### Abstract

Systematic quantum chemical calculations have been performed to obtain precise estimates of the equilibrium and vibrationally averaged molecular structure and electric dipole moment of vinylacetylene (VA, 1-buten-3-yne). Anharmonic (cubic and semi-diagonal quartic) MP2/cc-pVTZ force fields in normal coordinates were computed to account for anharmonic vibrational effects, including zero-point contributions to the rotational constants and the electric dipole moment. A simultaneous weighted least-squares structural refinement was performed, resulting in the best semispectroscopic estimate of the r_{e} structure of VA. The refinement was based on experimentally measured ground-state rotational constants of two isotopologs of VA corrected to equilibrium values using MP2/cc-pVTZ vibration-rotation interaction constants and all-electron CCSD(T)/ aug-cc-pVTZ structural constraints. The semispectroscopic r^{e} structure of VA agrees excellently with the high-level CCSD(T)/aug-cc-pVTZ ab initio structure. The most dependable, CCSD(T)/cc-pVQZ//CCSD(T)/ aug-cc-pVTZ equilibrium electric dipole moment of VA, in D, is μ_{a} = 0.4088, μ_{b} = 0.0004, and μ_{c} = 0. The vibrationally corrected a-component of 0.4214 D is in excellent agreement with one of the available experimental values. The present analysis shows that μ_{b} is negligible even after vibrational correction. A simple quantitative structure-property relationship (QSPR) model resulted in a highly similar estimate, 0.45 D, for the electric dipole moment of VA.

Original language | English |
---|---|

Pages (from-to) | 4824-4828 |

Number of pages | 5 |

Journal | Journal of Physical Chemistry A |

Volume | 109 |

Issue number | 21 |

DOIs | |

Publication status | Published - Jun 2 2005 |

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### ASJC Scopus subject areas

- Physical and Theoretical Chemistry

### Cite this

**Semispectroscopic and quantitative structure-property relationship estimates of the equilibrium and vibrationally averaged structure and dipole moment of l-buten-3-yne.** / Tasi, G.; Szöri, Milan; Császár, A.

Research output: Contribution to journal › Article

*Journal of Physical Chemistry A*, vol. 109, no. 21, pp. 4824-4828. https://doi.org/10.1021/jp058005b

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TY - JOUR

T1 - Semispectroscopic and quantitative structure-property relationship estimates of the equilibrium and vibrationally averaged structure and dipole moment of l-buten-3-yne

AU - Tasi, G.

AU - Szöri, Milan

AU - Császár, A.

PY - 2005/6/2

Y1 - 2005/6/2

N2 - Systematic quantum chemical calculations have been performed to obtain precise estimates of the equilibrium and vibrationally averaged molecular structure and electric dipole moment of vinylacetylene (VA, 1-buten-3-yne). Anharmonic (cubic and semi-diagonal quartic) MP2/cc-pVTZ force fields in normal coordinates were computed to account for anharmonic vibrational effects, including zero-point contributions to the rotational constants and the electric dipole moment. A simultaneous weighted least-squares structural refinement was performed, resulting in the best semispectroscopic estimate of the re structure of VA. The refinement was based on experimentally measured ground-state rotational constants of two isotopologs of VA corrected to equilibrium values using MP2/cc-pVTZ vibration-rotation interaction constants and all-electron CCSD(T)/ aug-cc-pVTZ structural constraints. The semispectroscopic re structure of VA agrees excellently with the high-level CCSD(T)/aug-cc-pVTZ ab initio structure. The most dependable, CCSD(T)/cc-pVQZ//CCSD(T)/ aug-cc-pVTZ equilibrium electric dipole moment of VA, in D, is μa = 0.4088, μb = 0.0004, and μc = 0. The vibrationally corrected a-component of 0.4214 D is in excellent agreement with one of the available experimental values. The present analysis shows that μb is negligible even after vibrational correction. A simple quantitative structure-property relationship (QSPR) model resulted in a highly similar estimate, 0.45 D, for the electric dipole moment of VA.

AB - Systematic quantum chemical calculations have been performed to obtain precise estimates of the equilibrium and vibrationally averaged molecular structure and electric dipole moment of vinylacetylene (VA, 1-buten-3-yne). Anharmonic (cubic and semi-diagonal quartic) MP2/cc-pVTZ force fields in normal coordinates were computed to account for anharmonic vibrational effects, including zero-point contributions to the rotational constants and the electric dipole moment. A simultaneous weighted least-squares structural refinement was performed, resulting in the best semispectroscopic estimate of the re structure of VA. The refinement was based on experimentally measured ground-state rotational constants of two isotopologs of VA corrected to equilibrium values using MP2/cc-pVTZ vibration-rotation interaction constants and all-electron CCSD(T)/ aug-cc-pVTZ structural constraints. The semispectroscopic re structure of VA agrees excellently with the high-level CCSD(T)/aug-cc-pVTZ ab initio structure. The most dependable, CCSD(T)/cc-pVQZ//CCSD(T)/ aug-cc-pVTZ equilibrium electric dipole moment of VA, in D, is μa = 0.4088, μb = 0.0004, and μc = 0. The vibrationally corrected a-component of 0.4214 D is in excellent agreement with one of the available experimental values. The present analysis shows that μb is negligible even after vibrational correction. A simple quantitative structure-property relationship (QSPR) model resulted in a highly similar estimate, 0.45 D, for the electric dipole moment of VA.

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U2 - 10.1021/jp058005b

DO - 10.1021/jp058005b

M3 - Article

C2 - 16833826

AN - SCOPUS:20544472379

VL - 109

SP - 4824

EP - 4828

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 21

ER -