10 Years of the ACS PHYS Astrochemistry Subdivision

Fortenberry, Ryan C.; McMahon, Robert J.; Kaiser, Ralf I.

doi:10.1021/acs.jpca.2c06091

Cited by 6 publications

(6 citation statements)

References 47 publications

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“…Unfortunately, the CcCR + QZ ν 1 (1913.7 cm −1 ) now performs worse than the pure CcCR (1843.3 cm −1 ) with the experiment attributed at 1848.5 cm −1 . 107 This implies that the core correlation in the least, which is typically the dominant correction term, 35,39,111 is needed to describe the H−P stretch, but such produces cubic and quartic terms in the bend that are too large.…”

Section: Hpo Thementioning

confidence: 99%

Performance of EOM-CCSD(T)(a)*-Based Quartic Force Fields in Computing Fundamental, Anharmonic Vibrational Frequencies of Molecular Electronically Excited States with Application to the Ã¹A″ State of :CCH₂ (Vinylidene)

Watrous,

Davis,

Fortenberry

2024

J. Phys. Chem. A

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Highly accurate anharmonic vibrational frequencies of electronically excited states are not as easily computed as their ground electronic state counterparts, but recently developed approximate triple excited state methods may be changing that. One emerging excited state method is equation of motion coupled cluster theory at the singles and doubles level with perturbative triples computed via the (a)* formalism, EOMEE-CCSD(T)(a)*. One of the most employed means for the ready computation of vibrational anharmonic frequencies for ground electronic states is second-order vibrational perturbation theory (VPT2), a theory based on quartic force fields (QFFs),fourth-order Taylor series expansions of the potential portion of the internuclear Watson Hamiltonian. The combination of these two is herein benchmarked for its performance for use as a means of computing rovibrational spectra of electronically excited states. Specifically, the EOMEE-CCSD(T)(a)* approach employing a complete basis set extrapolation along with core electron inclusion and relativity (the so-called "CcCR" approach) defining the QFF produces anharmonic fundamental vibrational frequencies within 2.83%, on the average, of reported gas-phase experimentally assigned values for the test set including the A A

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Section: Hpo Thementioning

confidence: 99%

Performance of EOM-CCSD(T)(a)*-Based Quartic Force Fields in Computing Fundamental, Anharmonic Vibrational Frequencies of Molecular Electronically Excited States with Application to the Ã¹A″ State of :CCH₂ (Vinylidene)

Watrous,

Davis,

Fortenberry

2024

J. Phys. Chem. A

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“…As has often been described, − astrochemistry is an interdependent triangle (Figure ) comprised of observation, modeling, and the generation of reference data. (This last branch is often called “laboratory astrophysics” but more on that later.)…”

Section: Introductionmentioning

confidence: 99%

Quantum Chemistry and Astrochemistry: A Match Made in the Heavens

Fortenberry

2024

J. Phys. Chem. A

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Quantum chemistry can uniquely answer astrochemical questions that no other technique can provide. Computations can be parallelized, automated, and left to run continuously providing exceptional molecular throughput that cannot be done through experimentation. Additionally, the granularity of the individual computations that are required of potential energy surfaces, reaction mechanism pathways, or other quantum chemically derived observables produces a unique mosaic that make up the larger whole. These pieces can be dissected for their individual contributions or evaluated in an ad hoc fashion for each of their roles in generating the larger whole. No other scientific approach is capable of reporting such fine-grained insights. Quantum chemistry also works from a bottom-up approach in providing properties directly from the desired molecule instead of a top-down perspective as required of experiment where molecules have to be linked to observed phenomena. Furthermore, modern quantum chemistry is well within the range of "chemical accuracy" and is approaching "spectroscopic accuracy." As such, the seemingly difficult questions asked by astrochemistry that would not be asked initially for any other application require quantum chemical reference data. While the results of quantum chemical computations are needed to interpret astrochemical observation, modeling, or laboratory experimentation, such hard questions, regardless of the original need to answer them, produce unique solutions. While questions in astrochemistry often require novel developments in and implementations of quantum chemistry as outlined herein, the applications of these solutions will stretch beyond astrochemistry and may yet impact fields much closer to Earth.

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“…And again and again and again and again. Thus, astrochemistry and its interdependent triangle 26 of observation, modeling, and reference data production were born.…”

Section: ■ Introductionmentioning

confidence: 99%

A Vision for the Future of Astrochemistry in the Interstellar Medium by 2050

Fortenberry

2023

ACS Phys. Chem Au

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By 2050, many, but not nearly all, unattributed astronomical spectral features will be conclusively linked to molecular carriers (as opposed to nearly none today in the visible and IR); amino acids will have been observed remotely beyond our solar system; the largest observatories ever constructed on the surface of the Earth or launched beyond it will be operational; high-throughput computation either from brute force or machine learning will provide unprecedented amounts of reference spectral and chemical reaction data; and the chemical fingerprints of the universe delivered by those of us who call ourselves astrochemists will provide astrophysicists with unprecedented resolution for determining how the stars evolve, planets form, and molecules that lead to life originate. Astrochemistry is a relatively young field, but with the entire universe as its playground, the discipline promises to persist as long as telescopic observations are made that require reference data and complementary chemical modeling. While the recent commissionings of the James Webb Space Telescope and Atacama Large Millimeter Array are ushering in the second "golden age" of astrochemistry (with the first being the radio telescopic boom period of the 1970s), this current period of discovery should facilitate unprecedented advances within the next 25 years. Astrochemistry forces the asking of hard questions beyond the physical conditions of our "pale blue dot", and such questions require creative solutions that are influential beyond astrophysics. By 2050, more creative solutions will have been provided, but even more will be needed to answer the continuing question of our astrochemical ignorance.

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10 Years of the ACS PHYS Astrochemistry Subdivision

Cited by 6 publications

References 47 publications

Performance of EOM-CCSD(T)(a)*-Based Quartic Force Fields in Computing Fundamental, Anharmonic Vibrational Frequencies of Molecular Electronically Excited States with Application to the Ã¹A″ State of :CCH₂ (Vinylidene)

Performance of EOM-CCSD(T)(a)*-Based Quartic Force Fields in Computing Fundamental, Anharmonic Vibrational Frequencies of Molecular Electronically Excited States with Application to the Ã¹A″ State of :CCH₂ (Vinylidene)

Quantum Chemistry and Astrochemistry: A Match Made in the Heavens

A Vision for the Future of Astrochemistry in the Interstellar Medium by 2050

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10 Years of the ACS PHYS Astrochemistry Subdivision

Cited by 6 publications

References 47 publications

Performance of EOM-CCSD(T)(a)*-Based Quartic Force Fields in Computing Fundamental, Anharmonic Vibrational Frequencies of Molecular Electronically Excited States with Application to the Ã1A″ State of :CCH2 (Vinylidene)

Performance of EOM-CCSD(T)(a)*-Based Quartic Force Fields in Computing Fundamental, Anharmonic Vibrational Frequencies of Molecular Electronically Excited States with Application to the Ã1A″ State of :CCH2 (Vinylidene)

Quantum Chemistry and Astrochemistry: A Match Made in the Heavens

A Vision for the Future of Astrochemistry in the Interstellar Medium by 2050

Contact Info

Product

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Performance of EOM-CCSD(T)(a)*-Based Quartic Force Fields in Computing Fundamental, Anharmonic Vibrational Frequencies of Molecular Electronically Excited States with Application to the Ã¹A″ State of :CCH₂ (Vinylidene)

Performance of EOM-CCSD(T)(a)*-Based Quartic Force Fields in Computing Fundamental, Anharmonic Vibrational Frequencies of Molecular Electronically Excited States with Application to the Ã¹A″ State of :CCH₂ (Vinylidene)