Non-adiabatic quantum interference in the ultracold Li + LiNa → Li2 + Na reaction

Kendrick, Brian Kent; Li, Hui; Li, Ming; Kotochigova, Svetlana; Croft, James F. E.; Balakrishnan, Naduvalath

doi:10.1039/d0cp05499b

Title: Non-adiabatic quantum interference in the ultracold Li + LiNa → Li₂ + Na reaction

Journal Article · Fri Feb 12 00:00:00 EST 2021 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/d0cp05499b· OSTI ID:1825404

^[1];

^[2]; Li, Ming ^[2];

^[2];

^[3];

^[4]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Temple Univ., Philadelphia, PA (United States)
Dodd-Walls Centre for Photonic and Quantum Technologies, Dunedin (New Zealand); Univ. of Otago, Dunedin (New Zealand)
Univ. of Nevada, Las Vegas, NV (United States)

Electronically non-adiabatic effects play an important role in many chemical reactions. However, how these effects manifest in cold and ultracold chemistry remains largely unexplored. Here for the first time we present from first principles the non-adiabatic quantum dynamics of the reactive scattering between ultracold alkali-metal LiNa molecules and Li atoms. We show that non-adiabatic dynamics induces quantum interference effects that dramatically alter the ultracold rotationally resolved reaction rate coefficients. The interference effect arises from the conical intersection between the ground and an excited electronic state that is energetically accessible even for ultracold collisions. These unique interference effects might be exploited for quantum control applications such as a quantum molecular switch. The non-adiabatic dynamics are based on full-dimensional ab initio potential energy surfaces for the two electronic states that includes the non-adiabatic couplings and an accurate treatment of the long-range interactions. A statistical analysis of rotational populations of the Li2 product reveals a Poisson distribution implying the underlying classical dynamics are chaotic. The Poisson distribution is robust and amenable to experimental verification and appears to be a universal property of ultracold reactions involving alkali metal dimers.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; National Science Foundation (NSF)

Grant/Contract Number:: 89233218CNA000001; PHY-1806334; W911NF-19-1-0283

OSTI ID:: 1825404

Report Number(s):: LA-UR-20-24177

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 23, Issue 9; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (65)

Quantum control of molecular collisions at 1 kelvin Perreault, William E.; Mukherjee, Nandini; Zare, Richard N. Science, Vol. 358, Issue 6361 https://doi.org/10.1126/science.aao3116	journal	October 2017
Extension of the Pack–Parker quantum reactive scattering method to include direct calculation of time delays Darakjian, Zareh; Hayes, Edward F. The Journal of Chemical Physics, Vol. 93, Issue 12 https://doi.org/10.1063/1.459268	journal	December 1990
Interaction of the van der Waals Type Between Three Atoms Axilrod, B. M.; Teller, E. The Journal of Chemical Physics, Vol. 11, Issue 6 https://doi.org/10.1063/1.1723844	journal	June 1943
Quantum interference in H + HD → H ₂ + D between direct abstraction and roaming insertion pathways Xie, Yurun; Zhao, Hailin; Wang, Yufeng Science, Vol. 368, Issue 6492 https://doi.org/10.1126/science.abb1564	journal	May 2020
Treatment of intershell correlation effects in a b i n i t i o calculations by use of core polarization potentials. Method and application to alkali and alkaline earth atoms Müller, Wolfgang; Flesch, Joachim; Meyer, Wilfried The Journal of Chemical Physics, Vol. 80, Issue 7 https://doi.org/10.1063/1.447083	journal	April 1984
Direct observation of bimolecular reactions of ultracold KRb molecules Hu, M. -G.; Liu, Y.; Grimes, D. D. Science, Vol. 366, Issue 6469 https://doi.org/10.1126/science.aay9531	journal	November 2019
ARPACK Users' Guide Lehoucq, R. B.; Sorensen, D. C.; Yang, C. Software, Environments, and Tools https://doi.org/10.1137/1.9780898719628	book	January 1998
Conical Intersections: Electronic Structure, Dynamics and Spectroscopy Domcke, Wolfgang; Yarkony, David R.; Köppel, Horst Advanced Series in Physical Chemistry, Vol. 15 https://doi.org/10.1142/5406	book	July 2004
A general method for constructing multidimensional molecular potential energy surfaces from ab initio calculations Ho, Tak‐San; Rabitz, Herschel The Journal of Chemical Physics, Vol. 104, Issue 7 https://doi.org/10.1063/1.470984	journal	February 1996
Unified theory of nuclear reactions Feshbach, Herman Annals of Physics, Vol. 5, Issue 4 https://doi.org/10.1016/0003-4916(58)90007-1	journal	December 1958
Universal Scattering of Ultracold Atoms and Molecules in Optical Potentials Li, Hui; Li, Ming; Makrides, Constantinos Atoms, Vol. 7, Issue 1 https://doi.org/10.3390/atoms7010036	journal	March 2019
On the Behavior of Cross Sections Near Thresholds Wigner, Eugene P. Physical Review, Vol. 73, Issue 9 https://doi.org/10.1103/PhysRev.73.1002	journal	May 1948
Pseudopotential calculations including core-valence correlation: Alkali compounds Fuentealba, P.; Szentpály, L. v.; Stoll, H. Journal of Molecular Structure: THEOCHEM, Vol. 93 https://doi.org/10.1016/0166-1280(83)80104-3	journal	May 1983
The molecular Aharonov–Bohm effect redux Zygelman, B. Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 50, Issue 2 https://doi.org/10.1088/1361-6455/50/2/025102	journal	December 2016
An optimal adiabatic-to-diabatic transformation of the 1 2A′ and 2 2A′ states of H3 Abrol, Ravinder; Kuppermann, Aron The Journal of Chemical Physics, Vol. 116, Issue 3 https://doi.org/10.1063/1.1419257	journal	January 2002
Symmetry and the geometric phase in ultracold hydrogen-exchange reactions Croft, J. F. E.; Hazra, J.; Balakrishnan, N. The Journal of Chemical Physics, Vol. 147, Issue 7 https://doi.org/10.1063/1.4998226	journal	August 2017
The High-Lying Vibrational Levels and Dissociation Energy of the a3Σ+u State of 7Li2 Linton, C.; Martin, F.; Ross, A. J. Journal of Molecular Spectroscopy, Vol. 196, Issue 1 https://doi.org/10.1006/jmsp.1999.7858	journal	July 1999
An efficient internally contracted multiconfiguration–reference configuration interaction method Werner, Hans‐Joachim; Knowles, Peter J. The Journal of Chemical Physics, Vol. 89, Issue 9 https://doi.org/10.1063/1.455556	journal	November 1988
Perspective: Ultracold molecules and the dawn of cold controlled chemistry Balakrishnan, N. The Journal of Chemical Physics, Vol. 145, Issue 15 https://doi.org/10.1063/1.4964096	journal	October 2016
Superposition of reactive and nonreactive scattering amplitudes in the presence of a conical intersection Mead, C. Alden The Journal of Chemical Physics, Vol. 72, Issue 6 https://doi.org/10.1063/1.439600	journal	March 1980
Generalized discrete variable approximation in quantum mechanics Light, J. C.; Hamilton, I. P.; Lill, J. V. The Journal of Chemical Physics, Vol. 82, Issue 3 https://doi.org/10.1063/1.448462	journal	February 1985
The multichannel log-derivative method for scattering calculations Johnson, B. R. Journal of Computational Physics, Vol. 13, Issue 3 https://doi.org/10.1016/0021-9991(73)90049-1	journal	November 1973
Complex scattering lengths in multi-channel atom–molecule collisions Balakrishnan, N.; Kharchenko, V.; Forrey, R. C. Chemical Physics Letters, Vol. 280, Issue 1-2 https://doi.org/10.1016/S0009-2614(97)01052-X	journal	November 1997
A second order multiconfiguration SCF procedure with optimum convergence Werner, Hans‐Joachim; Knowles, Peter J. The Journal of Chemical Physics, Vol. 82, Issue 11 https://doi.org/10.1063/1.448627	journal	June 1985
Universality and chaoticity in ultracold K+KRb chemical reactions Croft, J. F. E.; Makrides, C.; Li, M. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15897	journal	July 2017
Theory and applications of atomic and ionic polarizabilities Mitroy, J.; Safronova, M. S.; Clark, Charles W. Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 43, Issue 20 https://doi.org/10.1088/0953-4075/43/20/202001	journal	October 2010
Geometric phase effects in H+O ₂ scattering. I. Surface function solutions in the presence of a conical intersection Kendrick, Brian; Pack, Russell T. The Journal of Chemical Physics, Vol. 104, Issue 19 https://doi.org/10.1063/1.471460	journal	May 1996
Cold quantum-controlled rotationally inelastic scattering of HD with H2 and D2 reveals collisional partner reorientation Perreault, William E.; Mukherjee, Nandini; Zare, Richard N. Nature Chemistry, Vol. 10, Issue 5 https://doi.org/10.1038/s41557-018-0028-5	journal	April 2018
Constructive and Destructive Interference in Nonadiabatic Tunneling via Conical Intersections Xie, Changjian; Kendrick, Brian K.; Yarkony, David R. Journal of Chemical Theory and Computation, Vol. 13, Issue 5 https://doi.org/10.1021/acs.jctc.7b00124	journal	April 2017
Hyperspherical surface functions for nonzero total angular momentum. I. Eckart singularities Kendrick, Brian K.; Pack, Russell T.; Walker, Robert B. The Journal of Chemical Physics, Vol. 110, Issue 14 https://doi.org/10.1063/1.478574	journal	April 1999
Interactive tool for visualization of adiabatic adjustment in APH coordinates for computational studies of vibrational motion and chemical reactions Teplukhin, Alexander; Babikov, Dmitri Chemical Physics Letters, Vol. 614 https://doi.org/10.1016/j.cplett.2014.09.015	journal	October 2014
Importance of Geometric Phase Effects in Ultracold Chemistry Hazra, Jisha; Kendrick, Brian K.; Balakrishnan, Naduvalath The Journal of Physical Chemistry A, Vol. 119, Issue 50 https://doi.org/10.1021/acs.jpca.5b06410	journal	September 2015
An efficient method for the evaluation of coupling coefficients in configuration interaction calculations Knowles, Peter J.; Werner, Hans-Joachim Chemical Physics Letters, Vol. 145, Issue 6 https://doi.org/10.1016/0009-2614(88)87412-8	journal	April 1988
Certain Explicit Relationships between Phase Shift and Scattering Potential Levinson, Norman Physical Review, Vol. 89, Issue 4 https://doi.org/10.1103/PhysRev.89.755	journal	February 1953
An efficient second-order MC SCF method for long configuration expansions Knowles, Peter J.; Werner, Hans-Joachim Chemical Physics Letters, Vol. 115, Issue 3 https://doi.org/10.1016/0009-2614(85)80025-7	journal	April 1985
On the determination of Born–Oppenheimer nuclear motion wave functions including complications due to conical intersections and identical nuclei Mead, C. Alden; Truhlar, Donald G. The Journal of Chemical Physics, Vol. 70, Issue 5 https://doi.org/10.1063/1.437734	journal	March 1979
Reactions of ultracold alkali-metal dimers Żuchowski, Piotr S.; Hutson, Jeremy M. Physical Review A, Vol. 81, Issue 6 https://doi.org/10.1103/PhysRevA.81.060703	journal	June 2010
Cold and ultracold molecules: science, technology and applications Carr, Lincoln D.; DeMille, David; Krems, Roman V. New Journal of Physics, Vol. 11, Issue 5 https://doi.org/10.1088/1367-2630/11/5/055049	journal	May 2009
( $X$ )1 $^{1} Σ^{+}$ state of LiNa studied by Fourier-transform spectroscopy Steinke, Michael; Knöckel, Horst; Tiemann, Eberhard Physical Review A, Vol. 85, Issue 4 https://doi.org/10.1103/PhysRevA.85.042720	journal	April 2012
Non-adiabatic quantum reactive scattering in hyperspherical coordinates Kendrick, Brian K. The Journal of Chemical Physics, Vol. 148, Issue 4 https://doi.org/10.1063/1.5014989	journal	January 2018
The geometric phase controls ultracold chemistry Kendrick, B. K.; Hazra, Jisha; Balakrishnan, N. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8918	journal	July 2015
Geometric Phase Effects in Nonadiabatic Dynamics near Conical Intersections Ryabinkin, Ilya G.; Joubert-Doriol, Loïc; Izmaylov, Artur F. Accounts of Chemical Research, Vol. 50, Issue 7 https://doi.org/10.1021/acs.accounts.7b00220	journal	June 2017
Proper construction of ab initio global potential surfaces with accurate long-range interactions Ho, Tak-San; Rabitz, Herschel The Journal of Chemical Physics, Vol. 113, Issue 10 https://doi.org/10.1063/1.1288268	journal	September 2000
Unraveling the Stereodynamics of Cold Controlled $HD − H_{2}$ Collisions Croft, James F. E.; Balakrishnan, Naduvalath; Huang, Meng Physical Review Letters, Vol. 121, Issue 11 https://doi.org/10.1103/PhysRevLett.121.113401	journal	September 2018
Quantum dynamics of complex-forming bimolecular reactions Guo, H. International Reviews in Physical Chemistry, Vol. 31, Issue 1 https://doi.org/10.1080/0144235X.2011.649999	journal	January 2012
Extensive analysis of the X1Σ+g ground state of 7Li2 by laser-induced fluorescence Fourier transform spectrometry Barakat, B.; Bacis, R.; Carrot, F. Chemical Physics, Vol. 102, Issue 1-2 https://doi.org/10.1016/0301-0104(86)85133-3	journal	February 1986
Theoretical Study of Geometric Phase Effects in the Hydrogen-Exchange Reaction Juanes-Marcos, J. C. Science, Vol. 309, Issue 5738 https://doi.org/10.1126/science.1114890	journal	August 2005
Quantal Phase Factors Accompanying Adiabatic Changes Berry, M. V. Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 392, Issue 1802 https://doi.org/10.1098/rspa.1984.0023	journal	March 1984
Accurate quantum calculations on three-body collisions in recombination and collision-induced dissociation. I. Converged probabilities for the H+Ne2 system Parker, Gregory A.; Walker, Robert B.; Kendrick, Brian K. The Journal of Chemical Physics, Vol. 117, Issue 13 https://doi.org/10.1063/1.1503313	journal	October 2002
Geometric Phase Effects in Chemical Reaction Dynamics and Molecular Spectra Kendrick, Brian K. The Journal of Physical Chemistry A, Vol. 107, Issue 35 https://doi.org/10.1021/jp021865x	journal	September 2003
Quantum chaos in atom–diatom reactive collisions Honvault, Pascal; Launay, Jean-Michel Chemical Physics Letters, Vol. 329, Issue 3-4 https://doi.org/10.1016/S0009-2614(00)01024-1	journal	October 2000
Statistical quantum mechanical approach to diatom–diatom capture dynamics and application to ultracold KRb + KRb reaction Yang, Dongzheng; Huang, Jing; Hu, Xixi The Journal of Chemical Physics, Vol. 152, Issue 24 https://doi.org/10.1063/5.0014805	journal	June 2020
Controlled state-to-state atom-exchange reaction in an ultracold atom–dimer mixture Rui, Jun; Yang, Huan; Liu, Lan Nature Physics, Vol. 13, Issue 7 https://doi.org/10.1038/nphys4095	journal	April 2017
Quantum-State Controlled Chemical Reactions of Ultracold Potassium-Rubidium Molecules Ospelkaus, S.; Ni, K. -K.; Wang, D. Science, Vol. 327, Issue 5967 https://doi.org/10.1126/science.1184121	journal	February 2010
Nonadiabatic Ultracold Quantum Reactive Scattering of Hydrogen with Vibrationally Excited HD( v = 5–9) Kendrick, Brian K. The Journal of Physical Chemistry A, Vol. 123, Issue 46 https://doi.org/10.1021/acs.jpca.9b07318	journal	October 2019
Observation of the geometric phase effect in the H + HD → H ₂ + D reaction Yuan, Daofu; Guan, Yafu; Chen, Wentao Science, Vol. 362, Issue 6420 https://doi.org/10.1126/science.aav1356	journal	December 2018
Non-adiabatic quantum reactive scattering calculations for the ultracold hydrogen exchange reaction: H + H2( $v = 4 - 8, j = 0$ ) $\to$ H + H2( $v^{'}, j^{'}$ ) Kendrick, Brian K. Chemical Physics, Vol. 515 https://doi.org/10.1016/j.chemphys.2018.07.001	journal	November 2018
Geometric Phase Appears in the Ultracold Hydrogen Exchange Reaction Kendrick, B. K.; Hazra, Jisha; Balakrishnan, N. Physical Review Letters, Vol. 115, Issue 15 https://doi.org/10.1103/PhysRevLett.115.153201	journal	October 2015
A Method of Diatomics in Molecules. I. General Theory and Application to H ₂ O Ellison, Frank O. Journal of the American Chemical Society, Vol. 85, Issue 22 https://doi.org/10.1021/ja00905a002	journal	November 1963
Toolkit for the Construction of Reproducing Kernel-Based Representations of Data: Application to Multidimensional Potential Energy Surfaces Unke, Oliver T.; Meuwly, Markus Journal of Chemical Information and Modeling, Vol. 57, Issue 8 https://doi.org/10.1021/acs.jcim.7b00090	journal	July 2017
Quantum reactive scattering in three dimensions using hyperspherical (APH) coordinates. Theory Pack, Russell T.; Parker, Gregory A. The Journal of Chemical Physics, Vol. 87, Issue 7 https://doi.org/10.1063/1.452944	journal	October 1987
Statistical Theory of the Energy Levels of Complex Systems. I Dyson, Freeman J. Journal of Mathematical Physics, Vol. 3, Issue 1 https://doi.org/10.1063/1.1703773	journal	January 1962
Collisions of ultracold ²³ Na ⁸⁷ Rb molecules with controlled chemical reactivities Ye, Xin; Guo, Mingyang; González-Martínez, Maykel L. Science Advances, Vol. 4, Issue 1 https://doi.org/10.1126/sciadv.aaq0083	journal	January 2018
Long-Lived Ultracold Molecules with Electric and Magnetic Dipole Moments Rvachov, Timur M.; Son, Hyungmok; Sommer, Ariel T. Physical Review Letters, Vol. 119, Issue 14 https://doi.org/10.1103/PhysRevLett.119.143001	journal	October 2017
Long-lived complexes and signatures of chaos in ultracold $K_{2}$ +Rb collisions Croft, J. F. E.; Balakrishnan, N.; Kendrick, B. K. Physical Review A, Vol. 96, Issue 6 https://doi.org/10.1103/PhysRevA.96.062707	journal	December 2017

Similar Records

Quantum reactive scattering calculations for the cold and ultracold Li + LiNa → Li₂ + Na reaction

Journal Article · Sun Mar 28 00:00:00 EDT 2021 · Journal of Chemical Physics · OSTI ID:1825404

Kendrick, Brian K.

Non-adiabatic quantum reactive scattering calculations for the ultracold hydrogen exchange reaction: H + H₂(

v = 4 - 8, j = 0

)

\to

H + H₂(

v^{'}, j^{'}

)

Journal Article · Wed Jul 04 00:00:00 EDT 2018 · Chemical Physics · OSTI ID:1825404

Kendrick, Brian K.

Importance of geometric phase effects in ultracold chemistry

Journal Article · Fri Aug 28 00:00:00 EDT 2015 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory · OSTI ID:1825404

Hazra, Jisha; Kendrick, Brian K.; Balakrishnan, Naduvalath

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Inorganic and physical chemistry
non-adiabatic
quantum dynamics
ultracold chemistry
cold molecules

Title: Non-adiabatic quantum interference in the ultracold Li + LiNa → Li2 + Na reaction

Citation Formats

References (65)

Similar Records

Related Subjects

Title: Non-adiabatic quantum interference in the ultracold Li + LiNa → Li₂ + Na reaction