Quantum astrochemical spectroscopy

Fortenberry, Ryan C.

doi:10.1002/qua.25180

Cited by 71 publications

(44 citation statements)

References 124 publications

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“…However, the spectral data set is still somewhat incomplete, and additional corroboration for the known theoretical or even experimental data would give astronomers more trust in utilizing theoretical data for comparison to interstellar spectra. Such theoretically derived spectroscopic constants have been utilized in the detection of C 5 N − (Cernicharo et al 2008), and forced the community to provide more accurate experiments and theoretical results in the detection of C 3 H + (Pety et al 2012;Fortenberry et al 2013;Huang et al 2013b;Botschwina et al 2014;Brünken et al 2014;McGuire et al 2014;Fortenberry 2017). In any case, this work will utilize such theoretical approaches to provide the necessary rovibrational data for the HSS radical.…”

Section: Introductionmentioning

confidence: 99%

On the Detectability of the HSS, HSO, and HOS Radicals in the Interstellar Medium

Fortenberry

Francisco

2017

ApJ

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HSS has yet to be observed in the gas phase in the interstellar medium (ISM). HSS has been observed in cometary material and in high abundance. However, its agglomeration to such bodies or dispersal from them has not been observed. Similarly, HSO and HOS have not been observed in the ISM, either, even though models support their formation from reactions of known sulfur monoxide and hydrogen molecules, among other pathways. Consequently, this work provides high-level, quantum chemical rovibrational spectroscopic constants and vibrational frequencies in order to assist in interstellar searches for these radical molecules. Furthermore, the HSO −HOS isomerization energy is determined to be 3.63 kcal mol −1 , in line with previous work, and the dipole moment of HOS is 36% larger at 3.87 D than HSO, making the less stable isomer more rotationally intense. Finally, the S−S bond strength in HSS is shown to be relatively weak at 30% of the typical disulfide bond energy. Consequently, HSS may degrade into SH and sulfur atoms, making any ISM abundance of HSS likely fairly low, as recent interstellar surveys have observed.

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Section: Introductionmentioning

confidence: 99%

On the Detectability of the HSS, HSO, and HOS Radicals in the Interstellar Medium

Fortenberry

Francisco

2017

ApJ

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“…2,3,8 Its proton affinity is larger than that of atomic hydrogen, indicating that ionized argon could produce ArH + in clouds of atomic hydrogen without dissociating. 9,11,12 Additionally, the dissociation of argonium is remarkably slow allowing for it to exist longer than either of the predicted HeH + or NeH + molecules. Consequently, ArH + has been suggested as a tracer for interstellar atomic gas.…”

Section: Introductionmentioning

confidence: 99%

Formation of Potential Interstellar Noble Gas Molecules in Gas and Adsorbed Phases

Filipek

Fortenberry

2016

ACS Omega

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The discovery of naturally occurring ArH + in various regions of the interstellar medium has shown the need for more understanding of the reactions that lead to covalently bonded noble gas molecules. The test comes with trying to predict the formation of other small noble gas molecules. Many molecules have been observed in various interstellar environments, which possess the possibility of bonding with noble gases. This work explores how both argon and neon can form bonds to ligands made of these species through quantum chemical computations. Argon and neon are chosen as they are among the most abundant atoms in the universe but are more polarizable than the more common but smaller helium atom. Reactions leading to noble gas molecules are modeled in the gas phase as well as through the adsorbed phase by catalysis with a polycyclic aromatic hydrocarbon (PAH) surface. The adsorption energy of the neutral noble gas atoms to the surface increases as the size of the PAH also increases but this is still less than 10 kcal/mol. It is proposed and supported herein that an incoming molecule can bond with the noble gas atom adsorbed onto the PAH, form a stable structure, and allow the PAH to function as the leaving group. This work shows that the noble gas molecules ArCCH + , ArOH + , ArNH + , and NeCCH + are not only stable minima on their respective potential energy surfaces but also can be formed in either the gas phase or through PAH adsorption with known or hypothesized interstellar molecules. Most notably, NeCCH + does not appear to form in the gas phase but could be catalyzed on PAH surfaces. Hence, the interstellar detection of such molecules could also serve as a probe for the observation of interstellar PAHs.

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“…Computationally, the C 2 P radical also has 2ν 3 = ν 2 and 2ν 2 = ν 1 type-1 Fermi resonances included in the analysis for completeness, even though the estimated perturbations are less than 1.0 cm 1 . The CcCR method [53][54][55][56] has produced experimentally comparable vibrational frequencies to better than 1.0 cm 1 of TABLE II. The observed peaks, their binding energies (BEs), shifts (∆E) relative to the 0-0 transition (peak X), and assignments for the photoelectron spectra of C 2 P .…”

Section: Methodsmentioning

confidence: 96%

A high-resolution photoelectron imaging and theoretical study of CP− and C2P−

Czekner

Cheung

Johnson

et al. 2018

The Journal of Chemical Physics

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The discovery of interstellar anions has been a milestone in astrochemistry. In the search for new interstellar anions, CP and CP are viable candidates since their corresponding neutrals have already been detected astronomically. However, scarce data exist for these negatively charged species. Here we report the electron affinities of CP and CP along with the vibrational frequencies of their anions using high-resolution photoelectron imaging. These results along with previous spectroscopic data of the neutral species are used further to benchmark very accurate quartic force field quantum chemical methods that are applied to CP, CP, CP, and two electronic states of CP. The predicted electron affinities, vibrational frequencies, and rotational constants are in excellent agreement with the experimental data. The electron affinities of CP (2.8508 ± 0.0007 eV) and CP (2.6328 ± 0.0006 eV) are measured accurately and found to be quite high, suggesting that the CP and CP anions are thermodynamically stable and possibly observable. The current study suggests that the combination of high-resolution photoelectron imaging and quantum chemistry can be used to determine accurate molecular constants for exotic radical species of astronomical interest.

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Quantum astrochemical spectroscopy

Cited by 71 publications

References 124 publications

On the Detectability of the HSS, HSO, and HOS Radicals in the Interstellar Medium

On the Detectability of the HSS, HSO, and HOS Radicals in the Interstellar Medium

Formation of Potential Interstellar Noble Gas Molecules in Gas and Adsorbed Phases

A high-resolution photoelectron imaging and theoretical study of CP− and C2P−

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