Two Cycling Centers in One Molecule: Communication by Through-Bond Interactions and Entanglement of the Unpaired Electrons

Ivanov, Maxim V.; Gulania, Sahil; Krylov, Anna I.

doi:10.1021/acs.jpclett.0c00021

Title: Two Cycling Centers in One Molecule: Communication by Through-Bond Interactions and Entanglement of the Unpaired Electrons

Journal Article · 22 January 2020 · Journal of Physical Chemistry Letters

DOI: https://doi.org/10.1021/acs.jpclett.0c00021 · OSTI ID:1595346

Ivanov, Maxim V. ^[1]; Gulania, Sahil ^[2]; Krylov, Anna I. ^[2]

Univ. of Southern California, Los Angeles, CA (United States); University of Southern California
Univ. of Southern California, Los Angeles, CA (United States)

Many applications in quantum information science (QIS) rely on the ability to laser- cool molecules. The scope of applications can be expanded if laser-coolable molecules possess two or more cycling centers, i.e., moieties capable of scattering photons via multiple absorption-emission events. Here in this paper we employ equation-of-motion coupled-cluster method for double electron attachment (EOM-DEA-CCSD) to study the electronic structure of hypermetallic molecules with two alkaline earth metals connected by an acetylene linker. The electronic structure of the molecules is similar to that of two separated alkali metals; however, the interaction between the two electrons is weak and largely dominated by through-bond interactions. The communication between the two cycling centers is quantified by the extent of the entanglement of the two unpaired electrons associated with each center. This contribution highlights the rich electronic structure of hypermetallic molecules that may advance various applications in QIS and beyond.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Univ. of Southern California, Los Angeles, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019245

OSTI ID:: 1595346

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 4 Vol. 11; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (69)

The Quantum Chemistry of Open-Shell Species Krylov, Anna I. Reviews in Computational Chemistry https://doi.org/10.1002/9781119356059.ch4	book	January 2017
The Electronic Properties of Diradicals Salem, Lionel; Rowland, Colin Angewandte Chemie International Edition in English, Vol. 11, Issue 2 https://doi.org/10.1002/anie.197200921	journal	February 1972
Neutral and Charged Biradicals, Zwitterions, Funnels in S1, and Proton Translocation: Their Role in Photochemistry, Photophysics, and Vision Bonačić-Koutecký, Vlasta; Koutecký, Jaroslav; Michl, Josef Angewandte Chemie International Edition in English, Vol. 26, Issue 3 https://doi.org/10.1002/anie.198701701	journal	March 1987
The Multiradical Character of One- and Two-Dimensional Graphene Nanoribbons Plasser, Felix; Pašalić, Hasan; Gerzabek, Martin H. Angewandte Chemie International Edition, Vol. 52, Issue 9 https://doi.org/10.1002/anie.201207671	journal	January 2013
Proposal for Laser Cooling of Complex Polyatomic Molecules Kozyryev, Ivan; Baum, Louis; Matsuda, Kyle ChemPhysChem, Vol. 17, Issue 22 https://doi.org/10.1002/cphc.201601051	journal	November 2016
Visualisation of Electronic Excited‐State Correlation in Real Space Plasser, Felix ChemPhotoChem, Vol. 3, Issue 9 https://doi.org/10.1002/cptc.201900014	journal	April 2019
Q-Chem: an engine for innovation: Q-Chem: an engine for innovation Krylov, Anna I.; Gill, Peter M. W. Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 3, Issue 3 https://doi.org/10.1002/wcms.1122	journal	November 2012
Coupled-cluster theory and its equation-of-motion extensions: Coupled-cluster theory Bartlett, Rodney J. Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 1 https://doi.org/10.1002/wcms.76	journal	July 2011
Size-consistent wave functions for bond-breaking: the equation-of-motion spin-flip model Krylov, Anna I. Chemical Physics Letters, Vol. 338, Issue 4-6 https://doi.org/10.1016/S0009-2614(01)00287-1	journal	April 2001
Characterizing unpaired electrons from the one-particle density matrix Head-Gordon, Martin Chemical Physics Letters, Vol. 372, Issue 3-4 https://doi.org/10.1016/S0009-2614(03)00422-6	journal	April 2003
The predicted infrared spectrum of the hypermetallic molecule CaOCa in its lowest two electronic states and Ostojić, B.; Bunker, P. R.; Schwerdtfeger, P. Journal of Molecular Structure, Vol. 1023 https://doi.org/10.1016/j.molstruc.2012.03.048	journal	September 2012
Characterizing Bonding Patterns in Diradicals and Triradicals by Density-Based Wave Function Analysis: A Uniform Approach Orms, Natalie; Rehn, Dirk R.; Dreuw, Andreas Journal of Chemical Theory and Computation, Vol. 14, Issue 2 https://doi.org/10.1021/acs.jctc.7b01012	journal	January 2018
Benchmarking Excited-State Calculations Using Exciton Properties Mewes, Stefanie A.; Plasser, Felix; Krylov, Anna Journal of Chemical Theory and Computation, Vol. 14, Issue 2 https://doi.org/10.1021/acs.jctc.7b01145	journal	January 2018
Effect of Facial Encumbrance on Excimer Formation and Charge Resonance Stabilization in Model Bichromophoric Assemblies Uhler, Brandon; Ivanov, Maxim V.; Kokkin, Damian The Journal of Physical Chemistry C, Vol. 121, Issue 29 https://doi.org/10.1021/acs.jpcc.7b04255	journal	July 2017
Through-Space or Through-Bond? The Important Role of Cofaciality in Orbital Reordering and Its Implications for Hole (De)stabilization in Polychromophoric Assemblies Ivanov, Maxim V.; Wadumethrige, Shriya H.; Wang, Denan The Journal of Physical Chemistry C, Vol. 121, Issue 29 https://doi.org/10.1021/acs.jpcc.7b05804	journal	July 2017
Optical Control of Reactions between Water and Laser-Cooled Be ⁺ Ions Yang, Tiangang; Li, Anyang; Chen, Gary K. The Journal of Physical Chemistry Letters, Vol. 9, Issue 13 https://doi.org/10.1021/acs.jpclett.8b01437	journal	June 2018
Spin-Flip Equation-of-Motion Coupled-Cluster Electronic Structure Method for a Description of Excited States, Bond Breaking, Diradicals, and Triradicals Krylov, Anna I. Accounts of Chemical Research, Vol. 39, Issue 2 https://doi.org/10.1021/ar0402006	journal	February 2006
Ultracold Molecules under Control! Quéméner, Goulven; Julienne, Paul S. Chemical Reviews, Vol. 112, Issue 9 https://doi.org/10.1021/cr300092g	journal	April 2012
Analysis of Electronic Transitions as the Difference of Electron Attachment and Detachment Densities Head-Gordon, Martin; Grana, Ana M.; Maurice, David The Journal of Physical Chemistry, Vol. 99, Issue 39 https://doi.org/10.1021/j100039a012	journal	September 1995
Is the 1,3,5-Tridehydrobenzene Triradical a Cyclopropenyl Radical Analogue? Lardin, Harvey A.; Nash, John J.; Wenthold, Paul G. Journal of the American Chemical Society, Vol. 124, Issue 42 https://doi.org/10.1021/ja0276570	journal	October 2002
Does π−σ−π Through-Bond Coupling Significantly Increase C−C Bond Lengths? Battersby, Thomas R.; VernonClark, Russell; Siegel, Jay S. Journal of the American Chemical Society, Vol. 119, Issue 30 https://doi.org/10.1021/ja9622315	journal	July 1997
Bonding Patterns in Benzene Triradicals from Structural, Spectroscopic, and Thermochemical Perspectives Cristian, Ana-Maria C.; Shao, Yihan; Krylov, Anna I. The Journal of Physical Chemistry A, Vol. 108, Issue 31 https://doi.org/10.1021/jp049007j	journal	August 2004
Triradicals Krylov, Anna I. The Journal of Physical Chemistry A, Vol. 109, Issue 47 https://doi.org/10.1021/jp0528212	journal	December 2005
The Predicted Spectrum and Singlet–Triplet Interaction of the Hypermetallic Molecule SrOSr Ostojić, B.; Jensen, Per; Schwerdtfeger, P. The Journal of Physical Chemistry A, Vol. 117, Issue 39 https://doi.org/10.1021/jp310531s	journal	March 2013
Spectroscopy, Structure, and Ionization Energy of BeOBe ^† Merritt, Jeremy M.; Bondybey, Vladimir E.; Heaven, Michael C. The Journal of Physical Chemistry A, Vol. 113, Issue 47 https://doi.org/10.1021/jp904653v	journal	November 2009
Laser cooling of a diatomic molecule Shuman, E. S.; Barry, J. F.; DeMille, D. Nature, Vol. 467, Issue 7317 https://doi.org/10.1038/nature09443	journal	September 2010
Magneto-optical trapping of a diatomic molecule Barry, J. F.; McCarron, D. J.; Norrgard, E. B. Nature, Vol. 512, Issue 7514 https://doi.org/10.1038/nature13634	journal	August 2014
Molecules cooled below the Doppler limit Truppe, S.; Williams, H. J.; Hambach, M. Nature Physics, Vol. 13, Issue 12 https://doi.org/10.1038/nphys4241	journal	August 2017
Laser cooling of optically trapped molecules Anderegg, Loïc; Augenbraun, Benjamin L.; Bao, Yicheng Nature Physics, Vol. 14, Issue 9 https://doi.org/10.1038/s41567-018-0191-z	journal	June 2018
Emulating optical cycling centers in polyatomic molecules Li, Ming; Kłos, Jacek; Petrov, Alexander Communications Physics, Vol. 2, Issue 1 https://doi.org/10.1038/s42005-019-0245-2	journal	November 2019
Laser cooling of BeCl and BeBr molecules in an ab initio method Wan, Ming-jie; Shao, Ju-xiang; Huang, Duo-hui Physical Chemistry Chemical Physics, Vol. 17, Issue 40 https://doi.org/10.1039/C5CP03677A	journal	January 2015
Towards a rational design of laser-coolable molecules: insights from equation-of-motion coupled-cluster calculations Ivanov, Maxim V.; Bangerter, Felix H.; Krylov, Anna I. Physical Chemistry Chemical Physics, Vol. 21, Issue 35 https://doi.org/10.1039/C9CP03914G	journal	January 2019
The predicted spectrum of the hypermetallic molecule MgOMg Ostojić, B.; Bunker, P. R.; Schwerdtfeger, P. Physical Chemistry Chemical Physics, Vol. 13, Issue 16 https://doi.org/10.1039/c0cp02996c	journal	January 2011
Electronic states and spin-forbidden cooling transitions of AlH and AlF Wells, Nathan; Lane, Ian C. Physical Chemistry Chemical Physics, Vol. 13, Issue 42 https://doi.org/10.1039/c1cp21313j	journal	January 2011
Naphthalene dimer: Electronic states, excimers, and triplet decay East, Allan L. L.; Lim, Edward C. The Journal of Chemical Physics, Vol. 113, Issue 20 https://doi.org/10.1063/1.1319345	journal	November 2000
Singlet-triplet gaps in diradicals by the spin-flip approach: A benchmark study Slipchenko, Lyudmila V.; Krylov, Anna I. The Journal of Chemical Physics, Vol. 117, Issue 10 https://doi.org/10.1063/1.1498819	journal	September 2002
Analytic gradients for the spin-conserving and spin-flipping equation-of-motion coupled-cluster models with single and double substitutions Levchenko, Sergey V.; Wang, Tao; Krylov, Anna I. The Journal of Chemical Physics, Vol. 122, Issue 22 https://doi.org/10.1063/1.1877072	journal	June 2005
Photodissociation dynamics of the NO dimer. I. Theoretical overview of the ultraviolet singlet excited states Levchenko, Sergey V.; Reisler, Hanna; Krylov, Anna I. The Journal of Chemical Physics, Vol. 125, Issue 8 https://doi.org/10.1063/1.2222355	journal	August 2006
Dyson orbitals for ionization from the ground and electronically excited states within equation-of-motion coupled-cluster formalism: Theory, implementation, and examples Melania Oana, C.; Krylov, Anna I. The Journal of Chemical Physics, Vol. 127, Issue 23 https://doi.org/10.1063/1.2805393	journal	December 2007
Pulsed-field ionization zero electron kinetic energy spectrum of the ground electronic state of BeOBe ⁺ Antonov, Ivan O.; Barker, Beau J.; Heaven, Michael C. The Journal of Chemical Physics, Vol. 134, Issue 4 https://doi.org/10.1063/1.3541255	journal	January 2011
New tools for the systematic analysis and visualization of electronic excitations. I. Formalism Plasser, Felix; Wormit, Michael; Dreuw, Andreas The Journal of Chemical Physics, Vol. 141, Issue 2 https://doi.org/10.1063/1.4885819	journal	July 2014
Entanglement entropy of electronic excitations Plasser, Felix The Journal of Chemical Physics, Vol. 144, Issue 19 https://doi.org/10.1063/1.4949535	journal	May 2016
Ultracold molecules and ultracold chemistry Bell, Martin T.; P. Softley, Timothy Molecular Physics, Vol. 107, Issue 2 https://doi.org/10.1080/00268970902724955	journal	January 2009
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package Shao, Yihan; Gan, Zhengting; Epifanovsky, Evgeny Molecular Physics, Vol. 113, Issue 2 https://doi.org/10.1080/00268976.2014.952696	journal	September 2014
Laser-coolable polyatomic molecules with heavy nuclei Isaev, T. A.; Zaitsevskii, A. V.; Eliav, E. Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 50, Issue 22 https://doi.org/10.1088/1361-6455/aa8f34	journal	October 2017
Challenges of laser-cooling molecular ions Nguyen, Jason H. V.; Viteri, C. Ricardo; Hohenstein, Edward G. New Journal of Physics, Vol. 13, Issue 6 https://doi.org/10.1088/1367-2630/13/6/063023	journal	June 2011
A scalable quantum computing platform using symmetric-top molecules Yu, Phelan; Cheuk, Lawrence W.; Kozyryev, Ivan New Journal of Physics, Vol. 21, Issue 9 https://doi.org/10.1088/1367-2630/ab428d	journal	September 2019
Laser-cooled polyatomic molecules for improved electron electric dipole moment searches Augenbraun, Benjamin L.; Lasner, Zack D.; Frenett, Alexander New Journal of Physics, Vol. 22, Issue 2 https://doi.org/10.1088/1367-2630/ab687b	journal	February 2020
Ultracold molecules for quantum simulation: rotational coherences in CaF and RbCs Blackmore, Jacob A.; Caldwell, Luke; Gregory, Philip D. Quantum Science and Technology, Vol. 4, Issue 1 https://doi.org/10.1088/2058-9565/aaee35	journal	December 2018
Quantum Theory of Many-Particle Systems. I. Physical Interpretations by Means of Density Matrices, Natural Spin-Orbitals, and Convergence Problems in the Method of Configurational Interaction Löwdin, Per-Olov Physical Review, Vol. 97, Issue 6 https://doi.org/10.1103/PhysRev.97.1474	journal	March 1955
Hypermetallic polar molecules for precision measurements O'Rourke, Matthew J.; Hutzler, Nicholas R. Physical Review A, Vol. 100, Issue 2 https://doi.org/10.1103/PhysRevA.100.022502	journal	August 2019
Ab initio study of parity and time-reversal violation in laser-coolable triatomic molecules Gaul, Konstantin; Berger, Robert Physical Review A, Vol. 101, Issue 1 https://doi.org/10.1103/PhysRevA.101.012508	journal	January 2020
Laser cooling and slowing of CaF molecules Zhelyazkova, V.; Cournol, A.; Wall, T. E. Physical Review A, Vol. 89, Issue 5 https://doi.org/10.1103/PhysRevA.89.053416	journal	May 2014
Laser cooling of the alkaline-earth-metal monohydrides: Insights from an ab initio theory study Gao, Yufeng; Gao, Tao Physical Review A, Vol. 90, Issue 5 https://doi.org/10.1103/PhysRevA.90.052506	journal	November 2014
Exciton analysis of many-body wave functions: Bridging the gap between the quasiparticle and molecular orbital pictures Bäppler, Stefanie A.; Plasser, Felix; Wormit, Michael Physical Review A, Vol. 90, Issue 5 https://doi.org/10.1103/PhysRevA.90.052521	journal	November 2014
Candidates for direct laser cooling of diatomic molecules with the simplest Σ 1 − Σ 1 electronic system Li, Chuanliang; Li, Yachao; Ji, Zhonghua Physical Review A, Vol. 97, Issue 6 https://doi.org/10.1103/PhysRevA.97.062501	journal	June 2018
Dipolar quantum logic for freely rotating trapped molecular ions Hudson, Eric R.; Campbell, Wesley C. Physical Review A, Vol. 98, Issue 4 https://doi.org/10.1103/PhysRevA.98.040302	journal	October 2018
2D Magneto-Optical Trapping of Diatomic Molecules Hummon, Matthew T.; Yeo, Mark; Stuhl, Benjamin K. Physical Review Letters, Vol. 110, Issue 14 https://doi.org/10.1103/PhysRevLett.110.143001	journal	April 2013
Polyatomic Candidates for Cooling of Molecules with Lasers from Simple Theoretical Concepts Isaev, Timur A.; Berger, Robert Physical Review Letters, Vol. 116, Issue 6 https://doi.org/10.1103/PhysRevLett.116.063006	journal	February 2016
Sisyphus Laser Cooling of a Polyatomic Molecule Kozyryev, Ivan; Baum, Louis; Matsuda, Kyle Physical Review Letters, Vol. 118, Issue 17 https://doi.org/10.1103/PhysRevLett.118.173201	journal	April 2017
Precision Measurement of Time-Reversal Symmetry Violation with Laser-Cooled Polyatomic Molecules Kozyryev, Ivan; Hutzler, Nicholas R. Physical Review Letters, Vol. 119, Issue 13 https://doi.org/10.1103/PhysRevLett.119.133002	journal	September 2017
Laser Cooled YbF Molecules for Measuring the Electron’s Electric Dipole Moment Lim, J.; Almond, J. R.; Trigatzis, M. A. Physical Review Letters, Vol. 120, Issue 12 https://doi.org/10.1103/PhysRevLett.120.123201	journal	March 2018
3D Magneto-Optical Trap of Yttrium Monoxide Collopy, Alejandra L.; Ding, Shiqian; Wu, Yewei Physical Review Letters, Vol. 121, Issue 21 https://doi.org/10.1103/PhysRevLett.121.213201	journal	November 2018
Quantum Computation with Trapped Polar Molecules DeMille, D. Physical Review Letters, Vol. 88, Issue 6 https://doi.org/10.1103/PhysRevLett.88.067901	journal	January 2002
Ultracold Chemistry Hutson, J. M. Science, Vol. 327, Issue 5967 https://doi.org/10.1126/science.1186703	journal	February 2010
Synthesis of mixed hypermetallic oxide BaOCa ⁺ from laser-cooled reagents in an atom-ion hybrid trap Puri, Prateek; Mills, Michael; Schneider, Christian Science, Vol. 357, Issue 6358 https://doi.org/10.1126/science.aan4701	journal	September 2017
Laser-cooling molecules: Concept, candidates, and supporting hyperfine-resolved measurements of rotational lines in the A-X(0,0) band of CaH Rosa, M. D. The European Physical Journal D, Vol. 31, Issue 2 https://doi.org/10.1140/epjd/e2004-00167-2	journal	November 2004
H- and J-Aggregate Behavior in Polymeric Semiconductors Spano, Frank C.; Silva, Carlos Annual Review of Physical Chemistry, Vol. 65, Issue 1 https://doi.org/10.1146/annurev-physchem-040513-103639	journal	April 2014
Equation-of-Motion Coupled-Cluster Methods for Open-Shell and Electronically Excited Species: The Hitchhiker's Guide to Fock Space Krylov, Anna I. Annual Review of Physical Chemistry, Vol. 59, Issue 1 https://doi.org/10.1146/annurev.physchem.59.032607.093602	journal	May 2008

Cited By (1)

Establishing a nearly closed cycling transition in a polyatomic molecule Baum, Louis; Vilas, Nathaniel B.; Hallas, Christian Physical Review A, Vol. 103, Issue 4 https://doi.org/10.1103/physreva.103.043111	journal	April 2021

Similar Records

Equation-of-motion coupled-cluster method with double electron-attaching operators: Theory, implementation, and benchmarks

Journal Article · 2021 · Journal of Chemical Physics · OSTI ID:1852700

Gulania, Sahil; Kjønstad, Eirik F.; Stanton, John F.; +2 more

Hypermetallic polar molecules for precision measurements

Journal Article · 2019 · Physical Review A · OSTI ID:1592983

O'Rourke, Matthew J.; Hutzler, Nicholas R.

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

Journal Article · 2022 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:1907810

Yu, Phelan; Lopez, Adrian; Goddard III, William A.; +1 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Electronic structure
Metals
Molecular interactions
Molecules
Natural orbitals

Title: Two Cycling Centers in One Molecule: Communication by Through-Bond Interactions and Entanglement of the Unpaired Electrons

Citation Formats

References (69)

Cited By (1)

Similar Records

Related Subjects