Complete, Theoretical Rovibronic Spectral Characterization of the Carbon Monoxide, Water, and Formaldehyde Cations
New high-level ab initio quartic force field (QFF) methods are explored which provide spectroscopic data for the electronically excited states of the carbon monoxide, water, and formaldehyde cations, sentinel species for expanded, recent cometary spectral analysis. QFFs based on equation-of-motion i...
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| Format: | Article |
| Language: | English |
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MDPI AG
2023-02-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/4/1782 |
| _version_ | 1797619016414527488 |
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| author | Megan C. Davis Xinchuan Huang Ryan C. Fortenberry |
| author_facet | Megan C. Davis Xinchuan Huang Ryan C. Fortenberry |
| author_sort | Megan C. Davis |
| collection | DOAJ |
| description | New high-level ab initio quartic force field (QFF) methods are explored which provide spectroscopic data for the electronically excited states of the carbon monoxide, water, and formaldehyde cations, sentinel species for expanded, recent cometary spectral analysis. QFFs based on equation-of-motion ionization potential (EOM-IP) with a complete basis set extrapolation and core correlation corrections provide assignment for the fundamental vibrational frequencies of the <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mover accent="true"><mi mathvariant="normal">A</mi><mo>˜</mo></mover></semantics></math></inline-formula><inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msup><mrow></mrow><mn>2</mn></msup></semantics></math></inline-formula>B<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>1</mn></msub></semantics></math></inline-formula> and <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mover accent="true"><mi mathvariant="normal">B</mi><mo>˜</mo></mover></semantics></math></inline-formula><inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msup><mrow></mrow><mn>2</mn></msup></semantics></math></inline-formula>A<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>1</mn></msub></semantics></math></inline-formula> states of the formaldehyde cation; only three of these frequencies have experimental assignment available. Rotational constants corresponding to these vibrational excitations are also provided for the first time for all electronically excited states of both of these molecules. EOM-IP-CCSDT/CcC computations support tentative re-assignment of the <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>ν</mi><mn>1</mn></msub></semantics></math></inline-formula> and <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>ν</mi><mn>3</mn></msub></semantics></math></inline-formula> frequencies of the <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mover accent="true"><mi mathvariant="normal">B</mi><mo>˜</mo></mover></semantics></math></inline-formula><inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msup><mrow></mrow><mn>2</mn></msup><msub><mi>B</mi><mn>2</mn></msub></mrow></semantics></math></inline-formula> state of the water cation to approximately 2409.3 cm<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msup><mrow></mrow><mrow><mo>−</mo><mn>1</mn></mrow></msup></semantics></math></inline-formula> and 1785.7 cm<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msup><mrow></mrow><mrow><mo>−</mo><mn>1</mn></mrow></msup></semantics></math></inline-formula>, respectively, due to significant disagreement between experimental assignment and all levels of theory computed herein, as well as work by previous authors. The EOM-IP-CCSDT/CcC QFF achieves agreement to within 12 cm<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msup><mrow></mrow><mrow><mo>−</mo><mn>1</mn></mrow></msup></semantics></math></inline-formula> for the fundamental vibrational frequencies of the electronic ground state of the water cation compared to experimental values and to the high-level theoretical benchmarks for variationally-accessible states. Less costly EOM-IP based approaches are also explored using approximate triples coupled cluster methods, as well as electronically excited state QFFs based on EOM-CC3 and the previous (T)+EOM approach. The novel data, including vibrationally corrected rotational constants for all states studied herein, provided by these computations should be useful in clarifying comet evolution or other remote sensing applications in addition to fundamental spectroscopy. |
| first_indexed | 2024-03-11T08:20:59Z |
| format | Article |
| id | doaj.art-5d0c2a69032c45d8a9766d4dac391ff0 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-11T08:20:59Z |
| publishDate | 2023-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-5d0c2a69032c45d8a9766d4dac391ff02023-11-16T22:23:08ZengMDPI AGMolecules1420-30492023-02-01284178210.3390/molecules28041782Complete, Theoretical Rovibronic Spectral Characterization of the Carbon Monoxide, Water, and Formaldehyde CationsMegan C. Davis0Xinchuan Huang1Ryan C. Fortenberry2Department of Chemistry & Biochemistry, University of Mississippi, University, MS 38677-1848, USASETI Institute, Mountain View, CA 94043, USADepartment of Chemistry & Biochemistry, University of Mississippi, University, MS 38677-1848, USANew high-level ab initio quartic force field (QFF) methods are explored which provide spectroscopic data for the electronically excited states of the carbon monoxide, water, and formaldehyde cations, sentinel species for expanded, recent cometary spectral analysis. QFFs based on equation-of-motion ionization potential (EOM-IP) with a complete basis set extrapolation and core correlation corrections provide assignment for the fundamental vibrational frequencies of the <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mover accent="true"><mi mathvariant="normal">A</mi><mo>˜</mo></mover></semantics></math></inline-formula><inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msup><mrow></mrow><mn>2</mn></msup></semantics></math></inline-formula>B<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>1</mn></msub></semantics></math></inline-formula> and <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mover accent="true"><mi mathvariant="normal">B</mi><mo>˜</mo></mover></semantics></math></inline-formula><inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msup><mrow></mrow><mn>2</mn></msup></semantics></math></inline-formula>A<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>1</mn></msub></semantics></math></inline-formula> states of the formaldehyde cation; only three of these frequencies have experimental assignment available. Rotational constants corresponding to these vibrational excitations are also provided for the first time for all electronically excited states of both of these molecules. EOM-IP-CCSDT/CcC computations support tentative re-assignment of the <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>ν</mi><mn>1</mn></msub></semantics></math></inline-formula> and <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mi>ν</mi><mn>3</mn></msub></semantics></math></inline-formula> frequencies of the <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mover accent="true"><mi mathvariant="normal">B</mi><mo>˜</mo></mover></semantics></math></inline-formula><inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msup><mrow></mrow><mn>2</mn></msup><msub><mi>B</mi><mn>2</mn></msub></mrow></semantics></math></inline-formula> state of the water cation to approximately 2409.3 cm<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msup><mrow></mrow><mrow><mo>−</mo><mn>1</mn></mrow></msup></semantics></math></inline-formula> and 1785.7 cm<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msup><mrow></mrow><mrow><mo>−</mo><mn>1</mn></mrow></msup></semantics></math></inline-formula>, respectively, due to significant disagreement between experimental assignment and all levels of theory computed herein, as well as work by previous authors. The EOM-IP-CCSDT/CcC QFF achieves agreement to within 12 cm<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msup><mrow></mrow><mrow><mo>−</mo><mn>1</mn></mrow></msup></semantics></math></inline-formula> for the fundamental vibrational frequencies of the electronic ground state of the water cation compared to experimental values and to the high-level theoretical benchmarks for variationally-accessible states. Less costly EOM-IP based approaches are also explored using approximate triples coupled cluster methods, as well as electronically excited state QFFs based on EOM-CC3 and the previous (T)+EOM approach. The novel data, including vibrationally corrected rotational constants for all states studied herein, provided by these computations should be useful in clarifying comet evolution or other remote sensing applications in addition to fundamental spectroscopy.https://www.mdpi.com/1420-3049/28/4/1782quantum chemistrycomputational spectroscopycoupled cluster theoryastrochemistryUV/Vis spectrarovibronic spectra |
| spellingShingle | Megan C. Davis Xinchuan Huang Ryan C. Fortenberry Complete, Theoretical Rovibronic Spectral Characterization of the Carbon Monoxide, Water, and Formaldehyde Cations Molecules quantum chemistry computational spectroscopy coupled cluster theory astrochemistry UV/Vis spectra rovibronic spectra |
| title | Complete, Theoretical Rovibronic Spectral Characterization of the Carbon Monoxide, Water, and Formaldehyde Cations |
| title_full | Complete, Theoretical Rovibronic Spectral Characterization of the Carbon Monoxide, Water, and Formaldehyde Cations |
| title_fullStr | Complete, Theoretical Rovibronic Spectral Characterization of the Carbon Monoxide, Water, and Formaldehyde Cations |
| title_full_unstemmed | Complete, Theoretical Rovibronic Spectral Characterization of the Carbon Monoxide, Water, and Formaldehyde Cations |
| title_short | Complete, Theoretical Rovibronic Spectral Characterization of the Carbon Monoxide, Water, and Formaldehyde Cations |
| title_sort | complete theoretical rovibronic spectral characterization of the carbon monoxide water and formaldehyde cations |
| topic | quantum chemistry computational spectroscopy coupled cluster theory astrochemistry UV/Vis spectra rovibronic spectra |
| url | https://www.mdpi.com/1420-3049/28/4/1782 |
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