Issue 7, 2019

The rotation–vibration spectrum of methyl fluoride from first principles

Abstract

Accurate ab initio calculations on the rotation–vibration spectrum of methyl fluoride (CH3F) are reported. A new nine-dimensional potential energy surface (PES) and dipole moment surface (DMS) have been generated using high-level electronic structure methods. Notably, the PES was constructed from explicitly correlated coupled cluster calculations with extrapolation to the complete basis set limit and considered additional energy corrections to account for core-valence electron correlation, higher-order coupled cluster terms beyond perturbative triples, scalar relativistic effects, and the diagonal Born–Oppenheimer correction. The PES and DMS are evaluated through robust variational nuclear motion computations of pure rotational and vibrational energy levels, the equilibrium geometry of CH3F, vibrational transition moments, absolute line intensities of the ν6 band, and the rotation–vibration spectrum up to J = 40. The computed results show excellent agreement with a range of experimental sources, in particular the six fundamentals are reproduced with a root-mean-square error of 0.69 cm−1. This work represents the most accurate theoretical treatment of the rovibrational spectrum of CH3F to date.

Graphical abstract: The rotation–vibration spectrum of methyl fluoride from first principles

Supplementary files

Article information

Article type
Paper
Submitted
16 Mac 2018
Accepted
15 Mei 2018
First published
17 Mei 2018

Phys. Chem. Chem. Phys., 2019,21, 3496-3505

The rotation–vibration spectrum of methyl fluoride from first principles

A. Owens, A. Yachmenev, J. Küpper, S. N. Yurchenko and W. Thiel, Phys. Chem. Chem. Phys., 2019, 21, 3496 DOI: 10.1039/C8CP01721B

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements