Jump to main content
Jump to site search
SCHEDULED MAINTENANCE Close the message box

Maintenance work is planned for Monday 16 August 2021 from 07:00 to 23:59 (BST).

Website performance may be temporarily affected and you may not be able to access some PDFs or images. If this does happen, refreshing your web browser should resolve the issue. We apologise for any inconvenience this might cause and thank you for your patience.


Issue 7, 2019

Quantum approaches to vibrational dynamics and spectroscopy: is ease of interpretation sacrificed as rigor increases?

Author affiliations

Abstract

The subject of this Perspective is quantum approaches, beyond the harmonic approximation, to vibrational dynamics and IR spectroscopy. We begin with a pedagogical, unifying review of the most widely used quantum approaches. Some of the key details that lead to steep computational scaling of these approaches are reviewed, as well as some effective strategies to overcome or at least mitigate them. Considering in particular the application to IR spectroscopy, we stress the strength and weakness of each approach for spectral features that evolve from “simple” to “complex”. We use the 10-atom formic acid dimer as an ideal example of this evolution. The IR spectrum of this dimer and two isotopologs has been obtained computationally using our software, MULTIMODE, and approaches to obtain accurate, ab initio, full-dimensional potential energy and dipole moment surfaces, also developed by our group. The IR spectra obtained with the widely used “ab initio molecular dynamics” approach are also presented and assessed. The extension of quantum approaches to molecular clusters and even condensed phase applications, where molecular dynamics approaches are typically used, is discussed mainly in the context of the local monomer model. This approach is illustrated for a methane clathrate hydrate, where vibrational energies of the symmetric and asymmetric stretches of methane are given for a number of water cages and compared to experiment. The question about interpretation is also addressed throughout the Perspective.

Graphical abstract: Quantum approaches to vibrational dynamics and spectroscopy: is ease of interpretation sacrificed as rigor increases?

Article information


Submitted
05 Aug 2018
Accepted
24 Oct 2018
First published
26 Oct 2018

Phys. Chem. Chem. Phys., 2019,21, 3397-3413
Article type
Perspective

Quantum approaches to vibrational dynamics and spectroscopy: is ease of interpretation sacrificed as rigor increases?

C. Qu and J. M. Bowman, Phys. Chem. Chem. Phys., 2019, 21, 3397 DOI: 10.1039/C8CP04990D

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

Search articles by author

Spotlight

Advertisements