Exact Quantum Dynamics Research Articles

Surface hopping with a manifold of electronic states. I. Incorporating surface-leaking to capture lifetimes.

We investigate the incorporation of the surface-leaking (SL) algorithm into Tully's fewest-switches surface hopping (FSSH) algorithm to simulate some electronic relaxation induced by an electronic bath in conjunction with some electronic transitions between discrete states. The resulting SL-FSSH algorithm is benchmarked against exact quantum scattering calculations for three one-dimensional model problems. The results show excellent agreement between SL-FSSH and exact quantum dynamics in the wide band limit, suggesting the potential for a SL-FSSH algorithm. Discrepancies and failures are investigated in detail to understand the factors that will limit the reliability of SL-FSSH, especially the wide band approximation. Considering the easiness of implementation and the low computational cost, we expect this method to be useful in studying processes involving both a continuum of electronic states (where electronic dynamics are probabilistic) and processes involving only a few electronic states (where non-adiabatic processes cannot ignore short-time coherence).

The exact forces on classical nuclei in non-adiabatic charge transfer.

The decomposition of electronic and nuclear motion presented in Abedi et al. [Phys. Rev. Lett. 105, 123002 (2010)] yields a time-dependent potential that drives the nuclear motion and fully accounts for the coupling to the electronic subsystem. Here, we show that propagation of an ensemble of independent classical nuclear trajectories on this exact potential yields dynamics that are essentially indistinguishable from the exact quantum dynamics for a model non-adiabatic charge transfer problem. We point out the importance of step and bump features in the exact potential that are critical in obtaining the correct splitting of the quasiclassical nuclear wave packet in space after it passes through an avoided crossing between two Born-Oppenheimer surfaces and analyze their structure. Finally, an analysis of the exact potentials in the context of trajectory surface hopping is presented, including preliminary investigations of velocity-adjustment and the force-induced decoherence effect.

A continued fraction resummation form of bath relaxation effect in the spin-boson model.

In the spin-boson model, a continued fraction form is proposed to systematically resum high-order quantum kinetic expansion (QKE) rate kernels, accounting for the bath relaxation effect beyond the second-order perturbation. In particular, the analytical expression of the sixth-order QKE rate kernel is derived for resummation. With higher-order correction terms systematically extracted from higher-order rate kernels, the resummed quantum kinetic expansion approach in the continued fraction form extends the Pade approximation and can fully recover the exact quantum dynamics as the expansion order increases.

Large scale exact quantum dynamics calculations: Ten thousand quantum states of acetonitrile

‘Exact’ quantum dynamics (EQD) calculations of the vibrational spectrum of acetonitrile (CH3CN) are performed, using two different methods: (1) phase-space-truncated momentum-symmetrized Gaussian basis and (2) correlated truncated harmonic oscillator basis. In both cases, a simple classical phase space picture is used to optimize the selection of individual basis functions—leading to drastic reductions in basis size, in comparison with existing methods. Massive parallelization is also employed. Together, these tools—implemented into a single, easy-to-use computer code—enable a calculation of tens of thousands of vibrational states of CH3CN to an accuracy of 0.001–10cm−1.

SU(3) semiclassical representation of quantum dynamics of interacting spins.

We present a formalism for simulating quantum dynamics of lattice spin-1 systems by first introducing local hidden variables and then doing semiclassical (truncated Wigner) approximation in the extended phase space. In this way, we exactly take into account the local on-site Hamiltonian and approximately treat spin-spin interactions. In particular, we represent each spin with eight classical SU(3) variables. Three of them represent the usual spin components and five others are hidden variables representing local spin-spin correlations. We compare our formalism with exact quantum dynamics of fully connected spin systems and find very good agreement. As an application, we discuss quench dynamics of a Bose-Hubbard model near the superfluid-insulator transition for a 3D lattice system consisting of 1000 sites.

Ultracold chemistry with alkali-metal–rare-earth molecules

A first principles study of the dynamics of $^6$Li($^{2}$S) + $^6$Li$^{174}$Yb($^2\Sigma^+$)$ \to ^6$Li$_2(^1\Sigma^+$) + $^{174}$Yb($^1$S) reaction is presented at cold and ultracold temperatures. The computations involve determination and analytic fitting of a three-dimensional potential energy surface for the Li$_2$Yb system and quantum dynamics calculations of varying complexities, ranging from exact quantum dynamics within the close-coupling scheme, to statistical quantum treatment, and universal models. It is demonstrated that the two simplified methods yield zero-temperature limiting reaction rate coefficients in reasonable agreement with the full close-coupling calculations. The effect of the three-body term in the interaction potential is explored by comparing quantum dynamics results from a pairwise potential that neglects the three-body term to that derived from the full interaction potential. Inclusion of the three-body term in the close-coupling calculations was found to reduce the limiting rate coefficients by a factor of two. The reaction exoergicity populates vibrational levels as high as $v=19$ of the $^6$Li$_2$ molecule in the limit of zero collision energy. Product vibrational distributions from the close-coupling calculations reveal sensitivity to inclusion of three-body forces in the interaction potential. Overall, the results indicate that a simplified model based on the long-range potential is able to yield reliable values of the total reaction rate coefficient in the ultracold limit but a more rigorous approach based on statistical quantum or quantum close-coupling methods is desirable when product rovibrational distribution is required.

How to calculate linear absorption spectra with lifetime broadening using fewest switches surface hopping trajectories: a simple generalization of ground-state Kubo theory.

In this paper, we develop a surface hopping approach for calculating linear absorption spectra using ensembles of classical trajectories propagated on both the ground and excited potential energy surfaces. We demonstrate that our method allows the dipole-dipole correlation function to be determined exactly for the model problem of two shifted, uncoupled harmonic potentials with the same harmonic frequency. For systems where nonadiabatic dynamics and electronic relaxation are present, preliminary results show that our method produces spectra in better agreement with the results of exact quantum dynamics calculations than spectra obtained using the standard ground-state Kubo formalism. As such, our proposed surface hopping approach should find immediate use for modeling condensed phase spectra, especially for expensive calculations using ab initio potential energy surfaces.

Can the ring polymer molecular dynamics method be interpreted as real time quantum dynamics?

The ring polymer molecular dynamics (RPMD) method has gained popularity in recent years as a simple approximation for calculating real time quantum correlation functions in condensed media. However, the extent to which RPMD captures real dynamical quantum effects and why it fails under certain situations have not been clearly understood. Addressing this issue has been difficult in the absence of a genuine justification for the RPMD algorithm starting from the quantum Liouville equation. To this end, a new and exact path integral formalism for the calculation of real time quantum correlation functions is presented in this work, which can serve as a rigorous foundation for the analysis of the RPMD method as well as providing an alternative derivation of the well established centroid molecular dynamics method. The new formalism utilizes the cyclic symmetry of the imaginary time path integral in the most general sense and enables the expression of Kubo-transformed quantum time correlation functions as that of physical observables pre-averaged over the imaginary time path. Upon filtering with a centroid constraint function, the formulation results in the centroid dynamics formalism. Upon filtering with the position representation of the imaginary time path integral, we obtain an exact quantum dynamics formalism involving the same variables as the RPMD method. The analysis of the RPMD approximation based on this approach clarifies that an explicit quantum dynamical justification does not exist for the use of the ring polymer harmonic potential term (imaginary time kinetic energy) as implemented in the RPMD method. It is analyzed why this can cause substantial errors in nonlinear correlation functions of harmonic oscillators. Such errors can be significant for general correlation functions of anharmonic systems. We also demonstrate that the short time accuracy of the exact path integral limit of RPMD is of lower order than those for finite discretization of path. The present quantum dynamics formulation also serves as the basis for developing new quantum dynamical methods that utilize the cyclic nature of the imaginary time path integral.

Ballistic Spreading of Entanglement in a Diffusive Nonintegrable System

We study the time evolution of the entanglement entropy of a one-dimensional nonintegrable spin chain, starting from random nonentangled initial pure states. We use exact diagonalization of a nonintegrable quantum Ising chain with transverse and longitudinal fields to obtain the exact quantum dynamics. We show that the entanglement entropy increases linearly with time before finite-size saturation begins, demonstrating a ballistic spreading of the entanglement, while the energy transport in the same system is diffusive. Thus, we explicitly demonstrate that the spreading of entanglement is much faster than the energy diffusion in this nonintegrable system.

Nonlinear Absorption Dynamics Using Field‐Induced Surface Hopping: Zinc Porphyrin in Water

We wish to present the application of our field-induced surface-hopping (FISH) method to simulate nonlinear absorption dynamics induced by strong nonresonant laser fields. We provide a systematic comparison of the FISH approach with exact quantum dynamics simulations on a multistate model system and demonstrate that FISH allows for accurate simulations of nonlinear excitation processes including multiphoton electronic transitions. In particular, two different approaches for simulating two-photon transitions are compared. The first approach is essentially exact and involves the solution of the time-dependent Schrödinger equation in an extended manifold of excited states, while in the second one only transiently populated nonessential states are replaced by an effective quadratic coupling term, and dynamics is performed in a considerably smaller manifold of states. We illustrate the applicability of our method to complex molecular systems by simulating the linear and nonlinear laser-driven dynamics in zinc (Zn) porphyrin in the gas phase and in water. For this purpose, the FISH approach is connected with the quantum mechanical-molecular mechanical approach (QM/MM) which is generally applicable to large classes of complex systems. Our findings that multiphoton absorption and dynamics increase the population of higher excited states of Zn porphyrin in the nonlinear regime, in particular in solution, provides a means for manipulating excited-state properties, such as transient absorption dynamics and electronic relaxation.

ROVIBRATIONAL BOUND STATES OF THE Ar2Ne COMPLEX

We report exact quantum dynamics calculations of the eigenstate energy levels for the bound rovibrational states of the Ar2Ne complex, across the range of J values for which such states are observed (J = 0–35). All calculations have been carried out using the ScalIT suite of parallel codes. These codes employ a combination of highly efficient methods, including phase-space optimized discrete variable representation, optimal separable basis, and preconditioned inexact spectral transform (PIST) methods, together with an effective massive parallelization scheme. The Ar2Ne energy levels were computed using a pair-wise Aziz potential plus a three-body correction, in Jacobi co-ordinates. Effective potentials for the radial co-ordinates are constructed, which reveal important physical insight into the two distinct dissociation pathways, Ar2Ne → NeAr + Ar and Ar2Ne → Ar2 + Ne . A calculation of the bound vibrational (J = 0) levels, computed using the Tang–Toennies potential, is also performed for comparison with results from the previous literature.

Accurate quantum dynamics calculations using symmetrized Gaussians on a doubly dense Von Neumann lattice

In a series of earlier articles [B. Poirier, J. Theor. Comput. Chem. 2, 65 (2003); B. Poirier and A. Salam, J. Chem. Phys. 121, 1690 (2004); and ibid. 121, 1704 (2004)], a new method was introduced for performing exact quantum dynamics calculations. The method uses a "weylet" basis set (orthogonalized Weyl-Heisenberg wavelets) combined with phase space truncation, to defeat the exponential scaling of CPU effort with system dimensionality--the first method ever able to achieve this long-standing goal. Here, we develop another such method, which uses a much more convenient basis of momentum-symmetrized Gaussians. Despite being non-orthogonal, symmetrized Gaussians are collectively local, allowing for effective phase space truncation. A dimension-independent code for computing energy eigenstates of both coupled and uncoupled systems has been created, exploiting massively parallel algorithms. Results are presented for model isotropic uncoupled harmonic oscillators and coupled anharmonic oscillators up to 27 dimensions. These are compared with the previous weylet calculations (uncoupled harmonic oscillators up to 15 dimensions), and found to be essentially just as efficient. Coupled system results are also compared to corresponding exact results obtained using a harmonic oscillator basis, and also to approximate results obtained using first-order perturbation theory up to the maximum dimensionality for which the latter may be feasibly obtained (four dimensions).

Numerically exact quantum dynamics of bosons with time-dependent interactions of harmonic type

The exactly solvable quantum many-particle model with harmonic one- and two-particle interaction terms is extended to include time-dependency. We show that when the external trap potential and finite-range interparticle interaction have a time-dependency the exact solutions of the corresponding time-dependent many-boson Schr\"odinger equation are still available. We use these exact solutions to benchmark the recently developed multiconfigurational time-dependent Hartree method for bosons (MCTDHB) [Phys. Rev. Lett. {\bf 99}, 030402 (2007), Phys. Rev. A {\bf 77}, 033613 (2008)]. In particular, we benchmark the MCTDHB method for: (i) the ground state; (ii) the breathing many-body dynamics activated by a quench scenario where the interparticle interaction strength is suddenly turned on to a finite value; (iii) the non-equilibrium dynamic for driven scenarios where both the trap- and interparticle-interaction potentials are {\it time-dependent}. Excellent convergence of the ground state and dynamics is demonstrated. The great relevance of the self-consistency and time-adaptivity, which are the intrinsic features of the MCTDHB method, is demonstrated by contrasting the MCTDHB predictions and those obtained within the standard full configuration interaction method spanning the Fock space of the same size, but utilizing as one-particle basis set the fixed-shape eigenstates of the one-particle potential. Connections of the model's results to ultra-cold Bose-Einstein condensed systems are addressed.

Second Josephson excitations beyond mean field as a toy model for thermal pressure: exact quantum dynamics and the quantum phase model

A simple four-mode Bose–Hubbard model with intrinsic time-scale separation can be considered as a paradigm for mesoscopic quantum systems in thermal contact. In our previous work, we showed that in addition to coherent particle exchange, a novel slow collective excitation can be identified by a series of Holstein–Primakoff transformations. This resonant energy exchange mode is not predicted by the linear Bogoliubov theory, and its frequency is sensitive to interactions among Bogoliubov quasi-particles; it may be referred to as a second Josephson oscillation, in analogy to the second sound mode of liquid helium II. In this paper, we will explore this system beyond the Gross–Pitaevskii mean-field regime. We directly compare the classical mean-field dynamics to the exact full quantum many-particle dynamics and show good agreement over a wide range of system parameters. The second Josephson frequency becomes imaginary for stronger interactions however, indicating dynamical instability of the symmetric state. By means of a generalized quantum phase model for the full four-mode system, we then show that, in this regime, high-energy Bogoliubov quasiparticles tend to accumulate in one pair of sites, while the actual particles preferentially occupy the opposite pair. We interpret this as a simple model of thermal pressure.

Cooling of quantum systems through optimal control and dissipation

Based on an exact non-Markovian open systems quantum dynamics, we demonstrate how to reduce the entropy of an open system through a cooperative effect of driving and dissipation. We illustrate the controlled dynamics in phase space in terms of Wigner functions and discuss the applicability of approximate approaches using master equations.

Reduced and Exact Quantum Dynamics of the Vibrational Relaxation of a Molecular System Interacting with a Finite-Dimensional Bath

We investigate the vibrational relaxation of a Morse oscillator, nonlinearly coupled to a finite-dimensional bath of harmonic oscillators at zero temperature, using two different approaches: Reduced dynamics with the help of the Lindblad formalism of reduced density matrix theory in combination with Fermi's Golden Rule, and exact dynamics (within the chosen model) with the multiconfiguration time-dependent Hartree (MCTDH) method. Two different models have been constructed, the situation where the bath spectrum is exactly resonant with the anharmonic oscillator transition frequencies, and the case for which the subsystem is slightly off-resonant with the environment. At short times, reduced dynamics calculations describe the relaxation process qualitatively well but fail to reproduce recurrences observed with MCTDH for longer times. Lifetimes of all the vibrational levels of the Morse oscillator have been calculated, and both Lindblad and MCTDH results show the same dependence of the lifetimes on the initial vibrational state quantum number. A prediction, which should be generic for adsorbate systems is a striking, sharp increase of lifetimes of the subsystem vibrational levels close to the dissociation limit. This is contradictory with harmonic/linear extrapolation laws, which predict a monotonic decrease of the lifetime with initial vibrational quantum number.

Evaluation of the importance of spin-orbit couplings in the nonadiabatic quantum dynamics with quantum fidelity and with its efficient “on-the-fly” ab initio semiclassical approximation

We propose to measure the importance of spin-orbit couplings (SOCs) in the nonadiabatic molecular quantum dynamics rigorously with quantum fidelity. To make the criterion practical, quantum fidelity is estimated efficiently with the multiple-surface dephasing representation (MSDR). The MSDR is a semiclassical method that includes nuclear quantum effects through interference of mixed quantum-classical trajectories without the need for the Hessian of potential energy surfaces. Two variants of the MSDR are studied, in which the nuclei are propagated either with the fewest-switches surface hopping or with the locally mean field dynamics. The fidelity criterion and MSDR are first tested on one-dimensional model systems amenable to numerically exact quantum dynamics. Then, the MSDR is combined with "on-the-fly" computed electronic structure to measure the importance of SOCs and nonadiabatic couplings in the photoisomerization dynamics of CH(2)NH(2)(+) considering 20 electronic states and in the collision of F + H(2) considering six electronic states.

Flux-correlation approach to characterizing reaction pathways in quantum systems: a study of condensed-phase proton-coupled electron transfer

We introduce a simple method for characterizing reactive pathways in quantum systems. Flux auto-correlation and cross-correlation functions are employed to develop a quantitative measure of dynamical coupling in quantum transition events, such as reactive tunnelling and resonant energy transfer. We utilize the method to study condensed-phase proton-coupled electron transfer (PCET) reactions and to determine the relative importance of competing concerted and sequential reaction pathways. Results presented here include numerically exact quantum dynamics simulations for model condensed-phase PCET reactions. This work demonstrates the applicability of the new method for the analysis of both approximate and exact quantum dynamics simulations.

Herman–Kluk allows analysis of quantum discrete breathers in higher dimensional systems

Discrete breathers (DBs) provide an important example of spatial localization of energy encountered in non-linear many-body systems. Studying the quantum equivalent of DBs has always been restricted to small or simple systems. We show that Herman–Kluk (HK), a well studied semi-classical method, can be used successfully to observe the dynamics of a quantum state for systems that are too large for conventional quantum mechanical methods. HK reduces the growth of computational cost that comes with increase of system size. We show that HK performs very well for a quartic potential, when compared to exact quantum dynamics. As an application of the approach, we compute and analyse the spectrum of quantum DBs in a seven-dimensional potential. This result advances our ability to model experimental systems in many fields, including solar energy harvesting, quantum computing, nano-science, medicine, etc.

First principle study of proton transfer in the green fluorescent protein (GFP): Ab initio PES in a cluster model

In this paper we perform high level complete active space self-consistent field (CASSCF) and multi-reference configuration interaction (MRCI) calculations to generate three-dimensional potential energy surfaces for the proton chain transfer in the green fluorescent protein (GFP) based on a minimal quantum mechanical cluster model. Both the electronic ground state and the first excited state are considered within an approximate rigid model. We focus on the energetic terms of the proton transfers in this paper, and the exact quantum dynamics simulations for proton transfer on the ground and excited states will be reported later. Our results from MRCI quantum mechanical calculations are contrasted with those of other computational studies using both CASPT2 method and DFT method, and are compared with the experimental findings for GFP in the full protein environment.