The time-dependent Schrodinger for an atom in a radiation field has a very special form, at least within the dipole approximation: The time-dependence of the Hamiltonian is contained entirely in a c-number which appears as a factor in the interaction, V(t), of the atom with the radiation field. In the velocity gauge this factor is the vector potential, A(t), of the field — we have V(t)= − (e/µc)A (t) • p, where e, µ, and p are the charge, reduced mass, and canonical momentum (in the center of mass frame) of the electron — while in the length gauge this factor is the electric field vector F(t) — we have V(t) = –eF(t) • x, where x is the position coordinate. To our knowledge, this factorization property has not been fully exploited in previous approaches to solving the timedependent Schrodinger equation1. As we show here, in an application to multiphoton ionization of atomic hydrogen, it is an extremely useful property; and although at first sight it would seem to be a unique feature of the atom-radiation system, this is not so, for, as Solov’ev2 has pointed out, the time-dependent Schrödinger equation for colliding atoms or ions can be transformed into a form in which a scaled time-dependence also appears only in c-number factors of the (transformed) interactions.
Time-dependent unitary transformations are used to study the Schrödinger equation for explicitly time-dependent Hamiltonians of the form H(t)=R(t)⋅J, where R is an arbitrary real vector-valued function of time and J is the angular momentum operator. The solution of the Schrödinger equation for the most general Hamiltonian of this form is shown to be equivalent to the special case R=(1,0,ν(t)). This corresponds to the problem of a driven two-level atom for the spin half representation of J. It is also shown that by requiring the magnitude of R to depend on its direction in a particular way, one can solve the Schrödinger equation exactly. In particular, it is shown that for every Hamiltonian of the form H(t)=R(t)⋅J there is another Hamiltonian with the same eigenstates for which the Schrödinger equation is exactly solved. The application of the results to the exact solution of the parallel transport equation and exact holomony calculation for SU(2) principal bundles (Yang–Mills gauge theory) is also pointed out.
For quantum mechanics of a charged particle in a classical external electromagnetic field, there is an apparent puzzle that the matrix element of the canonical momentum and Hamiltonian operators is gauge dependent. A resolution to this puzzle was recently provided by us [X.-S. Chen et al., Phys. Rev. Lett. 100, 232002 (2008)]. Based on the separation of the electromagnetic potential into pure-gauge and gauge-invariant parts, we have proposed a new set of momentum and Hamiltonian operators which satisfy both the requirement of gauge invariance and the relevant commutation relations. In this paper we report a check for the case of the hydrogen-atom problem: Starting from the Hamiltonian of the coupled electron, proton, and electromagnetic field, under the infinite proton mass approximation, we derive the gauge-invariant hydrogen-atom Hamiltonian and verify explicitly that this Hamiltonian is different from the Dirac Hamiltonian, which is the time translation generator of the system. The gauge-invariant Hamiltonian is the energy operator, whose eigenvalue is the energy of the hydrogen atom. It is generally time dependent. In this case, one can solve the energy eigenvalue equation at any specific instant of time. It is shown that the energy eigenvalues are gauge independent, and by suitably choosing the phase factor of the time-dependent eigenfunction, one can ensure that the time-dependent eigenfunction satisfies the Dirac equation.
The interaction of a low-intensity laser field with a nonrelativistic one-electron atom is considered to the first order of perturbation theory and in the electric dipole approximation. The radiation field is turned on adiabatically modifying the initial unperturbed atomic state, which is either an angular-momentum eigenstate
∣nlm〉 or a Stark state
∣nnem〉. The first-order correction to the wave function is expressed both in the length and velocity gauges in terms of a vector function called the linear-response vector and depending on the field-free energy eigenstate. We derive in a unifying manner the linear-response vectors in the position representation, as closed-form contour integrals, starting from a unique generating function built up with the Coulomb Green function. The linear-response vectors are then evaluated in momentum space via a Fourier transformation: they are obtained as integral representations and also in explicit form, as generalized hypergeometric functions. With reference to the static limit, we complement earlier results and find the reduced linear-response vectors in momentum space, as Fourier transforms of their coordinate-representation counterparts. The low-frequency behavior of the length-gauge first-order correction to the ground-state wave function is established in coordinate as well as in momentum space. We finally point out the high-frequency limit of the linear response in the velocity gauge.
In all the applications of the formalism of quantum theory, we have considered mainly time-independent potential functions, V ( r , t ) = V ( r ). Such potentials made it easier to solve exactly the Schrodinger's equation or by solving the Schrodinger's equation approximately by using perturbation theory. The solution of the Schrodinger equation for time-independent potentials is obtained by using method of separable variables. The solution of time-independent Schrodinger gives stationary states, and the time dependence of the wave function is obtained by adding a phase factor to the stationary state. The schematic that follows describes such an approach ( Figure 7.1 ).
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.
A thorough unified treatment is given of the quantum-mechanical operators and wave functions for a molecular system (composed of
N moving charged particles) in static uniform electric and magnetic fields
E and
B. The treatment is rigorous within the nonrelativistic approximation. The system may either be neutral or charged. The fields may have arbitrary intensities and orientations. Close correspondence is maintained between the classical and quantum-mechanical treatments. The wave functions are expressed both in the time-independent energy representation and in time-dependent wave packets. Three types of momentum play important roles. For single-particle systems they are the canonical momentum
P, the mechanical momentum $\mathit{\ensuremath{\Pi}}=\mathit{P}\ensuremath{-}(\frac{e}{c})\mathit{A}=M\stackrel{\ifmmode \dot{}\else \.{}\fi{}}{R}$, and the pseudomomentum $\mathcal{K}=\mathit{\ensuremath{\Pi}}\ensuremath{-}(\frac{e}{c})\mathit{R}\ifmmode\times\else\texttimes\fi{}\mathit{B}\ensuremath{-}e\mathit{E}t$. The pseudomomentum is a constant of the motion. Except in the absence of magnetic fields, not all of the components of either $\mathit{\ensuremath{\Pi}}$ or
K commute. This complicates the quantum-mechanical formalism. The components of the pseudomomentum have simple classical interpretations, and in quantum mechanics they are related to the operator which performs a boost to a reference frame moving with constant velocity
v. In this moving frame, the electric field intensity is ${\mathit{E}}^{\ensuremath{'}}=\mathit{E}+(\frac{\mathit{v}}{c})\ifmmode\times\else\texttimes\fi{}\mathit{B}$. Thus, in a frame moving with the drift velocity ${\mathit{v}}_{d}=(\frac{c}{{B}^{2}})\mathit{E}\ifmmode\times\else\texttimes\fi{}\mathit{B}$, the components of the electric field intensity perpendicular to
B vanish. In this paper, the velocity boost operators are used to show the relationships between wave functions expressed in reference frames moving with repsect to each other. The dynamics of the
N-particle systems are simplified by making the Power-Zienau-Woolley transformation (which reduces as a special case to a unitary transformation used by Lamb) and by using center-of-mass and internal coordinates. Generalizing previous works, it is shown how the pseudomomentum is involved in separating these degrees of freedom for
N particles in both
E and
B. For neutral molecules, the Schr\"odinger equation is "pseudoseparated" and the internal degrees of freedom are coupled to the center of mass motion only by the "motional Stark Effect," which involves the constant of motion
K. For ionic systems, only one component of the center of mass is coupled to the internal motion. Quantitative estimates of the weak center-of-mass coupling are made for both neutral and ionic
n=1 and
n=2 quantum states of two-body systems by perturbation expansions in powers of the field strengths. In the usual nonrigorous treatments of systems in magnetic fields, no distinction is made between $\mathit{\ensuremath{\Pi}}$ and
K and both are approximated by $M\stackrel{\ifmmode \dot{}\else \.{}\fi{}}{R}$, where
M is the mass of the molecule and
R is taken to be the classical orbital position of a single particle having the same mass and charge. This is an excellent approximation for ground-state molecules and ions in weak fields. However, the resulting errors can be much larger if the system is in either intense fields or high-lying states (e.g., Rydberg levels). These are the conditions under which the rigorous formalism should be most useful. The determination of the wave functions and energy levels for many-particle ionic systems is complicated due to the coupling with the center of mass. The suggestion is made that it might be useful to boost the reference frame so that it moves with the velocity $\stackrel{\ifmmode \dot{}\else \.{}\fi{}}{R}$ of a single classical particle. The Schr\"odinger equation in this frame could serve as a more suitable basis for perturbative or variational treatments.