Pathways to Detection of Strongly-Bound Inorganic Species: The Vibrational and Rotational Spectral Data of AlH2OH, HMgOH, AlH2NH2, and HMgNH2

Watrous, Alexandria G.; Davis, Megan C.; Fortenberry, Ryan C.

doi:10.3389/fspas.2021.643348

Cited by 17 publications

(22 citation statements)

References 67 publications

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“…Lastly, refractory astrochemistry is an emerging area which connects interstellar chemistry with planet formation. , Understanding the role played by metals and metal-ions is expected to be critical in this field. In addition to the studies presented in refs , in the introduction, the contemporary computational work by Fortenberry and DeYonker also strongly suggests the significance of the metal-ions. − We overall urge experimental astrochemists to further probe metal/metal-ion-mediated astrochemistry, with a particular focus on Mg and Al.…”

Section: Discussionmentioning

confidence: 99%

Pathways for the Formation of Formamide, a Prebiotic Biomonomer: Metal-Ions in Interstellar Gas-Phase Chemistry

Thripati

Ramabhadran

2021

J. Phys. Chem. A

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The chemistry occurring in the interstellar medium (ISM) is an active area of contemporary research. New aspects of interstellar chemistry are getting unraveled regularly. In this context, the role of metal-ions in the chemistry occurring in the ISM is not well-studied so far. Herein, we highlight the role of metal-ions in interstellar chemistry. For this purpose, we choose the problem of gas-phase formamide formation in interstellar molecular clouds. Formamide is a key biomonomer and contains the simplest peptide [−(CO)–NH−] linkage. With its two electronegative atoms (“O” and “N”), it provides an excellent platform to probe the role of the metal-ions. The metal-ions chosen are Na+, K+, Al+, Mg+, and Mg2+all of them present in the ISM. The metal-ions are studied in three different forms as bare positively charged ions, as hydrated metal-ions co-ordinated with a molecule of water, and when the metal-ions are part of a neutral covalent molecule. With the aid of electronic structure calculations [CCSD(T) and DFT methods], we study different gas-phase pathways which result in the generation of interstellar formamide. Throughout our study, we find that metal-ions lower the barriers (with Mg+, Mg++, and Al+ offering maximal stabilization of the transition states) and facilitate the reactions. The chemical factors influencing the reactions, how we consider the putative conditions in the ISM, the astrochemical implications of this study, and its connection with terrestrial prebiotic chemistry and refractory astrochemistry are subsequently presented. Based on our results, we also recommend the detection of two new closed-shell molecules, NH2CH2OH (aminomethanol) and CH2NH2 + (iminium ion), and two open-shell molecules, CONH2 (carbamyl radical) and HCONH (an isomer of carbamyl radical), in the ISM.

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Section: Discussionmentioning

confidence: 99%

Pathways for the Formation of Formamide, a Prebiotic Biomonomer: Metal-Ions in Interstellar Gas-Phase Chemistry

Thripati

Ramabhadran

2021

J. Phys. Chem. A

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“…The diatomic species that contain these bonds have an equal number of valence electrons occupying bonding and antibonding orbitals, which yields a bond order of 0, meaning that bond formation is not energetically favorable much like that present in noble gas dimers. Additionally, group 2 elements prefer 180°bond angles implying a strong preference for the valence electrons to be found on opposite sides of the atoms (Bassett and Fortenberry, 2018;Palmer and Fortenberry, 2018;Doerksen and Fortenberry, 2020;Watrous et al, 2021). In returning to the bond lengths, the Be Be, Be Mg, and Mg Mg bonds are close to the sum of their constituent atom's Van der Waals radii rather than their covalent radii.…”

Section: Resultsmentioning

confidence: 96%

“…For example, while AlH 2 OH has not been observed in any astrophysical regions thus far and its spectra have only recently been provided quantum chemically (Watrous et al, 2021), the reduced but related AlOH molecule has been detected in astrophysical environments (Apponi et al, 1993;Tenenbaum and Ziurys, 2010). However, its higher energy isomer, HAlO, has not been observed (Trabelsi and Francisco, 2018).…”

Section: Introductionmentioning

confidence: 99%

Further Astrochemical Insights From Bond Strengths of Small Molecules Containing Atoms From the First Three Rows of the Periodic Table

Doerksen

Fortenberry

2021

Front. Astron. Space Sci.

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The atoms contributing to the strongest “single bonds” on the periodic table do not continue to produce the strongest “double bonds” or “triple bonds.” In fact, the opposite appears to be the case. This quantum chemical examination of nominal X = Y and X ≡ Y bonds in model molecules of atoms from the first three rows of the periodic table shows that the strongest “double bond” is in formaldehyde once the astrophysically-depleted Be and B atoms are removed from consideration. The strongest “triple bond” is a close match between acetylene and N2. However, these results indicate that astrophysical regions containing a high abundance of hydride species will likely be areas where inorganic oxide formation is favored. Those where H2 molecules have already been dissociated will favor organic/volatile astrochemistry.

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“…As shown by the symmetry labels in Equations (28)–(33), borane is treated in

symmetry rather than its full

symmetry to simplify the coordinate system. The SIC coordinate systems utilized herein for BH

and BH

OH have been previously applied to the structurally similar AlH

[ 43 ] and AlH

OH [ 44 ] molecules, respectively. The total numbers of single-point energy computations to generate the QFFs for BH

, BH

OH, BH

, and HBO are 19585, 3161, 413, and 55.…”

Section: Computational Detailsmentioning

confidence: 99%

Anharmonic Vibrational Frequencies of Water Borane and Associated Molecules

Westbrook

Fortenberry

2021

Molecules

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Water borane (BH3OH2) and borinic acid (BH2OH) have been proposed as intermediates along the pathway of hydrogen generation from simple reactants: water and borane. However, the vibrational spectra for neither water borane nor borinic acid has been investigaged experimentally due to the difficulty of isolating them in the gas phase, making accurate quantum chemical predictions for such properties the most viable means of their determination. This work presents theoretical predictions of the full rotational and fundamental vibrational spectra of these two potentially application-rich molecules using quartic force fields at the CCSD(T)-F12b/cc-pCVTZ-F12 level with additional corrections included for the effects of scalar relativity. This computational scheme is further benchmarked against the available gas-phase experimental data for the related borane and HBO molecules. The differences are found to be within 3 cm−1 for the fundamental vibrational frequencies and as close as 15 MHz in the B0 and C0 principal rotational constants. Both BH2OH and BH3OH2 have multiple vibrational modes with intensities greater than 100 km mol−1, namely ν2 and ν4 in BH2OH, and ν1, ν3, ν4, ν9, and ν13 in BH3OH2. Finally, BH3OH2 has a large dipole moment of 4.24 D, which should enable it to be observable by rotational spectroscopy, as well.

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Pathways to Detection of Strongly-Bound Inorganic Species: The Vibrational and Rotational Spectral Data of AlH2OH, HMgOH, AlH2NH2, and HMgNH2

Cited by 17 publications

References 67 publications

Pathways for the Formation of Formamide, a Prebiotic Biomonomer: Metal-Ions in Interstellar Gas-Phase Chemistry

Pathways for the Formation of Formamide, a Prebiotic Biomonomer: Metal-Ions in Interstellar Gas-Phase Chemistry

Further Astrochemical Insights From Bond Strengths of Small Molecules Containing Atoms From the First Three Rows of the Periodic Table

Anharmonic Vibrational Frequencies of Water Borane and Associated Molecules

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