyperfine levels of molecules by atoms, molecules, and electrons, as well as fine-structure excitation of some atoms that are relevant to interstellar and circumstellar astrophysical applications. Submissions of new published collisional rate coefficients sets are welcome, and they will be critically evaluated before inclusion in the database. In addition, BASECOL2012 provides spectroscopic data queried dynamically from various spectroscopic databases using the VAMDC technology. …

Einstein A Coefficients For Rovibronic Lines Of The A2Π → X2Σ+ And B'2Σ+ → X 2Σ+ Transitions Of Mgh, Ehsan Gharibnezhad, Alireza Ahayesteh, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

Einstein A coefficients have been calculated for rovibronic lines of the A²Π →X²Σ⁺ and B'²Σ⁺ →X²Σ⁺ transitions of 24MgH. Using the experimentally determined analytic potential energy curve for the X²Σ⁺ state, and the Rydberg-Klein-Rees potentials for the A²Π and B'²Σ⁺ states, combined with the most recent ab initio transition dipole moments, rovibronic transition moments were computed. The rovibronic transition frequencies were obtained accurately by subtracting the published term values of the X²Σ⁺, A²Π and B' …

Nature Of The Gas And Dust Around 51 Oph, W F. Thi, F Menard, G Meeus, A Carmona, P Riviere-Marichalar, J C. Augereau, I Kamp, P Woitke, C Pinte, I Mendigutia, C Eiroa, B Montesinos, Sean D. Brittain, W Dent

Publications

Circumstellar disc evolution is paramount for the understanding of planet formation. The GASPS program aims at determining the circumstellar gas and solid mass around ~250 pre-main-sequence Herbig Ae and TTauri stars. We aim to understand the origin and nature of the circumstellar matter orbiting 51 Oph, a young (Myr) luminous B9.5 star. We obtained continuum and line observations with the PACS instrument on board the Herschel Space Observatory and continuum data at 1.2 mm with the IRAM 30m telescope. The SED and line fluxes were modelled using the physico-chemo radiative transfer code ProDiMo. We detected a strong emission by OI …

Hot Methane Line Lists For Exoplanet And Brown Dwarf Atmospheres, Robert J. Hargreaves, Christopher A. Beale, Laurent Michaux, Melis Irfan, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

We present comprehensive experimental line lists of methane (CH₄) at high temperatures obtained by recording Fourier transform infrared emission spectra. Calibrated line lists are presented for the temperatures 300-1400°C at twelve 100°C intervals spanning the 960-5000 cm^-1 (2.0-10.4 μm) region of the infrared. This range encompasses the dyad, pentad, and octad regions, i.e., all fundamental vibrational modes along with a number of combination, overtone and hot bands. Using our CH₄ spectra, we have estimated empirical lower state energies (E_low in cm^-1) and our values have been incorporated into the line lists along …

On The Electronic Spectroscopy Of Closed Shell Cations Derived From Resonance Stabilized Radicals: Insights From Theory And Franck-Condon Analysis, T. P. Troy, S. H. Kable, T. W. Schmidt, Scott Reid

Chemistry Faculty Research and Publications

Context. Recent attention has been directed on closed-shell aromatic cations as potential carriers of the diffuse interstellar bands. The spectra of mass-selected, matrix-isolated benzylium, and tropylium cations were recently reported. The visible spectrum of benzylium exhibits a large Franck-Condon (FC) envelope, inconsistent with diffuse interstellar band carriers.

Aims. We perform a computational analysis of the experimentally studied benzylium spectrum before extending the methods to a range of larger, closed-shell aromatic cations to determine the potential for this class of systems as diffuse interstellar band carriers.

Methods. Density functional theory (DFT), time-dependent ((TD)DFT), and multi-configurational self-consistent field second-order perturbation theory (MRPT2) …

Rovibrationally Resolved Direct Photodissociation Through The Lyman And Werner Transitions Of H2 For Fuv/X-Ray-Irradiated Environments, C. D. Gay, N. P. Abel, R. L. Porter, P. C. Stancil, Gary J. Ferland, G. Shaw, P. A. M. Vanhoof, R. J. R. Williams

Physics and Astronomy Faculty Publications

Using ab initio potential curves and dipole transition moments, cross-section calculations were performed for the direct continuum photodissociation of H2 through the B¹Σ⁺u ← X¹Σ⁺_g (Lyman) and C¹Π_u ← X¹Σ⁺_g (Werner) transitions. Partial cross-sections were obtained for wavelengths from 100 Å to the dissociation threshold between the upper electronic state and each of the 301 bound rovibrational levels v''J'' within the ground electronic state. The resulting cross-sections are incorporated into three representative classes of interstellar gas models: diffuse clouds, photon-dominated regions, and …

Discovery Of Co Gas In The Inner Disk Of Tw Hydrae, Terrence W. Rettig, Joe Haywood, Theodore Simon, Sean D. Brittain, Erika Gibb

Publications

We report the detection of rovibrationally excited CO emission from the inner disk of the classical T Tauri star (cTTS) TW Hya. We observe ~6 × 1021 g of CO gas with a rotational temperature of 430 ± 40 K. The linearity of the excitation plot suggests that the CO is optically thin. Atypical for cTTSs, hot CO was not detected, implying that TW Hya has cleared its inner disk region out to a radial distance of ~0.5 AU. We discuss implications for the structure of the disk as it relates to replenishment and planet formation.