Dynamic signatures of electronically nonadiabatic coupling in sodium hydride: a rigorous test for the symmetric quasi-classical model applied to realistic, ab initio electronic states in the adiabatic representation
Abstract
Sodium hydride (NaH) in the gas phase presents a seemingly simple electronic structure making it a potentially tractable system for the detailed investigation of nonadiabatic molecular dynamics from both computational and experimental standpoints. The single vibrational degree of freedom, as well as the strong nonadiabatic coupling that arises from the excited electronic states taking on considerable ionic character, provides a realistic chemical system to test the accuracy of quasi-classical methods to model population dynamics where the results are directly comparable against quantum mechanical benchmarks. Here, using a simulated pump–probe type experiment, this work presents computational predictions of population transfer through the avoided crossings of NaH via symmetric quasi-classical Meyer–Miller (SQC/MM), Ehrenfest, and exact quantum dynamics on realistic, ab initio potential energy surfaces. The main driving force for population transfer arises from the ground vibrational level of the D1Σ+ adiabatic state that is embedded in the manifold of near-dissociation C1Σ+ vibrational states. When coupled through a sharply localized first-order derivative coupling most of the population transfers between t = 15 and t = 30 fs depending on the initially excited vibronic wavepacket. While quantum mechanical effects are expected due to the reduced mass of NaH, predictions of the population dynamics frommore »
- Authors:
-
- Univ. of California, Berkeley, CA (United States)
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF); USDOE
- OSTI Identifier:
- 1906823
- Alternate Identifier(s):
- OSTI ID: 1845050
- Grant/Contract Number:
- AC02-05CH11231; CHE-1856707
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Chemistry Chemical Physics. PCCP
- Additional Journal Information:
- Journal Volume: 24; Journal Issue: 8; Journal ID: ISSN 1463-9076
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Talbot, Justin J., Head-Gordon, Martin, Miller, William H., and Cotton, Stephen J. Dynamic signatures of electronically nonadiabatic coupling in sodium hydride: a rigorous test for the symmetric quasi-classical model applied to realistic, ab initio electronic states in the adiabatic representation. United States: N. p., 2022.
Web. doi:10.1039/d1cp04090a.
Talbot, Justin J., Head-Gordon, Martin, Miller, William H., & Cotton, Stephen J. Dynamic signatures of electronically nonadiabatic coupling in sodium hydride: a rigorous test for the symmetric quasi-classical model applied to realistic, ab initio electronic states in the adiabatic representation. United States. https://doi.org/10.1039/d1cp04090a
Talbot, Justin J., Head-Gordon, Martin, Miller, William H., and Cotton, Stephen J. Fri .
"Dynamic signatures of electronically nonadiabatic coupling in sodium hydride: a rigorous test for the symmetric quasi-classical model applied to realistic, ab initio electronic states in the adiabatic representation". United States. https://doi.org/10.1039/d1cp04090a. https://www.osti.gov/servlets/purl/1906823.
@article{osti_1906823,
title = {Dynamic signatures of electronically nonadiabatic coupling in sodium hydride: a rigorous test for the symmetric quasi-classical model applied to realistic, ab initio electronic states in the adiabatic representation},
author = {Talbot, Justin J. and Head-Gordon, Martin and Miller, William H. and Cotton, Stephen J.},
abstractNote = {Sodium hydride (NaH) in the gas phase presents a seemingly simple electronic structure making it a potentially tractable system for the detailed investigation of nonadiabatic molecular dynamics from both computational and experimental standpoints. The single vibrational degree of freedom, as well as the strong nonadiabatic coupling that arises from the excited electronic states taking on considerable ionic character, provides a realistic chemical system to test the accuracy of quasi-classical methods to model population dynamics where the results are directly comparable against quantum mechanical benchmarks. Here, using a simulated pump–probe type experiment, this work presents computational predictions of population transfer through the avoided crossings of NaH via symmetric quasi-classical Meyer–Miller (SQC/MM), Ehrenfest, and exact quantum dynamics on realistic, ab initio potential energy surfaces. The main driving force for population transfer arises from the ground vibrational level of the D1Σ+ adiabatic state that is embedded in the manifold of near-dissociation C1Σ+ vibrational states. When coupled through a sharply localized first-order derivative coupling most of the population transfers between t = 15 and t = 30 fs depending on the initially excited vibronic wavepacket. While quantum mechanical effects are expected due to the reduced mass of NaH, predictions of the population dynamics from both the SQC/MM and Ehrenfest models perform remarkably well against the quantum dynamics benchmark. Additionally, an analysis of the vibronic structure in the nonadiabatically coupled regime is presented using a variational eigensolver methodology.},
doi = {10.1039/d1cp04090a},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 8,
volume = 24,
place = {United States},
year = {Fri Feb 04 00:00:00 EST 2022},
month = {Fri Feb 04 00:00:00 EST 2022}
}
Works referenced in this record:
The Requisite Electronic Structure Theory To Describe Photoexcited Nonadiabatic Dynamics: Nonadiabatic Derivative Couplings and Diabatic Electronic Couplings
journal, May 2015
- Subotnik, Joseph E.; Alguire, Ethan C.; Ou, Qi
- Accounts of Chemical Research, Vol. 48, Issue 5
Derivative Couplings with Built-In Electron-Translation Factors: Application to Benzene
journal, July 2012
- Fatehi, Shervin; Subotnik, Joseph E.
- The Journal of Physical Chemistry Letters, Vol. 3, Issue 15
On the adiabatic representation of Meyer-Miller electronic-nuclear dynamics
journal, August 2017
- Cotton, Stephen J.; Liang, Ruibin; Miller, William H.
- The Journal of Chemical Physics, Vol. 147, Issue 6
A classical analog for electronic degrees of freedom in nonadiabatic collision processes
journal, April 1979
- Meyera), Hans‐Dieter; Miller, William H.
- The Journal of Chemical Physics, Vol. 70, Issue 7
Study of the exciton dynamics in perylene bisimide (PBI) aggregates with symmetrical quasiclassical dynamics based on the Meyer–Miller mapping Hamiltonian
journal, January 2020
- Zheng, Jie; Peng, Jiawei; Xie, Yu
- Physical Chemistry Chemical Physics, Vol. 22, Issue 32
A walk through the approximations of ab initio multiple spawning
journal, April 2018
- Mignolet, Benoit; Curchod, Basile F. E.
- The Journal of Chemical Physics, Vol. 148, Issue 13
Disentangling conical intersection and coherent molecular dynamics in methyl bromide with attosecond transient absorption spectroscopy
journal, July 2019
- Timmers, Henry; Zhu, Xiaolei; Li, Zheng
- Nature Communications, Vol. 10, Issue 1
Symmetrical windowing for quantum states in quasi-classical trajectory simulations: Application to electronically non-adiabatic processes
journal, December 2013
- Cotton, Stephen J.; Miller, William H.
- The Journal of Chemical Physics, Vol. 139, Issue 23
Ab initio two-component Ehrenfest dynamics
journal, September 2015
- Ding, Feizhi; Goings, Joshua J.; Liu, Hongbin
- The Journal of Chemical Physics, Vol. 143, Issue 11
Ab Initio Nonadiabatic Quantum Molecular Dynamics
journal, February 2018
- Curchod, Basile F. E.; Martínez, Todd J.
- Chemical Reviews, Vol. 118, Issue 7
ExoMol molecular line lists – X. The spectrum of sodium hydride
journal, May 2015
- Rivlin, Tom; Lodi, Lorenzo; Yurchenko, Sergei N.
- Monthly Notices of the Royal Astronomical Society, Vol. 451, Issue 1
Mixing of ionic and covalent configurations for sodium hydride, potassium hydride, and hydromagnesium(1+). Potential energy curves and couplings between molecular states
journal, December 1975
- Numrich, Robert W.; Truhlar, Donald G.
- The Journal of Physical Chemistry, Vol. 79, Issue 25
Dissociation energies and potential energy functions for the ground X 1 Σ + and “avoided-crossing” A 1 Σ + states of NaH
journal, January 2015
- Walji, Sadru-Dean; Sentjens, Katherine M.; Le Roy, Robert J.
- The Journal of Chemical Physics, Vol. 142, Issue 4
Dynamics at Conical Intersections
journal, April 2018
- Schuurman, Michael S.; Stolow, Albert
- Annual Review of Physical Chemistry, Vol. 69, Issue 1
Quasi-Diabatic Scheme for Nonadiabatic On-the-Fly Simulations
journal, October 2019
- Zhou, Wanghuai; Mandal, Arkajit; Huo, Pengfei
- The Journal of Physical Chemistry Letters, Vol. 10, Issue 22
Isomerization Through Conical Intersections
journal, May 2007
- Levine, Benjamin G.; Martínez, Todd J.
- Annual Review of Physical Chemistry, Vol. 58, Issue 1
Direct mapping of curve-crossing dynamics in IBr by attosecond transient absorption spectroscopy
journal, July 2019
- Kobayashi, Yuki; Chang, Kristina F.; Zeng, Tao
- Science, Vol. 365, Issue 6448
Communication: GAIMS—Generalized Ab Initio Multiple Spawning for both internal conversion and intersystem crossing processes
journal, March 2016
- Curchod, Basile F. E.; Rauer, Clemens; Marquetand, Philipp
- The Journal of Chemical Physics, Vol. 144, Issue 10
Ab initio symmetric quasi-classical approach to investigate molecular Tully models
journal, August 2021
- Weight, Braden M.; Mandal, Arkajit; Huo, Pengfei
- The Journal of Chemical Physics, Vol. 155, Issue 8
A symmetrical quasi-classical windowing model for the molecular dynamics treatment of non-adiabatic processes involving many electronic states
journal, March 2019
- Cotton, Stephen J.; Miller, William H.
- The Journal of Chemical Physics, Vol. 150, Issue 10
Cross sections for low-energy inelastic H Na collisions
journal, March 2010
- Belyaev, A. K.; Barklem, P. S.; Dickinson, A. S.
- Physical Review A, Vol. 81, Issue 3
Perspective: Nonadiabatic dynamics theory
journal, December 2012
- Tully, John C.
- The Journal of Chemical Physics, Vol. 137, Issue 22
Classical molecular dynamics simulation of electronically non-adiabatic processes
journal, January 2016
- Miller, William H.; Cotton, Stephen J.
- Faraday Discussions, Vol. 195
Analytic derivative couplings for spin-flip configuration interaction singles and spin-flip time-dependent density functional theory
journal, August 2014
- Zhang, Xing; Herbert, John M.
- The Journal of Chemical Physics, Vol. 141, Issue 6
The Fourier grid Hamiltonian method for bound state eigenvalues and eigenfunctions
journal, September 1989
- Marston, C. Clay; Balint‐Kurti, Gabriel G.
- The Journal of Chemical Physics, Vol. 91, Issue 6
Diabatization by Machine Intelligence
journal, September 2020
- Shu, Yinan; Truhlar, Donald G.
- Journal of Chemical Theory and Computation, Vol. 16, Issue 10
Ground state properties of alkali and alkaline–earth hydrides
journal, November 1987
- Fuentealba, P.; Reyes, O.; Stoll, H.
- The Journal of Chemical Physics, Vol. 87, Issue 9
Analytic derivative couplings between configuration-interaction-singles states with built-in electron-translation factors for translational invariance
journal, December 2011
- Fatehi, Shervin; Alguire, Ethan; Shao, Yihan
- The Journal of Chemical Physics, Vol. 135, Issue 23
Symmetric quasi-classical dynamics with quasi-diabatic propagation scheme
journal, July 2018
- Sandoval C., Juan Sebastián; Mandal, Arkajit; Huo, Pengfei
- The Journal of Chemical Physics, Vol. 149, Issue 4
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package
journal, September 2014
- Shao, Yihan; Gan, Zhengting; Epifanovsky, Evgeny
- Molecular Physics, Vol. 113, Issue 2
Predicting Accurate Electronic Excitation Transfer Rates via Marcus Theory with Boys or Edmiston−Ruedenberg Localized Diabatization †
journal, August 2010
- Subotnik, Joseph E.; Vura-Weis, Josh; Sodt, Alex J.
- The Journal of Physical Chemistry A, Vol. 114, Issue 33
Theoretical study of the X 1 Σ + states of the alkali hydrides NaH–CsH
journal, November 1986
- Langhoff, Stephen R.; Bauschlicher, Charles W.; Partridge, Harry
- The Journal of Chemical Physics, Vol. 85, Issue 9
A new symmetrical quasi-classical model for electronically non-adiabatic processes: Application to the case of weak non-adiabatic coupling
journal, October 2016
- Cotton, Stephen J.; Miller, William H.
- The Journal of Chemical Physics, Vol. 145, Issue 14
Dissociation energy of the ground state of NaH
journal, July 2010
- Huang, Hsien-Yu; Lu, Tsai-Lien; Whang, Thou-Jen
- The Journal of Chemical Physics, Vol. 133, Issue 4
Nonadiabatic Events and Conical Intersections
journal, May 2011
- Matsika, Spiridoula; Krause, Pascal
- Annual Review of Physical Chemistry, Vol. 62, Issue 1
Characterization of the outer well of NaH C1Σ+ state by fluorescence depletion spectroscopy
journal, June 2010
- Huang, Hsien-Yu; Chang, Yao-Yuan; Liao, Mei-Hui
- Chemical Physics Letters, Vol. 493, Issue 1-3
Trajectory-adjusted electronic zero point energy in classical Meyer-Miller vibronic dynamics: Symmetrical quasiclassical application to photodissociation
journal, May 2019
- Cotton, Stephen J.; Miller, William H.
- The Journal of Chemical Physics, Vol. 150, Issue 19
Permutationally Restrained Diabatization by Machine Intelligence
journal, January 2021
- Shu, Yinan; Varga, Zoltan; Sampaio de Oliveira-Filho, Antonio Gustavo
- Journal of Chemical Theory and Computation, Vol. 17, Issue 2
Ab initio Ehrenfest dynamics
journal, August 2005
- Li, Xiaosong; Tully, John C.; Schlegel, H. Bernhard
- The Journal of Chemical Physics, Vol. 123, Issue 8
Recent Progress in Surface Hopping: 2011–2015
journal, May 2016
- Wang, Linjun; Akimov, Alexey; Prezhdo, Oleg V.
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 11
On-the-fly ab initio molecular dynamics with multiconfigurational Ehrenfest method
journal, December 2012
- Saita, Kenichiro; Shalashilin, Dmitrii V.
- The Journal of Chemical Physics, Vol. 137, Issue 22
Time-dependent density functional theory Ehrenfest dynamics: Collisions between atomic oxygen and graphite clusters
journal, April 2007
- Isborn, Christine M.; Li, Xiaosong; Tully, John C.
- The Journal of Chemical Physics, Vol. 126, Issue 13
Excited state diabatization on the cheap using DFT: Photoinduced electron and hole transfer
journal, December 2020
- Mao, Yuezhi; Montoya-Castillo, Andrés; Markland, Thomas E.
- The Journal of Chemical Physics, Vol. 153, Issue 24
Ab Initio Multiple Spawning: Photochemistry from First Principles Quantum Molecular Dynamics
journal, June 2000
- Ben-Nun, M.; Quenneville, Jason; Martínez, Todd J.
- The Journal of Physical Chemistry A, Vol. 104, Issue 22
Calculations of non-adiabatic couplings within equation-of-motion coupled-cluster framework: Theory, implementation, and validation against multi-reference methods
journal, January 2018
- Faraji, Shirin; Matsika, Spiridoula; Krylov, Anna I.
- The Journal of Chemical Physics, Vol. 148, Issue 4
Conical Intersections: Theory, Computation and Experiment
book, November 2011
- Domcke, Wolfgang; Yarkony, David R.; Köppel, Horst
- Advanced Series in Physical Chemistry
Quasidiabatic states described by coupled-cluster theory
journal, May 2009
- Ichino, Takatoshi; Gauss, Jürgen; Stanton, John F.
- The Journal of Chemical Physics, Vol. 130, Issue 17
On-the-Fly Symmetrical Quasi-Classical Dynamics with Meyer–Miller Mapping Hamiltonian for the Treatment of Nonadiabatic Dynamics at Conical Intersections
journal, May 2021
- Hu, Deping; Xie, Yu; Peng, Jiawei
- Journal of Chemical Theory and Computation, Vol. 17, Issue 6
Model space diabatization for quantum photochemistry
journal, February 2015
- Li, Shaohong L.; Truhlar, Donald G.; Schmidt, Michael W.
- The Journal of Chemical Physics, Vol. 142, Issue 6
A Symmetrical Quasi-Classical Spin-Mapping Model for the Electronic Degrees of Freedom in Non-Adiabatic Processes
journal, August 2015
- Cotton, Stephen J.; Miller, William H.
- The Journal of Physical Chemistry A, Vol. 119, Issue 50
Introductory lecture: Nonadiabatic effects in chemical dynamics
journal, January 2004
- Jasper, Ahren W.; Zhu, Chaoyuan; Nangia, Shikha
- Faraday Discussions, Vol. 127
Beyond Time-Dependent Density Functional Theory Using Only Single Excitations: Methods for Computational Studies of Excited States in Complex Systems
journal, April 2016
- Herbert, John M.; Zhang, Xing; Morrison, Adrian F.
- Accounts of Chemical Research, Vol. 49, Issue 5
Surface hopping from the perspective of quantum–classical Liouville dynamics
journal, December 2016
- Kapral, Raymond
- Chemical Physics, Vol. 481
Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics
journal, April 2018
- Crespo-Otero, Rachel; Barbatti, Mario
- Chemical Reviews, Vol. 118, Issue 15
Performance evaluation of the symmetrical quasi-classical dynamics method based on Meyer-Miller mapping Hamiltonian in the treatment of site-exciton models
journal, November 2018
- Xie, Yu; Zheng, Jie; Lan, Zhenggang
- The Journal of Chemical Physics, Vol. 149, Issue 17
Analytic evaluation of the nonadiabatic coupling vector between excited states using equation-of-motion coupled-cluster theory
journal, September 2009
- Tajti, Attila; Szalay, Péter G.
- The Journal of Chemical Physics, Vol. 131, Issue 12
Symmetrical Windowing for Quantum States in Quasi-Classical Trajectory Simulations
journal, March 2013
- Cotton, Stephen J.; Miller, William H.
- The Journal of Physical Chemistry A, Vol. 117, Issue 32
The symmetrical quasi-classical approach to electronically nonadiabatic dynamics applied to ultrafast exciton migration processes in semiconducting polymers
journal, July 2018
- Liang, Ruibin; Cotton, Stephen J.; Binder, Robert
- The Journal of Chemical Physics, Vol. 149, Issue 4
Molecular dynamics with electronic transitions
journal, July 1990
- Tully, John C.
- The Journal of Chemical Physics, Vol. 93, Issue 2
Vibronic Dynamics of Photodissociating ICN from Simulations of Ultrafast X‐Ray Absorption Spectroscopy
journal, August 2020
- Morzan, Uriel N.; Videla, Pablo E.; Soley, Micheline B.
- Angewandte Chemie, Vol. 132, Issue 45
Theoretical Study of 1 Σ + States of Alkali Hydride XH Molecule (X = Na, K and Rb) in Adiabatic and Nonadiabatic Representations
journal, July 2009
- Khelifi, Neji
- The Journal of Physical Chemistry A, Vol. 113, Issue 29
Systematic trends in electronic properties of alkali hydridesThis article is part of a Special Issue on Spectroscopy at the University of New Brunswick in honour of Colan Linton and Ron Lees.
journal, May 2009
- Aymar, Mireille; Deiglmayr, Johannes; Dulieu, Olivier
- Canadian Journal of Physics, Vol. 87, Issue 5
Spectroscopy and Structure of the Alkali Hydride Diatomic Molecules and their Ions
journal, January 1991
- Stwalley, William C.; Zemke, Warren T.; Yang, Sze Cheng
- Journal of Physical and Chemical Reference Data, Vol. 20, Issue 1
Observation of double-well potential of NaH C 1 Σ + state: Deriving the dissociation energy of its ground state
journal, March 2018
- Chu, Chia-Ching; Huang, Hsien-Yu; Whang, Thou-Jen
- The Journal of Chemical Physics, Vol. 148, Issue 11