"Improved Semi-experimental Equilibrium Structure Determination And Theoretical Prediction Of Hydrazoic Acid (<span Class=""roman"">hn</span>_{<span Class=""roman"">3</span>})"

Owen, Andrew N.

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https://hdl.handle.net/2142/111260 Copy

Description

Title

"Improved Semi-experimental Equilibrium Structure Determination And Theoretical Prediction Of Hydrazoic Acid (hn₃)"

Author(s)

Owen, Andrew N.

Contributor(s)

• McMahon, Robert J.
• Woods, R. Claude
• Stanton, John F.
• Esselman, Brian J.
• Sahoo, Nitai P

Issue Date

2021-06-22

Keyword(s)

Comparing theory and experiment

Abstract

We conducted multiple high-level \textit{ab initio} calculations to obtain improved semi-experimental equilibrium structures ($r_{e}$$^{SE}$) of hydrazoic acid (\chem{HN_3}) using previously reported experimental data and to obtain improved, purely theoretical predictions of the structure. For the $r_{e}$$^{SE}$ structures, we used the isotopologue-dependent vibrational corrections to the ground rotational constants obtained from anharmonic VPT2 calculations at CCSD(T) using cc-pV$X$Z and cc-pCV$X$Z basis sets (where $X = D, T, Q, 5$), as well as the isotopologue-dependent electron-mass corrections at the same level of theory, to carry out nonlinear least-squares fits of the experimentally determined rotational constants for all but two of the \chem{HN_3} isotopologues. The extent of corrections that were calculated allowed for extrapolation of the $r_{e}$$^{SE}$ structure to the complete basis set limit. To achieve an improved theoretical prediction, we obtained a CCSD(T)/cc-pCV6Z optimization and included corrections for extrapolation to the complete basis set limit, for effects of electron correlation, for relativistic effects, and for the Born-Oppenheimer approximation. The parameters of the resulting theoretical structure agrees to within the $2\sigma$ uncertainties of the $r_{e}$$^{SE}$.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

Text

Language

eng

Permalink

http://hdl.handle.net/2142/111260

DOI

10.15278/isms.2021.TE04

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