Jump to main content
Jump to site search

Issue 13, 2021
Previous Article Next Article

“Inverted” CO molecules on NaCl(100): a quantum mechanical study

Author affiliations

Abstract

Somewhat surprisingly, inverted (“O-down”) CO adsorbates on NaCl(100) were recently observed experimentally after infrared vibrational excitation (Lau et al., Science, 2020, 367, 175–178). Here we characterize these species using periodic density functional theory and a quantum mechanical description of vibrations. We determine stationary points and minimum energy paths for CO inversion, for low (1/8 and 1/4 monolayers (ML)) and high (1 ML) coverages. Transition state theory is applied to estimate thermal rates for “C-down” to “O-down” isomerization and the reverse process. For the 1/4 ML p(1 × 1) structure, two-dimensional and three-dimensional potential energy surfaces and corresponding anharmonic vibrational eigenstates obtained from the time-independent nuclear Schrödinger equation are presented. We find (i) rather coverage-independent CO inversion energies (of about 0.08 eV or 8 kJ mol−1 per CO) and corresponding classical activation energies for “C-down” to “O-down” isomerization (of about 0.15 eV or 14 kJ mol−1 per CO); (ii) thermal isomerization rates at 22 K which are vanishingly small for the “C-down” to “O-down” isomerization but non-negligible for the back reaction; (iii) several “accidentally degenerate” pairs of eigenstates well below the barrier, each pair describing “C-down” to “O-down” localized states.

Graphical abstract: “Inverted” CO molecules on NaCl(100): a quantum mechanical study

Back to tab navigation

Article information


Submitted
02 Oct 2020
Accepted
11 Nov 2020
First published
12 Nov 2020

Phys. Chem. Chem. Phys., 2021,23, 7860-7874
Article type
Paper

“Inverted” CO molecules on NaCl(100): a quantum mechanical study

S. Sinha and P. Saalfrank, Phys. Chem. Chem. Phys., 2021, 23, 7860 DOI: 10.1039/D0CP05198E

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