Search

The searches for CP violating effects in diatomic molecules, such as $\text{HfF}^+$ and ThO, are typically interpreted as a probe of the electron's electric dipole moment ($e\text{EDM}$), a new electron-nucleon interaction, and a new electron-electron interaction. However, in the case of a non-vanishing nuclear spin, a new CP violating nucleon-nucleon long range force will also affect the measurement. Here, we use the $\text{HfF}^+$ $e\text{EDM}$ search and derive a new bound on this hypothetical interaction, which is the most stringent from terrestrial experiments in the 1 eV-10 keV mass range. These multiple new physics sources motivate independent searches in different molecular species for CP violation at low energy that result in model independent bounds, which are insensitive to cancellation among them., Comment: 9 pages, 4 figures

Ergodicity, the central tenet of statistical mechanics, requires that an isolated system will explore all of its available phase space permitted by energetic and symmetry constraints. Mechanisms for violating ergodicity are of great interest for probing non-equilibrium matter and for protecting quantum coherence in complex systems. For decades, polyatomic molecules have served as an intriguing and challenging platform for probing ergodicity breaking in vibrational energy transport, particularly in the context of controlling chemical reactions. Here, we report the observation of rotational ergodicity breaking in an unprecedentedly large and symmetric molecule, 12C60. This is facilitated by the first ever observation of icosahedral ro-vibrational fine structure in any physical system, first predicted for 12C60 in 1986. The ergodicity breaking exhibits several surprising features: first, there are multiple transitions between ergodic and non-ergodic regimes as the total angular momentum is increased, and second, they occur well below the traditional vibrational ergodicity threshold. These peculiar dynamics result from the molecules' unique combination of symmetry, size, and rigidity, highlighting the potential of fullerenes to uncover emergent phenomena in mesoscopic quantum systems.

We report the detection of the lowest energy conformer of $E$-1-cyano-1,3-butadiene ($E$-1-C$_4$H$_5$CN), a linear isomer of pyridine, using the fourth data reduction of the GOTHAM deep spectral survey toward TMC-1 with the 100 m Green Bank Telescope. We performed velocity stacking and matched filter analyses using Markov chain Monte Carlo simulations and find evidence for the presence of this molecule at the 5.1$\sigma$ level. We derive a total column density of $3.8^{+1.0}_{-0.9}\times 10^{10}$ cm$^{-2}$, which is predominantly found toward two of the four velocity components we observe toward TMC-1. We use this molecule as a proxy for constraining the gas-phase abundance of the apolar hydrocarbon 1,3-butadiene. Based on the three-phase astrochemical modeling code NAUTILUS and an expanded chemical network, our model underestimates the abundance of cyano-1,3-butadiene by a factor of 19, with a peak column density of $2.34 \times 10^{10}\ \mathrm{cm}^{-2}$ for 1,3-butadiene. Compared to the modeling results obtained in previous GOTHAM analyses, the abundance of 1,3-butadiene is increased by about two orders of magnitude. Despite this increase, the modeled abundances of aromatic species do not appear to change and remain underestimated by 1--4 orders of magnitude. Meanwhile, the abundances of the five-membered ring molecules increase proportionally with 1,3-butadiene by two orders of magnitudes. We discuss implications for bottom-up formation routes to aromatic and polycyclic aromatic molecules.

Using data from the GOTHAM (GBT Observations of TMC-1: Hunting for Aromatic Molecules) survey, we report the first astronomical detection of the C10H- anion. The astronomical observations also provided the necessary data to refine the spectroscopic parameters of C10H-. From the velocity stacked data and the matched filter response, C10H- is detected at >9{\sigma} confidence level at a column density of 4.04e11 cm-2. A dedicated search for the C10H radical was also conducted towards TMC-1. In this case, the stacked molecular emission of C10H was detected at a ~3.2{\sigma} confidence interval at a column density of 2.02e11 cm-2. However, since the determined confidence level is currently <5{\sigma}, we consider the identification of C10H as tentative. The full GOTHAM dataset was also used to better characterize the physical parameters including column density, excitation temperature, linewidth, and source size for the C4H, C6H and C8H radicals and their respective anions, and the measured column densities were compared to the predictions from a gas/grain chemical formation model and from a machine learning analysis. Given the measured values, the C10H-/C10H column density ratio is ~2.0 - the highest value measured between an anion and neutral species to date. Such a high ratio is at odds with current theories for interstellar anion chemistry. For the radical species, both models can reproduce the measured abundances found from the survey; however, the machine learning analysis matches the detected anion abundances much better than the gas/grain chemical model, suggesting that the current understanding of the formation chemistry of molecular anions is still highly uncertain., Comment: 38 Pages, 24 Figures, 12 Tables, 8 Appendices

We present laboratory rotational spectroscopy of five isomers of cyanoindene (2-, 4-, 5-, 6-, and 7-cyanoindene) using a cavity Fourier-transform microwave spectrometer operating between 6-40 GHz. Based on these measurements, we report the detection of 2-cyanoindene (1H-indene-2-carbonitrile; 2-C$_9$H$_7$CN) in GOTHAM line survey observations of the dark molecular cloud TMC-1 using the Green Bank Telescope at centimeter wavelengths. Using a combination of Markov Chain Monte Carlo (MCMC), spectral stacking, and matched filtering techniques, we find evidence for the presence of this molecule at the 6.3$\sigma$ level. This provides the first direct observation of the ratio of a cyano-substituted polycyclic aromatic hydrocarbon (PAH) to its pure hydrocarbon counterpart, in this case indene, in the same source. We discuss the possible formation chemistry of this species, including why we have only detected one of the isomers in TMC-1. We then examine the overall hydrocarbon:CN-substituted ratio across this and other simpler species, as well as compare to those ratios predicted by astrochemical models. We conclude that while astrochemical models are not yet sufficiently accurate to reproduce absolute abundances of these species, they do a good job at predicting the ratios of hydrocarbon:CN-substituted species, further solidifying -CN tagged species as excellent proxies for their fully-symmetric counterparts., Comment: Accepted in ApJL

Molecular electronic spectra can be represented in the time domain as auto-correlation functions of the initial vibrational wavepacket. We present a derivation of the harmonic vibrational auto-correlation function that is valid for both real and imaginary harmonic frequencies. The derivation rests on Lie algebra techniques that map otherwise complicated exponential operator arithmetic to simpler matrix formulae. The expressions for the zero- and finite-temperature harmonic auto-correlation functions have been carefully structured both to be free of branch-cut discontinuities and to remain numerically stable with finite-precision arithmetic. Simple extensions correct the harmonic Franck-Condon approximation for the lowest-order anharmonic and Herzberg-Teller effects. Quantitative simulations are shown for several examples, including the electronic absorption spectra of F$_2$, HOCl, CH$_2$NH, and NO$_2$., Comment: 34 pages, 4 figures

Quantum state-resolved spectroscopy was recently achieved for C60 molecules when cooled by buffer gas collisions and probed with a midinfrared frequency comb. This rovibrational quantum state resolution for the largest molecule on record is facilitated by the remarkable symmetry and rigidity of C60, which also present new opportunities and challenges to explore energy transfer between quantum states in this many-atom system. Here we combine state-specific optical pumping, buffer gas collisions, and ultrasensitive intracavity nonlinear spectroscopy to initiate and probe the rotation-vibration energy transfer and relaxation. This approach provides the first detailed characterization of C60 collisional energy transfer for a variety of collision partners, and determines the rotational and vibrational inelastic collision cross sections. These results compare well with our theoretical modeling of the collisions, and establish a route towards quantum state control of a new class of unprecedentedly large molecules.

We have conducted an extensive search for nitrogen-, oxygen- and sulfur-bearing heterocycles toward Taurus Molecular Cloud 1 (TMC-1) using the deep, broadband centimeter-wavelength spectral line survey of the region from the GOTHAM large project on the Green Bank Telescope. Despite their ubiquity in terrestrial chemistry, and the confirmed presence of a number of cyclic and polycyclic hydrocarbon species in the source, we find no evidence for the presence of any heterocyclic species. Here, we report the derived upper limits on the column densities of these molecules obtained by Markov Chain Monte Carlo (MCMC) analysis and compare this approach to traditional single-line upper limit measurements. We further hypothesize why these molecules are absent in our data, how they might form in interstellar space, and the nature of observations that would be needed to secure their detection., Comment: Accepted in the Journal of Physical Chemistry A

We discuss the detection of 14 rovibrational lines of CH$^+$, obtained with the iSHELL spectrograph on NASA's Infrared Telescope Facility (IRTF) on Maunakea. Our observations in the 3.49 - 4.13 $\mu$m spectral region, obtained with a 0.375" slit width that provided a spectral resolving power $\lambda/\Delta \lambda \sim 80,000$, have resulted in the unequivocal detection of the $R(0) - R(3)$ and $P(1)-P(10)$ transitions within the $v=1-0$ band of CH$^+$. The $R$-branch transitions are anomalously weak relative to the $P$-branch transitions, a behavior that is explained accurately by rovibronic calculations of the transition dipole moment reported in a companion paper (Changala et al. 2021). Nine infrared transitions of H$_2$ were also detected in these observations, comprising the $S(8)$, $S(9)$, $S(13)$ and $S(15)$ pure rotational lines; the $v=1-0$ $O(4) - O(7)$ lines, and the $v=2-1$ $O(5)$ line. We present a photodissociation region model, constrained by the CH$^+$ and H$_2$ line fluxes that we measured, that includes a detailed treatment of the excitation of CH$^+$ by inelastic collisions, optical pumping, and chemical ("formation") pumping. The latter process is found to dominate the excitation of the observed rovibrational lines of CH$^+$, and the model is remarkably successful in explaining both the absolute and relative strengths of the CH$^+$ and H$_2$ lines., Comment: 38 pages, 15 figures, accepted for publication in the Astrophysical Journal

The unusual infrared emission patterns of CH$^+$, recently detected in the planetary nebula NGC 7027, are examined theoretically with high-accuracy rovibrational wavefunctions and $ab$ $initio$ dipole moment curves. The calculated transition dipole moments quantitatively reproduce the observed $J$-dependent intensity variation, which is ascribed to underlying centrifugal distortion-induced interference effects. We discuss the implications of this anomalous behavior for astrochemical modeling of CH$^+$ production and excitation, and provide a simple expression to estimate the magnitude of this effect for other light diatomic molecules with small dipole derivatives., Comment: 21 pages, 6 figures, accepted for publication in the Astrophysical Journal

Polycyclic Aromatic Hydrocarbons (PAHs) have long been invoked in the study of interstellar and protostellar sources, but the unambiguous identification of any individual PAH has proven elusive until very recently. As a result, the formation mechanisms for this important class of molecules remain poorly constrained. Here we report the first interstellar detection of a pure hydrocarbon PAH, indene (C$_9$H$_8$), as part of the GBT Observations of TMC-1: Hunting for Aromatic Molecules (GOTHAM) survey. This detection provides a new avenue for chemical inquiry, complementing the existing detections of CN-functionalized aromatic molecules. From fitting the GOTHAM observations, indene is found to be the most abundant organic ring detected in TMC-1 to date. And from astrochemical modeling with NAUTILUS, the observed abundance is greater than the model's prediction by several orders of magnitude suggesting that current formation pathways in astrochemical models are incomplete. The detection of indene in relatively high abundance implies related species such as cyanoindene, cyclopentadiene, toluene, and styrene may be detectable in dark clouds., Comment: 18 pages, 2 figures and 3 tables in the main text. 1 table and 1 figure in the Appendix. Published in The Astrophysical Journal Letters. Supplementary data available in the DataVerse entry provided in text

Breath analysis enables rapid, non-invasive diagnostics, as well as long-term monitoring, of human health through the identification and quantification of exhaled biomarkers. Here, for the first time, we demonstrate the remarkable capabilities of mid-infrared (mid-IR) cavity-enhanced direct frequency comb spectroscopy (CE-DFCS) applied to breath analysis. We simultaneously detect and monitor as a function of time four breath biomarkers - CH$_3$OH, CH$_4$, H$_2$O and HDO - as well as illustrating the feasibility of detecting at least six more (H$_2$CO, C$_2$H$_6$, OCS, C$_2$H$_4$, CS$_2$ and NH$_3$) without modifications to the experimental apparatus. We achieve ultra-high detection sensitivity at the parts-per-trillion level. This is made possible by the combination of the broadband spectral coverage of a frequency comb, the high spectral resolution afforded by the individual comb teeth, and the sensitivity enhancement resulting from a high-finesse cavity. Exploiting recent advances in frequency comb, optical coating, and photodetector technologies, we can access a large variety of biomarkers with strong carbon-hydrogen bond spectral signatures in the mid-IR.

Using radio observations with the Green Bank Telescope, evidence has now been found for a second five-membered ring in the dense cloud Taurus Molecular Cloud-1 (TMC-1). Based on additional observations of an ongoing, large-scale, high-sensitivity spectral line survey (GOTHAM) at centimeter wavelengths toward this source, we have used a combination of spectral stacking, Markov chain Monte Carlo (MCMC), and matched filtering techniques to detect 2-cyanocyclopentadiene, a low-lying isomer of 1-cyanocyclopentadiene, which was recently discovered there by the same methods. The new observational data also yields a considerably improved detection significance for the more stable isomer and evidence for several individual transitions between 23 - 32 GHz. Through our MCMC analysis, we derive total column densities of $8.3\times10^{11}$ and $1.9\times10^{11}$ cm$^{-2}$ for 1- and 2-cyanocyclopentadiene respectively, corresponding to a ratio of 4.4(6) favoring the former. The derived abundance ratios point towards a common formation pathway - most likely being cyanation of cyclopentadiene by analogy to benzonitrile., Comment: 6 pages, 3 figures and 1 table in the main text. 2 tables and 2 figures in the Appendix. Accepted for publication in The Astrophysical Journal Letters. Supplementary data available in the DataVerse entry provided in text

The remarkable physical properties of buckminsterfullerene, C$_{60}$, have attracted intense research activity since its original discovery. Total quantum state resolved measurements of isolated C$_{60}$ molecules have been of particularly long-standing interest. However, such observations have to date been unsuccessful due to the difficulty in preparing cold, gas-phase C$_{60}$ in sufficiently high densities. Here we report high resolution infrared absorption spectroscopy of C$_{60}$ in the 8.5 $\mu$m spectral region. A combination of cryogenic buffer gas cooling and cavity-enhanced direct frequency comb spectroscopy has enabled the observation of quantum state resolved rovibrational transitions. Characteristic nuclear spin statistical intensity patterns provide striking confirmation of the indistinguishability of the sixty $^{12}$C atoms, while rovibrational fine structure encodes further details of the molecule's rare icosahedral symmetry. These observations establish new possibilities in the study and control of emergent complexity in finite-sized quantum systems such as fullerenes., Comment: Main text: 15 pages, 4 figures, 1 table. Supplementary Materials: 4 pages, 1 figure, 1 table

We use time-resolved direct frequency comb spectroscopy in the mid-infrared to obtain high-resolution rovibrational spectra of products produced from the OD+CO reaction. In this work, we present spectral analyses for isotopologues of the transient DOCO radicals from this reaction in the OD stretch region. The analyses were performed with aid of two different theoretical approaches based on both perturbation theory and variational calculations used for prediction of rovibrational spectra of polyatomic molecules. We discuss the advantages and challenges of our current approach for studying spectroscopy and dynamics of transient molecules., Comment: 4 figures, 3 tables

Quantitative and mechanistically-detailed kinetics of the reaction of hydroxyl radical (OH) with carbon monoxide (CO) have been a longstanding goal of contemporary chemical kinetics. This fundamental prototype reaction plays an important role in atmospheric and combustion chemistry, motivating studies for accurate determination of the reaction rate coefficient and its pressure and temperature dependence at thermal reaction conditions. This intricate dependence can be traced directly to details of the underlying dynamics (formation, isomerization, and dissociation) involving the reactive intermediates cis- and trans-HOCO, which can only be observed transiently. Using time-resolved frequency comb spectroscopy, comprehensive mechanistic elucidation of the kinetics of the isotopic analogue deuteroxyl radical (OD) with CO has been realized. By monitoring the concentrations of reactants, intermediates, and products in real-time, the branching and isomerization kinetics and absolute yields of all species in the OD+CO reaction are quantified as a function of pressure and collision partner., Comment: 19 pages, 4 figures

Time-resolved direct frequency comb spectroscopy (TRFCS) was used to study the kinetics of the deuterated analogue of the OH+CO->H+CO2 reaction, which is important for atmospheric and combustion chemistry. Complementing our recent work on quantifying the formation rate of the transient trans-DOCO radical, we report measurements of the kinetics of the activated product channel, D+CO2, at room temperature. Simultaneous measurements of the time-dependence of OD and CO2 concentrations allowed us to directly determine the formation rate, branching yield, and dependence on pressure and bath gas of the activated product. Together with the trans-DOCO formation rate, these new measurements provide absolute yields of branching channels for both products of OD+CO in the low-pressure limit., Comment: 17 pages, 5 figures

We report on the first singly-resonant (SR), synchronously pumped optical parametric oscillator (OPO) based on orientation-patterned gallium arsenide (OP-GaAs). Together with a doubly resonant (DR) degenerate OPO based on the same OP-GaAs material, the output spectra cover 3 to 6 ${\mu}$m within ~3 dB of relative power. The DR-OPO has the highest output power reported to date from a femtosecond, synchronously pumped OPO based on OP-GaAs. We discovered strong three photon absorption with a coefficient of 0.35 ${\pm}$ 0.06 cm${^3}$/GW${^2}$ for our OP-GaAs sample, which limits the output power of these OPOs as mid-IR light sources. We present a detailed study of the three photon loss on the performance of both the SR and DR-OPOs, and compare them to those without this loss mechanism.

We present a perturbative method for ab initio calculations of rotational and rovibrational effective Hamiltonians of both rigid and non-rigid molecules. Our approach is based on a curvilinear implementation of second order vibrational M{\o}ller-Plesset perturbation theory (VMP2) extended to include rotational effects via a second order contact transformation. Though more expensive, this approach is significantly more accurate than standard second order vibrational perturbation theory (VPT2) for systems that are poorly described to zeroth order by rectilinear normal mode harmonic oscillators. We apply this method and demonstrate its accuracy on two molecules: Si$_2$C, a quasilinear triatomic with significant bending anharmonicity, and CH$_3$NO$_2$, which contains a completely unhindered methyl rotor. In addition to these two examples, we discuss several key technical aspects of the method, including an efficient implementation of Eckart and quasi-Eckart frame embedding that does not rely on numerical finite differences., Comment: 15 pages, 2 figures

The kinetics of the OH + CO reaction, fundamental to both atmospheric and combustion chemistry, are complex due to the formation of the HOCO intermediate. Despite extensive studies on this reaction, HOCO has not been observed at thermal reaction conditions. Exploiting the sensitive, broadband, and high-resolution capabilities of time-resolved cavity-enhanced direct frequency comb spectroscopy, we observe OD + CO reaction kinetics with the detection of stabilized trans-DOCO, the deuterated analogue of trans-HOCO, and its yield. By simultaneously measuring the time-dependent concentrations of both trans-DOCO and OD species, we observe unambiguous low-pressure termolecular dependence on the reaction rate coefficients for both N2 and CO bath gases. These results confirm the HOCO formation mechanism and quantify its yield., Comment: 39 pages, 14 figures

Cavity-enhanced frequency comb spectroscopy for molecule detection in the mid-infrared powerfully combines high resolution, high sensitivity, and broad spectral coverage. However, this technique, and essentially all spectroscopic methods, is limited in application to relatively small, simple molecules. Here we integrate comb spectroscopy with continuous, cold samples of molecules produced via buffer gas cooling, thus enabling the study of significantly more complex molecules. We report simultaneous gains in resolution, sensitivity, and bandwidth and demonstrate this combined capability with the first rotationally resolved direct absorption spectra in the CH stretch region of several complex molecules. These include nitromethane (CH$_3$NO$_2$), a model system that presents challenging questions to the understanding of large amplitude vibrational motion, as well as several large organic molecules with fundamental spectroscopic and astrochemical relevance, including naphthalene (C$_{10}$H$_8$), adamantane (C$_{10}$H$_{16}$), and hexamethylenetetramine (C$_{6}$N$_4$H$_{12}$). This general spectroscopic tool has the potential to significantly impact the field of molecular spectroscopy, simultaneously improving efficiency, spectral resolution, and specificity by orders of magnitude. This realization could open up new molecular species and new kinetics for precise investigations, including the study of complex molecules, weakly bound clusters, and cold chemistry.