This chapter focuses on the time-dependent Schrödinger equation and its solutions for several prototype systems. It provides the basis for discussing and understanding quantum dynamics in condensed phases, however, a full picture can be obtained only by including also dynamical processes that destroy the quantum mechanical phase. Such a full description of quantum dynamics cannot be handled by the Schrödinger equation alone; a more general approach based on the quantum Liouville equation is needed. This important part of the theory of quantum dynamics is discussed in Chapter 10. Given a system characterized by a Hamiltonian Ĥ , the time-dependent Schrödinger equation is For a closed, isolated system Ĥ is time independent; time dependence in the Hamiltonian enters via effect of time-dependent external forces. Here we focus on the earlier case. Equation (1) is a first-order linear differential equation that can be solved as an initial value problem.
This chapter focuses on the time-dependent Schrödinger equation and its solutions for several prototype systems. It provides the basis for discussing and understanding quantum dynamics in condensed phases, however, a full picture can be obtained only by including also dynamical processes that destroy the quantum mechanical phase. Such a full description of quantum dynamics cannot be handled by the Schrödinger equation alone; a more general approach based on the quantum Liouville equation is needed. This important part of the theory of quantum dynamics is discussed in Chapter 10. Given a system characterized by a Hamiltonian Ĥ , the time-dependent Schrödinger equation is For a closed, isolated system Ĥ is time independent; time dependence in the Hamiltonian enters via effect of time-dependent external forces. Here we focus on the earlier case. Equation (1) is a first-order linear differential equation that can be solved as an initial value problem.
Abstract This chapter begins the discussion of the time evolution of an active quantum system. From the earlier chapters, time dependent physics has been observed through the presence of the time evolution of the phase of each eigenstate. The Hamiltonian itself is time independent. This represents the same kind of evolution of a classical system like the vibration of a tuning fork when it has been struck or the oscillation of an LC circuit if the capacitor is charged to some voltage and then the switch is closed. In the quantum case, the Hamiltonian has also been time independent. The time evolution evolves according the full-time dependent Schrödinger equation, depending only on a single initial condition of the state vector or wave function and the corresponding time evolution of the phase factor for each eigenstate. However in this chapter, we consider the case of when there is a time dependent Hamiltonian such as a sinewave generator or laser. As in the case of resonant tunneling, we see the importance in dynamics of resonant coupling. With an oscillating potential energy term, we see the presence of Rabi oscillations in the probability amplitude of a two-state system on resonance, which can be viewed as a quantum flip-flop between two states of a quantum bit (qubit).
We solve the Schrodinger equation analytically for systems whose potentials have a certain time-dependence (which is monotonously decreasing) and general coordinate-dependences.Only a few time-dependent systems have been reported to be analytically solved whose potentials are constant, linear, and quadratic functions of coordinate with arbitrary time-dependences.From a different perspective, we focus on the time-dependent systems whose potentials are monotonously decreasing functions of time with arbitrary coordinate dependences.Time-dependent potential of any coordinate-dependence can be handled analytically by transforming it to a time-independent potential of known solutions if its time-dependence is monotonously decreasing.We do this by a unitary transformation of the wavefunction and variable transformations to change the Schrodinger equation to be time-independent in new variables.These variables are then determined by solving a set of simple differential equations.This way we are able to find and to obtain analytical solutions for time-dependent potentials which we mention above.
Abstract All quantum processes involve time. For an algorithm to work, something must change over time. This chapter shows how that is implemented and how time dependence can be calculated. The chapter shows how a linear transformation that connects a state at one time to another state at a short time later is equivalent to a derivative with respect to time. To implement that idea, two separate methods are employed. The first is the perhaps familiar calculus-based Schrödinger differential equation where the Hamiltonian operator determines the time dependence of the states of the quantum system. The second method makes use of the Heisenberg picture where the time dependence resides in the operators.
In the first two chapters we have examined the basic principles – superposition (p. 18), complementarity (p. 19), quantization (p. 44), statistical algorithm (p. 57), and correspondence (p. 72) (see also Subsec. 2.3.4) – and the basic entities, observables and states, of quantum mechanics, as well as the main differences with respect to classical mechanics. While what we have discussed so far is rather a static picture of observables and states, in this chapter we shall deal with quantum dynamics, i.e. with the time evolution of quantum-mechanical systems. Historically, after Bohr had provided a quantized description of the atom (see Subsec. 1.5.4), Einstein showed the quantized nature of photons (see Subsec. 1.2.1), and de Broglie hypothized the wave-like nature of matter (see Subsec. 1.5.5), the first building block of quantum mechanics was provided by the commutation relations, proposed by Heisenberg in 1925, whose consequence is represented by the uncertainty relation (see Subsec. 2.2.7 and Sec. 2.3). This was the subject of the previous chapters. The dynamical part of the theory was proposed by Schrödinger in 1926, and is known as the Schrödinger equation. It is also known as wave mechanics (see Subsec. 1.5.7). In this chapter we shall show that Heisenberg's and Schrödinger's formulations are only two different aspects of the same theory. We shall also come back to this point in Sec. 8.1.1. Here, first we shall derive the fundamental equation which rules quantum dynamics (Sec. 3.1), and, in Sec. 3.2, we shall summarize the main properties of the Schrödinger equation.
The time-independent Schrodinger equation: En= -1/2m [d/dx dWn/dx] / Wn(x) + V(x) ((1)) matches a classical conservation of energy equation where -1/2m [d/dx dWn/dx] / Wn(x) = KEclassical(x). In classical physics, however, one has x(t) so each x point is associated with a specific t for a given energy En. In the quantum time-independent equation, one has exp(-iEnt) as the time dependent factor and does not consider any link with x although if one is comparing ((1)) to a classical conservation equation then a link between x and t could be made to complete the analogy. This is usually not considered, but we examine this point as we argue it becomes important in the time-dependent situation. For the time-dependent Schrodinger case we consider two approaches. First, a linear combination of time independent solutions is taken i.e. W(x,t) = Sum over n an(En) exp(-iEnt) Wn(x) ((2)) Again each Wn(x) has an association with KEclassical(x) and so one may think in terms of (x,t) classical pairs for a given En. The second approach is to consider the function: exp(-iEnt + m Integral (0,x) v(y) dy) ((3)). This satisfies the time-dependent Schrodinger equation and yields a classical conservation of energy equation with v(x) being the classical velocity. Noting that En= .5m v(x)v(x) + V(x), ((3)) may be rewritten as: exp(i Integral L dt) where L = T-V is the Langrangian with T=.5mv(x)v(x). At this point En has been removed from the picture, but is replaced with: x(t)= X g(t)/g(T) ((4)) where (X,T) are a space-time pair corresponding to a particular energy E value. Using exp(i Action) ((5)) in the time-dependent Schrodinger equation yields a conservation equation which holds for a particular classical energy as long as (x,t) values in the equation are classically linked to the appropriate classical (X,T) values i.e. for a classical trajectory there is a specific family of X at time T for a given energy. For another energy, there is another family of (X,T) pairs. Thus the equation obtained represents energy conservation for many different energy values depending on which simultaneous values one uses for x and t. There is, however, no overlap as a specific (X,T) family corresponds to an energy E and another nonoverlapping family of (X,T) to another energy. This, however, is the same situation as ((2)) for which there are also families of (X,T) corresponding to each En. The only difference is that the En are quantized i.e. discrete. ((3)) and ((5)) are both solutions to the time-dependent Schrodinger equation which represent a variety of energies and families of (X,T) associated to the classical solution of the energy in question. We thus suggest that ((2)) and ((4)) are equivalent for this reason without using the idea of a complete set of basis functions represented by Wn(x). We consider these ideas as the Schrodinger propagator is given by ((5)), but with ((4)) generalized to: x(t)= Xi g(tf-t)/g(tf-ti) + Xf g(t-ti)/g(tf-ti) for the case that g(0)=0 (2) so that Xi,Xf, tf and ti enter the picture. This then should be equivalent to: Sum over n exp(-iEntf) Wn(xf) Wn* (xi) ((6)) In this note, we suggest that one may link ((5)) and ((6)) based on ideas of space-time families associated with different energies as well as the two being solutions of the time-dependent Schrodinger equation.
Abstract This chapter the reviews essential concepts and methods of time-dependent quantum mechanics. (1) Formal solutions of the time-dependent Schrödinger equation. (2) The two-level system. (3) Interacting systems: The time-dependent self-consistent field approximation and the Ehrenfest approximation. (4) The Born–Oppenheimer approximation and nuclear potential surfaces. (5) Time-dependent Hamiltonians: A two-level system in a time-dependent field. (6) Non-adiabatic dynamics: The surface-hopping method. (7) Expressing the time evolution in terms of the Green operator. (8) Representations (the Schrödinger and Heisenberg representations, the interaction representation). (9) Time-dependent perturbation theory. (10) Quantum dynamics of the free particles. (11) Quantum dynamics of the harmonic oscillator. (12) The raising/lowering operators formalism. (13) Tunneling.