Multivalent optical cycling centers: towards control of polyatomics with multi-electron degrees of freedom

Optical control of polyatomic molecules promises new opportunities in precision metrology and fundamental chemistry, as well as quantum information and many-body science. Contemporary experimental and theoretical efforts have mostly focused on cycling photons via excitation of a single electron loca...

Full description

Saved in:
Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2022-12, Vol.25 (1), p.154-17
Main Authors: Yu, Phelan, Lopez, Adrian, Goddard, William A, Hutzler, Nicholas R
Format: Article
Language:English
Subjects:
Complexity
Controllability
Cycles
Degrees of freedom
Design parameters
Electronic structure
Molecular structure
Optical activity
Optical control
Photons
Polyatomic molecules
Quantum chemistry
Quantum phenomena
Single electrons
Transition metals
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Optical control of polyatomic molecules promises new opportunities in precision metrology and fundamental chemistry, as well as quantum information and many-body science. Contemporary experimental and theoretical efforts have mostly focused on cycling photons via excitation of a single electron localized to an alkaline earth (group 2)-like metal center. In this paper, we consider pathways towards optical cycling in polyatomic molecules with multi-electron degrees of freedom, which arise from two or more cycling electrons localized to p-block post-transition metal and metalloid (group 13, 14, and 15) centers. We characterize the electronic structure and rovibrational branching of several prototypical candidates using ab initio quantum chemical methods. Despite increased internal complexity and challenging design parameters, we find several molecules possessing quasi-closed photon cycling schemes with highly diagonal, visible and near-infrared transitions. Furthermore, we identify new heuristics for engineering optically controllable and laser-coolable polyatomic molecules with multi-electron cycling centers. Our results help elucidate the interplay between hybridization, repulsion, and ionicity in optically active species and provide new directions for using polyatomic molecules with complex electronic structure as a resource for quantum science and measurement. Optical control of multivalent polyatomic molecules promises new opportunities in precision metrology and fundamental chemistry, as well as quantum information and many-body science.
ISSN:1463-9076
1463-9084
DOI:10.1039/d2cp03545f