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Journal of Chemical Theory and Computation

Variational Squeezed Davydov Ansatz for Realistic Chemical Systems with Nonlinear Vibronic Coupling

Jiarui Zeng, Yao Yao

Published Jan 31, 2022• 7 citations
Publisher

Abstract

Chemical systems normally possess strong nonlinear vibronic couplings at both zero and finite temperature. For the lowest-order quadratic couplings, here, we introduce a squeezing operator into a variational coherent-state-based method, Davydov ansatz, to simulate the quantum dynamics and the respective spectroscopy. Two molecular systems, pyrazine and the 2-pyridone dimer, are taken as calculated model systems, both of which involve nontrivial quadratic vibronic couplings in high- and low-frequency regions, respectively. Upon a comparison with the benchmarks, the method manifests its advantage for nonlinear couplings. The squeezed bases are also proven to be applicable for the finite temperature by adapting with the thermofield dynamics.

DOI
10.1021/acs.jctc.1c00859

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Chemical systems normally possess strong nonlinear vibronic couplings at both zero and finite temperature. For the lowest-order quadratic couplings, here, we introduce a squeezing operator into a variational coherent-state-based method, Davydov ansatz, to simulate the quantum dynamics and the respective spectroscopy. Two molecular systems, pyrazine and the 2-pyridone dimer, are taken as calculated model systems, both of which involve nontrivial quadratic vibronic couplings in high- and low-frequency regions, respectively. Upon a comparison with the benchmarks, the method manifests its advantage for nonlinear couplings. The squeezed bases are also proven to be applicable for the finite temperature by adapting with the thermofield dynamics.
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Electronic and/or vibronic coherence has been found by recent ultrafast spectroscopy experiments in many chemical, biological, and material systems. This indicates that there are strong and complicated interactions between electronic states and vibration modes in realistic chemical systems. Therefore, simulations of quantum dynamics with a large number of electronic and vibrational degrees of freedom are highly desirable. Due to the efficient compression and localized representation of quantum states in the matrix-product state (MPS) formulation, time-evolution methods based on the MPS framework, which we summarily refer to as tDMRG (time-dependent density-matrix renormalization group) methods, are considered to be promising candidates to study the quantum dynamics of realistic chemical systems. In this work, we benchmark the performances of four different tDMRG methods, including global Taylor, global Krylov, and local one-site and two-site time-dependent variational principles (1TDVP and 2TDVP), with a comparison to multiconfiguration time-dependent Hartree and experimental results. Two typical chemical systems of internal conversion and singlet fission are investigated: one containing strong and high-order local and nonlocal electron-vibration couplings and the other exhibiting a continuous phonon bath. The comparison shows that the tDMRG methods (particularly, the 2TDVP method) can describe the full quantum dynamics in large chemical systems accurately and efficiently. Several key parameters in the tDMRG calculation including the truncation error threshold, time interval, and ordering of local sites were also investigated to strike the balance between efficiency and accuracy of results.
This Perspective presents an overview of the development of the hierarchy of Davydov's Ansätze and a few of their applications in many-body problems in computational chemical physics. Davydov's solitons originated in the investigation of vibrational energy transport in proteins in the 1970s. Momentum-space projection of these solitary waves turned up to be accurate variational ground-state wave functions for the extended Holstein molecular crystal model, lending unambiguous evidence to the absence of formal quantum phase transitions in Holstein systems. The multiple Davydov Ansätze have been proposed, with increasing Ansatz multiplicity, as incremental improvements of their single-Ansatz parents. For a given Hamiltonian, the time-dependent variational formalism is utilized to extract accurate dynamic and spectroscopic properties using Davydov's Ansätze as its trial states. A quantity proven to disappear for large multiplicities, the Ansatz relative deviation is introduced to quantify how closely the Schrödinger equation is obeyed. Three finite-temperature extensions to the time-dependent variation scheme are elaborated, i.e., the Monte Carlo importance sampling, the method of thermofield dynamics, and the method of displaced number states. To demonstrate the versatility of the methodology, this Perspective provides applications of Davydov's Ansätze to the generalized Holstein Hamiltonian, variants of the spin-boson model, and systems of cavity-assisted singlet fission, where accurate dynamic and spectroscopic properties of the many-body systems are given by the Davydov trial states.
We perform benchmark simulations using the time-dependent variational approach with the multiple Davydov Ansatz (mDA) to study real-time nonequilibrium dynamics in a single qubit model coupled to two thermal baths with distinct temperatures. A broad region of the parameter space has been investigated, accompanied by a detailed analysis of the convergence behavior of the mDA method. In addition, we have compared our mD2 results to those from two widely adopted, numerically "exact" techniques: the methods of hierarchical equations of motion (HEOM) and the quasi-adiabatic path integral (QUAPI). It is found that the mDA approach in combination with thermal field dynamics yields numerically accurate, convergent results in nearly all regions of the parameter space examined, including those that pose serious challenges for QUAPI and HEOM. Our results reveal that mDA offers a highly adaptable framework capable of capturing long-time dynamics, even in challenging regimes where other methods face limitations. These findings underscore the potential of mDA as a versatile tool for exploring quantum thermodynamics, energy transfer processes, and non-equilibrium quantum systems.
By combining coherence thermofield dynamics with the single-Hessian approximation, we enable simulations of low- to medium-resolution vibronic spectra of weakly anharmonic systems at nonzero temperatures, at negligible additional cost relative to zero-temperature calculations. Single-Hessian coherence thermofield Gaussian wavepacket dynamics is exact in any harmonic potential, provided that the reference Hessian is that of the final surface. When applied to Morse systems of increasing anharmonicity and varying temperature, this method successfully captures excited-state anharmonicity and key temperature-dependent spectral features, including hot bands and broadening. By combining the method with on-the-fly ab initio dynamics, we demonstrate its utility by computing the absorption spectra of naphthalene, aminocoumarin C450, and phenyl radical, and the photoelectron spectrum of SeO2−_{2}^{-}2−​ . Within the ab initio single-Hessian approximation, after the zero-temperature spectrum is obtained at the cost of classical molecular dynamics (on the order of hours), all nonzero-temperature spectra are computed in seconds.
A vibrational electronic-thermofield coupled cluster (VE-TFCC) approach is developed to calculate thermal properties of non-adiabatic vibronic coupling systems. The thermofield (TF) theory and a mixed linear exponential ansatz based on second-quantized Bosonic construction operators are introduced to propagate the thermal density operator as a “pure state” in the Bogoliubov representation. Through this compact representation of the thermal density operator, the approach is basis-set-free and scales classically (polynomial) as the number of degrees of freedoms (DoF) in the system increases. The VE-TFCC approach is benchmarked with small test models and a real molecular compound (CoF 4 – anion) against the conventional sum over states (SOS) method and applied to calculate thermochemistry properties of a gas-phase reaction: CoF 3 + F – → CoF 4 – . Results shows that the VE-TFCC approach, in conjunction with vibronic models, provides an effective protocol for calculating thermodynamic properties of vibronic coupling systems.