The effect of non-adiabatic coupling on the computed rovibrational energy levels amounts to about 2 cm for H and must be included in high-accuracy calculations. Different strategies to obtain the corresponding energy shifts are reviewed in the article. A promising way is to introduce effective vibrational reduced masses that depend on the nuclear configuration. A new empirical method that uses the stockholder atoms-in-molecules approach to this effect is presented and applied to H. Furthermore, a highly accurate potential energy surface for the D isotopologue, which includes relativistic and leading quantum electrodynamic terms, is constructed and used to analyse the observed rovibrational frequencies for this molecule. Accurate band origins are obtained that improve existing data. This article is part of a discussion meeting issue 'Advances in hydrogen molecular ions: H, H and beyond'.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6710893 | PMC |
| http://dx.doi.org/10.1098/rsta.2018.0411 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
A Theoretical Study on Crossings Among Electronically Excited States and Laser Cooling of Group VIA (S, Se, and Te) Hydrides.
J Comput Chem
January 2025
Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China.
Various electronically excited states and the feasibility of direct laser cooling of SH, SeH, and TeH are investigated using the highly accurate ab initio and dynamical methods. For the detailed calculations of the seven low-lying Λ-S states of SH, we utilized the internally contracted multireference configuration interaction approach, considering the spin-orbit coupling (SOC) effects. Our calculated spectroscopic constants are in very good agreement with the available experimental results.
View Article and Find Full Text PDFSingle-Atom-Induced Hybridization States Promote the Direct Trapping of Hot Carriers by Reactants for Photocatalysis.
J Phys Chem Lett
January 2025
Key Laboratory of Quantum Materials and Devices of Ministry of Education, School of Physics, Southeast University, Nanjing 211189, China.
Single-atom manipulation has emerged as an effective strategy for enhancing the photocatalytic efficiency. However, the mechanism of photogenerated carrier dynamics under single-atom modulation remains unclear. Combining first-principles calculations and non-adiabatic molecular dynamics simulations, we systematically studied carrier transfer and recombination in the oxygen reduction reaction of single-atom-doped CN systems.
View Article and Find Full Text PDFExcited state dynamics of azanaphthalenes reveal opportunities for the rational design of photoactive molecules.
Commun Chem
January 2025
Institute of Chemical Sciences, Heriot-Watt University, Edinburgh, UK.
Various photoactive molecules contain motifs built on aza-aromatic heterocycles, although a detailed understanding of the excited state photophysics and photochemistry in such systems is not fully developed. To help address this issue, the non-adiabatic dynamics operating in azanaphthalenes under hexane solvation was studied following 267 nm excitation using ultrafast transient absorption spectroscopy. Specifically, the species quinoline, isoquinoline, quinazoline, quinoxaline, 1,6-naphthyridine, and 1,8-naphthyridine were investigated, providing a systematic variation in the relative positioning of nitrogen heteroatom centres within a bicyclic aromatic structure.
View Article and Find Full Text PDFA semiclassical non-adiabatic phase-space approach to molecular translations and rotations: Surface hopping with electronic inertial effects.
J Chem Phys
December 2024
Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA.
We demonstrate that working with a correct phase-space electronic Hamiltonian captures electronic inertial effects. In particular, we show that phase space surface hopping dynamics do not suffer (at least to very high order) from non-physical non-adiabatic transitions between electronic eigenstates during the course of pure nuclear translational and rotational motion. This work opens up many new avenues for quantitatively investigating complex phenomena, including angular momentum transfer between chiral phonons and electrons as well as chiral-induced spin selectivity effects.
View Article and Find Full Text PDFHighly efficient NIR-Ⅱ window photoluminescence up to 1000 nm using heteroatomic fused-ring radicals.
Spectrochim Acta A Mol Biomol Spectrosc
December 2024
School of Chemistry and Environmental Engineering, Changchun University of Science and Technology, Jilin Provincial Science and Technology Innovation Center of Optical Materials and Chemistry, Jilin Provincial International Joint Research Center of Photo-functional Materials and Chemistry, Changchun 130022, China; State Key Laboratory of Supramolecular Structure and Materials, Institute of Theoretical Chemistry, College of Chemistry, Jilin University, Changchun 130021, China. Electronic address:
Neutral radicals have the potential to construct pure organic light-emitting diodes (OLEDs) with internal quantum efficiencies reaching 100%. However, neutral radical luminescent materials with emission wavelengths in the second near-infrared (NIR-II) window are rare. Herein, a serial of neutral donor-bridge-acceptor (D-π-A) type radical derivatives are investigated.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!