gth from a given initial state and how much transition strength is left over for all other
transitions out of
that state. Similar oscillator strength sum rules apply to molecules. For electronic-vibration-rotation
transitions we have a product of three linestrength factors, each of which follows an a priori known sum
rule. These sum rules are valuable both for building insight and for discovering the normalization scheme
implicitly built into a linestrength formula that you did not derive for yourself. 1.7 Eigenstates are
Stationary Our instinctive classical mechanical view of a molecule is of something that embodies a
hierarchy of motions: electron motions are fast, vibrational motions are slower, and rotational motions
are the slowest. But this dynamical view is inconsistent with both experimental reality (the frequency-
domain spectrum prominently displays transitions between discrete energy levels) and the
computational reality of the time-independent Schrödinger equation, H n D En n. n is an eigenfunction of
the time independent Hamiltonian, H, where each n is associated with an energy eigenvalue, En. The f ng
are both not moving and not directly observable! It is very strange that what we can observe in a
frequency domain experiment, energy levels and transition intensities, tells us nothing about
intramolecular electronic-vibrational-rotational motions (what is moving, how fast, and what are the
amplitudes of motion?) and nothing about the quantum mechanical wavefunction that is supposed to
tell us everything that is knowable about each non-moving quantum mechanical state of the molecule.
This quantum weirdness is part of what makes spectroscopy beautiful and mysterious. The energy level
and intensity patterns that we observe in a spectrum encode both dynamics and the set of
wavefunctions, f ng. When we assign the energy levels in a spectrum and fit them to an electronic-
vibrational-rotational model, we determine the numerical values of the important terms in the
molecular Hamiltonian. Each term in this Hamiltonian is the product of an abstract quantum mechanical
operator and an empirically determined molecular constant. This is not the exact Hamiltonian. It is an
effective Hamiltonian, Heff, which is merely a convenient fit model
computational reality of the time-independent Schrödinger equation, H n D En n. n is an eigenfunction of
the time independent Hamiltonian, H, where each n is associated with an energy eigenvalue, En. The f ng
are both not moving and not directly observable! It is very strange that what we can observe in a
frequency domain experiment, energy levels and transition intensities, tells us nothing about
intramolecular electronic-vibrational-rotational motions (what is moving, how fast, and what are the
amplitudes of motion?) and nothing about the quantum mechanical wavefunction that is supposed to
tell us everything that is knowable about each non-moving quantum mechanical state of the molecule.
This quantum weirdness is part of what makes spectroscopy beautiful and mysterious. The energy level
and intensity patterns that we observe in a spectrum encode both dynamics and the set of
wavefunctions, f ng. When we assign the energy levels in a spectrum and fit them to an electronic-
vibrational-rotational model, we determine the numerical values of the important terms in the
molecular Hamiltonian. Each term in this Hamiltonian is the product of an abstract quantum mechanical
operator and an empirically determined molecular constant. This is not the exact Hamiltonian. It is an
effective Hamiltonian, Heff, which is merely a convenient fit model
computational reality of the time-independent Schrödinger equation, H n D En n. n is an eigenfunction of
the time independent Hamiltonian, H, where each n is associated with an energy eigenvalue, En. The f ng
are both not moving and not directly observable! It is very strange that what we can observe in a
frequency domain experiment, energy levels and transition intensities, tells us nothing about
intramolecular electronic-vibrational-rotational motions (what is moving, how fast, and what are the
amplitudes of motion?) and nothing about the quantum mechanical wavefunction that is supposed to
tell us everything that is knowable about each non-moving quantum mechanical state of the molecule.
This quantum weirdness is part of what makes spectroscopy beautiful and mysterious. The energy level
and intensity patterns that we observe in a spectrum encode both dynamics and the set of
wavefunctions, f ng. When we assign the energy levels in a spectrum and fit them to an electronic-
vibrational-rotational model, we determine the numerical values of the important terms in the
molecular Hamiltonian. Each term in this Hamiltonian is the product of an abstract quantum mechanical
operator and an empirically determined molecular constant. This is not the exact Hamiltonian. It is an
effective Hamiltonian, Heff, which is merely a convenient fit modelcomputational reality of the time-
independent Schrödinger equation, H n D En n. n is an eigenfunction of the time independent
Hamiltonian, H, where each n is associated with an energy eigenvalue, En. The f ng are both not moving
and not directly observable! It is very strange that what we can observe in a frequency domain
experiment, energy levels and transition intensities, tells us nothing about intramolecular electronic-
vibrational-rotational motions (what is moving, how fast, and what are the amplitudes of motion?) and
nothing about the quantum mechanical wavefunction that is supposed to tell us everything that is
knowable about each non-moving quantum mechanical state of the molecule. This quantum weirdness
is part of what makes spectroscopy beautiful and mysterious. The energy level and intensity patterns
that we observe in a spectrum encode both dynamics and the set of wavefunctions, f ng. When we
assign the energy levels in a spectrum and fit them to an electronic-vibrational-rotational model, we
determine the numerical values of the important terms in the molecular Hamiltonian. Each term in this
Hamiltonian is the product of an abstract quantum mechanical operator and an empirically determined
molecular constant. This is not the exact Hamiltonian. It is an effective Hamiltonian, Heff, which is merely
a convenient fit model