Conditional Wave Function Theory: A Unified Treatment of Molecular Structure and Nonadiabatic Dynamics

Overview

Journal J Chem Theory Comput

Publisher American Chemical Society

Specialties Biochemistry
Chemistry

Date 2021 Nov 9

PMID 34752108

Authors

Guillermo Albareda

Kevin Lively

Shunsuke A Sato

Aaron Kelly

Angel Rubio

Affiliations

Soon will be listed here.

Abstract

We demonstrate that a conditional wave function theory enables a unified and efficient treatment of the equilibrium structure and nonadiabatic dynamics of correlated electron-ion systems. The conditional decomposition of the many-body wave function formally recasts the full interacting wave function of a closed system as a set of lower-dimensional (conditional) coupled "slices". We formulate a variational wave function ansatz based on a set of conditional wave function slices and demonstrate its accuracy by determining the structural and time-dependent response properties of the hydrogen molecule. We then extend this approach to include time-dependent conditional wave functions and address paradigmatic nonequilibrium processes including strong-field molecular ionization, laser-driven proton transfer, and nuclear quantum effects induced by a conical intersection. This work paves the road for the application of conditional wave function theory in equilibrium and out-of-equilibrium ab initio molecular simulations of finite and extended systems.

References

Chen H, Sangalli D, Bernardi M . Exciton-Phonon Interaction and Relaxation Times from First Principles. Phys Rev Lett. 2020; 125(10):107401. DOI: 10.1103/PhysRevLett.125.107401. View

Albareda G, Appel H, Franco I, Abedi A, Rubio A . Correlated electron-nuclear dynamics with conditional wave functions. Phys Rev Lett. 2014; 113(8):083003. DOI: 10.1103/PhysRevLett.113.083003. View

Rozzi C, Falke S, Spallanzani N, Rubio A, Molinari E, Brida D . Quantum coherence controls the charge separation in a prototypical artificial light-harvesting system. Nat Commun. 2013; 4:1602. PMC: 3615481. DOI: 10.1038/ncomms2603. View

Albareda G, Bofill J, Tavernelli I, Huarte-Larranaga F, Illas F, Rubio A . Conditional Born-Oppenheimer Dynamics: Quantum Dynamics Simulations for the Model Porphine. J Phys Chem Lett. 2015; 6(9):1529-35. DOI: 10.1021/acs.jpclett.5b00422. View

Eichberger M, Schafer H, Krumova M, Beyer M, Demsar J, Berger H . Snapshots of cooperative atomic motions in the optical suppression of charge density waves. Nature. 2010; 468(7325):799-802. DOI: 10.1038/nature09539. View

Ebbesen T . Hybrid Light-Matter States in a Molecular and Material Science Perspective. Acc Chem Res. 2016; 49(11):2403-2412. DOI: 10.1021/acs.accounts.6b00295. View

Vendrell O, Meyer H . Multilayer multiconfiguration time-dependent Hartree method: implementation and applications to a Henon-Heiles hamiltonian and to pyrazine. J Chem Phys. 2011; 134(4):044135. DOI: 10.1063/1.3535541. View

Suzuki Y, Lacombe L, Watanabe K, Maitra N . Exact Time-Dependent Exchange-Correlation Potential in Electron Scattering Processes. Phys Rev Lett. 2018; 119(26):263401. DOI: 10.1103/PhysRevLett.119.263401. View

Lively K, Albareda G, Sato S, Kelly A, Rubio A . Simulating Vibronic Spectra without Born-Oppenheimer Surfaces. J Phys Chem Lett. 2021; 12(12):3074-3081. PMC: 8020382. DOI: 10.1021/acs.jpclett.1c00073. View

10.

Kelly A, van Zon R, Schofield J, Kapral R . Mapping quantum-classical Liouville equation: projectors and trajectories. J Chem Phys. 2012; 136(8):084101. DOI: 10.1063/1.3685420. View

11.

Kreibich T, Gross E . Multicomponent density-functional theory for electrons and nuclei. Phys Rev Lett. 2001; 86(14):2984-7. DOI: 10.1103/PhysRevLett.86.2984. View

12.

Hertzog M, Wang M, Mony J, Borjesson K . Strong light-matter interactions: a new direction within chemistry. Chem Soc Rev. 2019; 48(3):937-961. PMC: 6365945. DOI: 10.1039/c8cs00193f. View

13.

Zhao L, Wildman A, Pavosevic F, Tully J, Hammes-Schiffer S, Li X . Excited State Intramolecular Proton Transfer with Nuclear-Electronic Orbital Ehrenfest Dynamics. J Phys Chem Lett. 2021; 12(14):3497-3502. DOI: 10.1021/acs.jpclett.1c00564. View

14.

Schwengelbeck , Faisal . Ionization of the one-dimensional Coulomb atom in an intense laser field. Phys Rev A. 1994; 50(1):632-640. DOI: 10.1103/physreva.50.632. View

15.

Hubener H, De Giovannini U, Schafer C, Andberger J, Ruggenthaler M, Faist J . Engineering quantum materials with chiral optical cavities. Nat Mater. 2020; 20(4):438-442. DOI: 10.1038/s41563-020-00801-7. View

16.

Ananth N . Mapping variable ring polymer molecular dynamics: a path-integral based method for nonadiabatic processes. J Chem Phys. 2013; 139(12):124102. DOI: 10.1063/1.4821590. View

17.

Khoromskaia V, Khoromskij B . Tensor numerical methods in quantum chemistry: from Hartree-Fock to excitation energies. Phys Chem Chem Phys. 2015; 17(47):31491-509. DOI: 10.1039/c5cp01215e. View

18.

Schaupp T, Engel V . A classical ride through a conical intersection. J Chem Phys. 2019; 150(3):034301. DOI: 10.1063/1.5080399. View

19.

Blaga C, Xu J, DiChiara A, Sistrunk E, Zhang K, Agostini P . Imaging ultrafast molecular dynamics with laser-induced electron diffraction. Nature. 2012; 483(7388):194-7. DOI: 10.1038/nature10820. View

20.

Yabana , Bertsch . Time-dependent local-density approximation in real time. Phys Rev B Condens Matter. 1996; 54(7):4484-4487. DOI: 10.1103/physrevb.54.4484. View