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

G. Tasi, Milan Szöri, A. Császár

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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 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.

Original languageEnglish
Pages (from-to)4824-4828
Number of pages5
JournalJournal of Physical Chemistry A
Volume109
Issue number21
DOIs
Publication statusPublished - Jun 2 2005

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Electric dipole moments
Dipole moment
electric moments
electric dipoles
dipole moments
moments
estimates
Ground state
Molecular structure
field theory (physics)
molecular structure
dipoles
vibration
ground state
Electrons
electrons
interactions

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

@article{5837697ea3af49db90d9103808d2260c,
title = "Semispectroscopic and quantitative structure-property relationship estimates of the equilibrium and vibrationally averaged structure and dipole moment of l-buten-3-yne",
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 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.",
author = "G. Tasi and Milan Sz{\"o}ri and A. Cs{\'a}sz{\'a}r",
year = "2005",
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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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