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Appendixc

Appendixc

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Quantum Mechanical Operators and Commutation C
I. Bra-Ket Notation

It is conventional to represent integrals that occur in quantum mechanics in a
notation that is independent of the number of coordinates involved. This is done because
the fundamental structure of quantum chemistry applies to all atoms and molecules,
regardless of how many electronic and atom-center coordinates arise. The most commonly

used notation, which is referred to as 'Dirac' or 'bra-ket' notation, can be summarized as

follows:
A. The wavefunction itself\u03a8 is represented as a so-called 'ket' |\u03a8>.
B. The complex conjugate\u03a8* of\u03a8 is represented as a 'bra' <\u03a8|; the complex conjugation

is implied by writing < |.
C. The integral, over all of the N coordinates (q1...qN) on which\u03a8 depends, of the
product of\u03a8* and\u03a8 is represented as a so-called 'bra-ket' or bracket:
\u2321\u2320 \u03a8* \u03a8dq1...dqN = < \u03a8| \u03a8>.
By convention, the two vertical lines that touch when <\u03a8 | is placed against |\u03a8 > are
merged into a single line in this notation.
D. Integrals involving one function (\u03a8*) and either another function (\u03a6) or the result of an
operator A acting on a function (e.g., A\u03a8 or A\u03a6) are denoted as follows:
\u2321\u2320\u03a8* \u03a6dq1...dqN = < \u03a8| \u03a6>

\u2321\u2320 \u03a8*A \u03a8dq1...dqN = < \u03a8| A\u03a8> = < \u03a8| A | \u03a8> \u2321\u2320 \u03a8*A \u03a6dq1...dqN = < \u03a8| A\u03a6> = < \u03a8| A | \u03a6> \u2321\u2320(A\u03a8)* \u03a6dq1...dqN = < A\u03a8| \u03a6> .

It is merely convention that an 'extra' vertical line (e.g., that appearing in <\u03a8 | A |\u03a6 >) is
inserted when an operator acting on the ket function appears in the integral.
II. Hermitian Operators

In quantum mechanics, physically measurable quantities are represented by hermitian operators. Such operators {R} have matrix representations, in any basis spanning the space of functions on which the {R} act, that are hermitian:

<\u03c6k|R|\u03c61> = <\u03c61|R|\u03c6k>* = <R\u03c6k|\u03c6l>.

The equality of the first and third terms expresses the so-called 'turn-over rule'; hermitian
operators can act on the function to their right or, equivalently, on the function to their left.
Operators that do not obey the above identity are not hermitian. For such operators,

it is useful to introduce the so-called adjoint operator as follows. If for the operator R,
another operator R+ can be found that obeys
<\u03c6k|R|\u03c61> = <R+\u03c6k|\u03c6l> = <\u03c61|R+|\u03c6k>*,
for all {\u03c6k} within the class of functions on which R and R+ operate, then R+ is defined to
be the adjoint of R. With this definition, it should be clear that hermitian operators are self-
adjoint (i.e., they obey R+= R).
The hermiticity property guarantees that the eigenvalues {\u03bbm} of such operators are
real numbers (i.e., not complex) and that the corresponding eigenfunctions {fm}, or their
representations {Vmk} within the {\u03c6k} basis
fm =\u03a3k Vmk\u03c6 k ,
corresponding to different eigenvalues are orthonormal and that the eigenfunctions
belonging to degenerate eigenvalues can be made orthonormal.
To prove these claims, start with R\u03c6k =\u03bbk\u03c6k. Multiplying on the left by the
complex conjugate of\u03c6k and integrating gives <\u03c6k|R|\u03c6k> =\u03bbk <\u03c6k|\u03c6k>. Taking the
complex conjugate of this equation and using the Hermiticity property <\u03c6k|R|\u03c61> =
<\u03c61|R|\u03c6k>* (applied with k=l) gives\u03bbk* =\u03bbk.

The orthogonality proof begins with R\u03c6k =\u03bbk\u03c6k, and R\u03c6l =\u03bbl \u03c6l. Multiplying the
first of these on the left by <\u03c6l| and the second by <\u03c6k|
gives <\u03c6l|R|\u03c6k> =\u03bbk <\u03c6l|\u03c6k> and <\u03c6k|R|\u03c6l> =\u03bbl <\u03c6k|\u03c6l>. The complex conjugate of the
second reads <\u03c6k|R|\u03c6l>* =\u03bbl <\u03c6k|\u03c6l>*; using the Hermiticity property this reduces to
<\u03c6l|R|\u03c6k> =\u03bbl <\u03c6l|\u03c6k>. If\u03bbk \u2260 \u03bbl, this result can be consistent with <\u03c6l|R|\u03c6k> =\u03bbk

<\u03c6l|\u03c6k> only if <\u03c6l|\u03c6k> vanishes.
III. Meaning of the Eigenvalues and Eigenfunctions

In quantum mechanics, the eigenvalues of an operator represent the only numerical
values that can be observed if the physical property corresponding to that operator is
measured. Operators for which the eigenvalue spectrum (i.e., the list of eigenvalues) is
discrete thus possess discrete spectra when probed experimentally.

For a system in a state
\u03c8 that is an eigenfunction of R
R\u03c8 =\u03bb\u03c8 ,
measurement of the property corresponding to R will yield the value\u03bb. For example, if an
electron is in a 2p-1 orbital andL2 is measured, the value L(L+1) h2 = 2h2 (and only this
value) will be observed; ifLz is measured, the value -1h (and only this value) will be

observed. If the electron were in a 2px orbital andL2 were measured, the value 2h2 will be
found; however, ifLz is measured, we can not say that only one value will be observed
because the 2px orbital is not an eigenfunction ofLz (measurements in such non-
eigenfunction situations are discussed below).

In general, if the property R is measured, any one of the eigenvalues {\u03bbm} of the

operator R may be observed. In a large number of such measurements (i.e., for an
ensemble of systems all in states described by\u03c8 that may or may not itself be an
eigenfunction of R), the probability or frequency of observing the particular eigenvalue\u03bbm
is given by |Cm|2, where Cm is the expansion coefficient of\u03c8 in the eigenfunctions of R:

\u03c8 = \u03a3\u00b5Cm fm .
In the special case treated earlier in which\u03c8 is an eigenfunction of R, all but one of the Cm
vanish; hence the probability of observing various\u03bbm values is zero except for the one
state for which Cm is non-zero.

For a measurement that results in the observation of the particular value\u03bbm , a
subsequent measurement of R on systems just found to have eigenvalue\u03bbm will result,
with 100% certainty, in observation of this same value\u03bbm . The quantum mechanical

interpretation of this experimental observation it to say that the act of measuring the
property belonging to the operator R causes the wavefunction to be altered. Once this

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