### 抄録

A global analytic potential energy surface for the ro-vibrational dynamics of cis- and trans-formic acid is presented, constructed using LASSO-based regression to reproduce CCSD(T)(F12*)/cc-pVTZ-F12 energies. The fit is accurate to 0.25% has an RMS deviation from the ab initio data of 9 cm^{−1} for the energy range 0−15000 cm^{−1}. Converged J = 0 vibrational eigenstates are reported, computed using vibrational configuration interaction with an internal coordinate path Hamiltonian for the torsional motion connecting the cis and trans rotamers. Methodological choices concerning the appropriate definitions of the curvilinear and diabatic bath coordinates are discussed. The zero point of the cis rotamer is 1412 cm^{−1} above that of the trans, which lies at 7354 cm^{−1}. The computed fundamentals match the bands recorded from gas-phase IR spectroscopy with an RMSD of only 3 cm^{−1}. A fresh assignment of the overtone spectra of both the cis and trans rotamers is presented for the energy range 0−4720 cm^{−1}, where 14 out of the 51 bands are reassigned on the basis of the VCI calculations.

元の言語 | 英語 |
---|---|

ページ（範囲） | 9815-9828 |

ページ数 | 14 |

ジャーナル | Journal of Physical Chemistry A |

巻 | 120 |

発行部数 | 49 |

DOI | |

出版物ステータス | 出版済み - 1 1 2016 |

外部発表 | Yes |

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### All Science Journal Classification (ASJC) codes

- Physical and Theoretical Chemistry

### これを引用

*Journal of Physical Chemistry A*,

*120*(49), 9815-9828. https://doi.org/10.1021/acs.jpca.6b09952

**Ab initio vibrational spectroscopy of cis- and trans-Formic acid from a global potential energy surface.** / Tew, David P.; Mizukami, Wataru.

研究成果: ジャーナルへの寄稿 › 記事

*Journal of Physical Chemistry A*, 巻. 120, 番号 49, pp. 9815-9828. https://doi.org/10.1021/acs.jpca.6b09952

}

TY - JOUR

T1 - Ab initio vibrational spectroscopy of cis- and trans-Formic acid from a global potential energy surface

AU - Tew, David P.

AU - Mizukami, Wataru

PY - 2016/1/1

Y1 - 2016/1/1

N2 - A global analytic potential energy surface for the ro-vibrational dynamics of cis- and trans-formic acid is presented, constructed using LASSO-based regression to reproduce CCSD(T)(F12*)/cc-pVTZ-F12 energies. The fit is accurate to 0.25% has an RMS deviation from the ab initio data of 9 cm−1 for the energy range 0−15000 cm−1. Converged J = 0 vibrational eigenstates are reported, computed using vibrational configuration interaction with an internal coordinate path Hamiltonian for the torsional motion connecting the cis and trans rotamers. Methodological choices concerning the appropriate definitions of the curvilinear and diabatic bath coordinates are discussed. The zero point of the cis rotamer is 1412 cm−1 above that of the trans, which lies at 7354 cm−1. The computed fundamentals match the bands recorded from gas-phase IR spectroscopy with an RMSD of only 3 cm−1. A fresh assignment of the overtone spectra of both the cis and trans rotamers is presented for the energy range 0−4720 cm−1, where 14 out of the 51 bands are reassigned on the basis of the VCI calculations.

AB - A global analytic potential energy surface for the ro-vibrational dynamics of cis- and trans-formic acid is presented, constructed using LASSO-based regression to reproduce CCSD(T)(F12*)/cc-pVTZ-F12 energies. The fit is accurate to 0.25% has an RMS deviation from the ab initio data of 9 cm−1 for the energy range 0−15000 cm−1. Converged J = 0 vibrational eigenstates are reported, computed using vibrational configuration interaction with an internal coordinate path Hamiltonian for the torsional motion connecting the cis and trans rotamers. Methodological choices concerning the appropriate definitions of the curvilinear and diabatic bath coordinates are discussed. The zero point of the cis rotamer is 1412 cm−1 above that of the trans, which lies at 7354 cm−1. The computed fundamentals match the bands recorded from gas-phase IR spectroscopy with an RMSD of only 3 cm−1. A fresh assignment of the overtone spectra of both the cis and trans rotamers is presented for the energy range 0−4720 cm−1, where 14 out of the 51 bands are reassigned on the basis of the VCI calculations.

UR - http://www.scopus.com/inward/record.url?scp=85029358649&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85029358649&partnerID=8YFLogxK

U2 - 10.1021/acs.jpca.6b09952

DO - 10.1021/acs.jpca.6b09952

M3 - Article

AN - SCOPUS:85029358649

VL - 120

SP - 9815

EP - 9828

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 49

ER -