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The Journal of Chemical Physics

Algebraic time-dependent variational approach to dynamical calculations

Shenghua Shi, HERSCHEL A. RABITZ

Published Jun 15, 1988• 23 citations
Publisher

Abstract

A set of time-dependent basis states is obtained with a group of unitary transformations generated by a Lie algebra. Applying the time-dependent variational principle to the trial function subspace constructed from the linear combination of the time-dependent basis states gives rise to a set of ‘‘classical’’ equations of motion for the group parameters and the expansion coefficients from which the time evolution of the system state can be determined. The formulation is developed for a general Lie algebra as well as for the commonly encountered algebra containing homogeneous polynominal products of the coordinate Q and momentum P operators (or equivalently the boson creation a° and annihilation a operators) of order 0, 1, and 2. Explicit expressions for the transition amplitudes are derived by virtue of the cannonical transformation properties of the unitary transformation. The applicability of the present formalism in a variety of problems is implied by two illustrative examples: (a) a parametric amplifier; (b) the collinear collision of an atom with a Morse oscillator.

DOI
10.1063/1.454315

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A set of time-dependent basis states is obtained with a group of unitary transformations generated by a Lie algebra. Applying the time-dependent variational principle to the trial function subspace constructed from the linear combination of the time-dependent basis states gives rise to a set of ‘‘classical’’ equations of motion for the group parameters and the expansion coefficients from which the time evolution of the system state can be determined. The formulation is developed for a general Lie algebra as well as for the commonly encountered algebra containing homogeneous polynominal products of the coordinate Q and momentum P operators (or equivalently the boson creation a° and annihilation a operators) of order 0, 1, and 2. Explicit expressions for the transition amplitudes are derived by virtue of the cannonical transformation properties of the unitary transformation. The applicability of the present formalism in a variety of problems is implied by two illustrative examples: (a) a parametric amplifier; (b) the collinear collision of an atom with a Morse oscillator.
The time-dependent variational principle associates to a Hamiltonian quantum system a set of trajectories running on a classical phase space with canonical equations of motion. When the quantum observables generate a Lie group G and the states are taken as functions on an appropriate homogeneous quotient space space := G/G 0 under under G , they can be equipped with a classical Poisson bracket which reproduces the commutators of the Lie group. The quantum system maps into a classical system whose equations of motion are governed by the expectation value of the quantum Hamiltonian H. We consider examples of this construction and show that the analysis of generalized classical systems provides insight into quantum many-body dynamics like chemical reactions.
We discuss the Schr\"odinger equation with a time-dependent Hamiltonian that can be written as a linear combination of operators which span a finite-dimensional Lie algebra. The equations of motion for the operators in the Heisenberg representation are shown to be useful in calculating matrix elements and transition probabilities, as well as in obtaining the time-evolution operator. A general time-dependent one-dimensional bilinear Hamiltonian is considered as an illustrative example, and the product form for the time-evolution operator is shown to be global.
The unitary operator V ( t ) that diagonalizes the time-dependent quadratic Hamiltonian (TDQH) into a time-dependent harmonic oscillator (TDHO) is obtained using a Lie algebra. The method involves a factorization of the TDQH into a TDHO through a unitary Bogoliubov transformation in terms of creation and annihilation operators with time-dependent coefficients. It is shown that this operator can be easily achieved by means of the factorization, together with the commonly known Wei–Norman theorem. We discuss the conditions under which this unitary operator converges to the evolution operator U ( t ) of the Schrödinger equation for the TDQH, giving then a straightforward calculation of the evolution operator with respect to the procedures published in the literature.
We study quantum dynamics generated by time-dependent Hamiltonians in Krylov space, the minimal subspace in which the evolution takes place. We establish a direct link between dynamics in the time-dependent Krylov subspace and the underlying Lie-algebraic structure of the Hamiltonian. We develop a general framework in which the dynamics in the time-dependent Krylov subspace is generated by ladder operators of the associated Lie algebra. In particular, we identify the minimal conditions under which the exact time-dependent Krylov dynamics is naturally determined by the interaction-picture Hamiltonian and governed by an embedded sl(2,C)\mathfrak{sl}(2,\mathbb{C})sl(2,C) subalgebra. We further show that an exact single-exponential representation of the time-evolution operator gives rise to a distinct time-independent Krylov dynamics in a unitarily related basis, from which the exact time-dependent Krylov dynamics can nevertheless be recovered. We also extend the framework to the oscillator algebra as the simplest extension of the nilpotent Heisenberg--Weyl algebra, and provide further examples, including the translated and dilated harmonic oscillator, systems governed by closed Virasoro subalgebras, a spin in a rotating magnetic field, and higher-dimensional generalizations for multi-level systems. In addition, we introduce a new quantum speed limit to the complexity growth rate generated by a time-dependent generator and show that, for evolutions governed by a Lie algebra, it retains the same functional form as in the time-independent case. Remarkably, saturation of this bound is strongly affected by temporal driving and persists only when the Hamiltonian commutes with itself at different times. These results establish a unified framework for characterizing operator growth and Krylov complexity in time-dependent quantum systems with underlying Lie-algebraic structures.
We use an algebraic method to model the molecular collision dynamics of a collinear triatomic system. Beginning with a forced oscillator, we develop a mathematical framework upon which inelastic and reactive collisions are modeled. The model is considered algebraic because it takes advantage of the properties of a Lie algebra in the derivation of a time-evolution operator. The time-evolution operator is shown to generate both phase-space and quantum dynamics of a forced oscillator simultaneously. The model is considered semi-classical because only the molecule's internal degrees-of-freedom are quantized. The relative translation between the colliding atom and molecule in an exchange reaction (AB+C ->A+BC) contains no bound states and any possible tunneling is neglected so the relative translation is treated classically. The purpose of this dissertation is to develop a working model for the quantum dynamics of a collinear reactive collision. After a reliable model is developed we apply statistical mechanics principles by averaging collisions with molecules in a thermal bath. The initial Boltzmann distribution is of the oscillator energies. The relative velocities of the colliding particles is considered a thermal average. Results are shown of quantum transition probabilities around the transition state that are highly dynamic due to the coupling between the translational and transverse coordinate.
In this paper, we present a variational treatment of the linear dependence for a non-orthogonal time-dependent basis set in solving the Schrödinger equation. The method is based on (i) the definition of a linearly independent working space and (ii) a variational construction of the propagator over finite time steps. The second point allows the method to properly account for changes in the dimensionality of the working space along the time evolution. In particular, the time evolution is represented by a semi-unitary transformation. Tests are carried out on a quartic double-well potential with Gaussian basis functions whose centers evolve according to classical equations of motion. We show that the resulting dynamics converges to the exact one and is unitary by construction.