Introduce a bookkeeping parameter in and expand and . Fix phase and normalization at this order by . The first-order Schrödinger equation is
angular momentum projection onto gives . angular momentum projection onto a different eigenstate gives
Completeness therefore yields the first-order nondegenerate perturbation theory result
Nonzero energy denominators are essential. The displayed state has unit norm through first order; exact normalization would change terms of second order. A continuum, if present, contributes its corresponding integral as well as any discrete sum.
For the oscillator in a static electric field, electrostatic potential energy is and . parity gives , and the supplied Gaussian wavefunctions give
Since , the two-state first-order ground state is
Thus , and the induced electric dipole is
It is aligned with the field for either sign of . The harmonic-oscillator electric polarizability is . The position operator connects only to , so the requested two-state calculation contains the complete first-order dipole response, rather than dropping other first-order terms.
Complete the square to find the exact electric-field displacement of a quantum harmonic oscillator:
The exact normalized ground wavefunction is , with energy . Its mean displacement is , so
The first-order dipole equals the exact dipole, because the restoring force is exactly linear and translating a harmonic well does not change its width or frequency. This agreement of one expectation value does not make the truncated wavefunction exact. The Hellmann–Feynman theorem provides an independent check: .
For perturbation theory to approximate the state, , or . The exact translated ground state has the original-oscillator expansion
It is a coherent state with mean occupation . Large fields require many oscillator levels, whereas the first-order state retains only two. The normalized two-state truncation of a displaced oscillator instead gives
which incorrectly tends towards zero for large instead of following the displaced well. In position space the truncated polynomial times Gaussian also develops a node absent from the exact ground state. Taking a linearized formula outside its small-state-correction regime is therefore invalid even though its dipole coefficient happens to be exact.
Figure 1.
Exact translated ground state compared with its normalized two-state truncation at weak and strong displacement
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The quoted expansion is nondegenerate perturbation theory for a known isolated eigenstate of a time-independent Hamiltonian. A useful small-mixing condition is for coupled states. First order is a diagonal expectation value; second order describes virtual mixing. A degenerate or nearly degenerate coupled subspace must first be treated by diagonalization there. Symmetry can eliminate terms, and convergence still needs checking. Ground-state second-order shifts are nonpositive because all denominators are negative.[ref]
For the rotational Stark effect, , where is the polar angle to the field. The source calls it azimuthal, which is inconsistent with this coupling. Rotor states have parity , while is odd, so every first-order matrix element within one fixed- manifold vanishes. The degeneracy therefore causes no first-order splitting.
Only with the same contribute in second order. Using their energy differences and ,
For this simplifies to the quadratic Stark shift of a polar linear rotor,
For , only contributes, with squared angular matrix element and denominator :
Here is the rotational energy constant, unlike the magnetic field in Question3.
The unperturbed line gives . The shifts are for and for . Subtracting the common lower-state shift gives transition shifts and . Their separation determines the dipole moment from a rotational Stark doublet:
The unit is the debye. Using external and gives , consistent with weak-field perturbation theory. The two shifted frequencies are about and ; polarization selects or . The inferred value is a magnitude; these shifts do not determine the dipole's sign.[ref][ref]
Figure 1.
Opposite-parity mixing produces quadratic rotor shifts and a polarization-dependent rotational doublet
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The square-root branches avoid one another when ; crossings with a parallel-spin branch are allowed because total spin projections differ. At zero field the positive- sketch has one lower singlet and a triplet above it. The source supplies no numerical moment ratio, so the two panels show explicit illustrative signed choices, including the exactly compensated case.
Figure 1.
Two-spin exchange and Zeeman energies depend on the signed moment ratio, with an exact parallel-spin degeneracy for opposite equal moments
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For spin one-half, , hence
They raise or lower the spin projection by one unit of and annihilate the corresponding endpoint. The exchange identity preserves total spin projection.
Write , and . In the listed order , direct action gives
The printed matrix instead uses . Permuting the listed indices to recovers its central block and diagonal entries. This is a basis-order mismatch in the source, not a different Hamiltonian.
The two-spin exchange spectrum with unequal signed magnetic moments is
Use the products as the signed magnetic coefficients in the stated Hamiltonian. Opposite physical charges must be represented in those signs; they do not by themselves imply equal moment magnitudes. Here denotes the source's magneton, not vacuum permeability.
Define and use radiation energy density per unit angular frequency, excluding the zero-point contribution. The Angular-frequency Einstein coefficients give rates per atom: for absorption, for stimulated emission, and for spontaneous emission. Stimulated emission adds a photon to the stimulating mode; spontaneous emission persists with no incident photons.
Figure 1.
Absorption, stimulated emission and spontaneous emission between two nondegenerate levels
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In thermal equilibrium the Boltzmann distribution gives . Balancing up and down rates yields
Matching the Planck law for every temperature fixes
No degeneracy factor is needed for these nondegenerate levels.[ref]
For plates of large area and spacing , the surviving low-frequency transverse electromagnetic mode has one polarization, , and in-plane wavevector. Periodic in-plane counting gives
Multiplying this single-polarization two-dimensional photon density of states by and the Bose-Einstein distribution produces the thermal radiation between parallel conducting plates:
The same rate balance therefore gives
These coefficients refer to the radiation polarization in their respective environments: isotropic free-space must not automatically be equated to the coefficient for a specified -polarized field.
For hydrogen, take the quantization axis along , neglect spin-orbit coupling, and assume perfect plates, a wide in-plane region and an unmodified atomic wavefunction: , with negligible surface-induced mixing or shifts. The electric-dipole selection rules for hydrogen require ; the allowed field has . Hence the polarization-selective spontaneous emission between conducting plates gives
The thin-cavity enhancement of a normal electric dipole applies: the dipole points along and couples to the enhanced mode density. For , the transition dipoles lie in the – plane and couple to none of these low-frequency modes: the electric-dipole decay rate is zero in the ideal model, so this channel's lifetime is infinite. Real finite, imperfect plates and additional decay or mixing channels limit the lifetime. The order-one orientation factor for the allowed transition does not change the requested lifetime scaling.
With and oscillator length , the first two harmonic oscillator eigenfunctions and energies are
The ground state is even and nodeless; the first excited state is odd with one node of a wavefunction. Their rms widths are and . Also, gives the characteristic extent directly.
For the shaken harmonic trap, expanding about the unshifted Hamiltonian gives
The scalar term gives only a common phase and no transitions. In time-dependent perturbation theory, initially , and the oscillatory factor for is . Thus
The odd operator makes transitions to even vanish by parity. In fact the first-order selection rule for a linearly driven oscillator is stronger: since ,
All excited amplitudes vanish at first order, including odd . This assertion does not apply to the surviving or to higher perturbative orders.
Put , . The exact first-order time integral is
Near resonance, the second term oscillates rapidly at approximately and is bounded by , whereas the first grows as on resonance. Thus justifies the rotating-wave approximation, . At zeros of the resonant term, the omitted small contribution can dominate the residual; the approximation has no uniform relative-error bound there.
Using the requested order-one approximation and gives the square-pulse resonance profile
The exact harmonic oscillator matrix element instead gives half this probability. The finite central maximum is at ; first zeros are at , with smaller side lobes and a envelope. Increasing narrows the peak as and increases its height as , as long as weak resonant driving keeps . Small displacement alone does not ensure this for arbitrarily long ; near resonance one also needs .
Figure 1.
Even and odd oscillator wavefunctions and the finite-duration sinc-squared excitation profile
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