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author | Robert McIntyre <rlm@mit.edu> |
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date | Mon, 17 Oct 2011 23:17:55 -0700 |
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1 #+TITLE: Bugs in quantum mechanics | |
2 #+AUTHOR: Dylan Holmes | |
3 #+DESCRIPTION: I explain hermitian operators and use them to solve a confusing problem in quantum mechanics. | |
4 #+KEYWORDS: quantum mechanics, self-adjoint, hermitian, square well, momentum | |
5 #+SETUPFILE: ../../aurellem/org/setup.org | |
6 #+INCLUDE: ../../aurellem/org/level-0.org | |
7 | |
8 | |
9 | |
10 #Bugs in Quantum Mechanics | |
11 #Bugs in the Quantum-Mechanical Momentum Operator | |
12 | |
13 | |
14 I studied quantum mechanics the same way I study most subjects\mdash{} | |
15 by collecting (and squashing) bugs in my understanding. One of these | |
16 bugs persisted throughout two semesters of | |
17 quantum mechanics coursework until I finally found | |
18 the paper | |
19 [[http://arxiv.org/abs/quant-ph/0103153][/Self-adjoint extensions of operators and the teaching of quantum | |
20 mechanics/]], which helped me stamp out the bug entirely. I decided to | |
21 write an article about the problem and its solution for a number of reasons: | |
22 | |
23 - Although the paper was not unreasonably dense, it was written for | |
24 teachers. I wanted to write an article for students. | |
25 - I wanted to popularize the problem and its solution because other | |
26 explanations are currently too hard to find. (Even Shankar's | |
27 excellent [[http://books.google.com/books/about/Principles_of_quantum_mechanics.html?id=2zypV5EbKuIC][textbook]] doesn't mention it, as far as I know.) | |
28 - Attempting an explanation is my way of making | |
29 sure that the bug really /is/ gone. | |
30 # entirely eradicated. | |
31 | |
32 * COMMENT | |
33 I recommend the | |
34 paper not only for students who are learning | |
35 quantum mechanics, but especially for teachers interested in debugging | |
36 them. | |
37 | |
38 * COMMENT | |
39 On my first exam in quantum mechanics, my professor asked us to | |
40 describe how certain measurements would affect a particle in a | |
41 box. Many of these measurement questions required routine application | |
42 of skills we had recently learned\mdash{}first, you recall (or | |
43 calculate) the eigenstates of the quantity | |
44 to be measured; second, you write the given state as a linear | |
45 sum of these eigenstates\mdash{} the coefficients on each term give | |
46 the probability amplitude. | |
47 | |
48 | |
49 * Two methods of calculation that give different results. | |
50 | |
51 In the infinitely deep well, there is a particle in the the | |
52 normalized state | |
53 | |
54 \(\psi(x) = \begin{cases}A\; x(x-a)&\text{for }0\lt{}x\lt{}a;\\0,&\text{for }x\lt{}0\text{ or }x>a.\end{cases}\) | |
55 | |
56 This is apparently a perfectly respectable state: it is normalized ($A$ is a | |
57 normalization constant), it is zero | |
58 everywhere outside of the well, and it is moreover continuous. | |
59 | |
60 Even so, we will find a problem if we attempt to calculate the average | |
61 energy-squared of this state (that is, the quantity \(\langle \psi | H^2 | \psi \rangle\)). | |
62 | |
63 ** First method | |
64 | |
65 For short, define a new variable[fn:1] \(|\bar \psi\rangle \equiv | |
66 H|\psi\rangle\). We can express the state $|\bar\psi\rangle$ as a | |
67 function of $x$ because we know how to express $H$ and $\psi$ in terms | |
68 of $x$: $H$ is the differential operator $\frac{-\hbar^2}{2m}\frac{d^2}{dx^2}$, and | |
69 $\psi(x)$ is the function defined above. So, we get \(\quad\bar\psi(x) = \frac{-A\hbar^2}{m}\). For future reference, observe that $\bar\psi(x)$ | |
70 is constant. | |
71 | |
72 Having introduced $|\bar\psi\rangle$, we can calculate the average energy-squared of $|\psi\rangle$ in the | |
73 following way. | |
74 | |
75 \(\begin{eqnarray} | |
76 \langle \psi | H^2 |\psi\rangle &=& \langle \psi H^\dagger | H | |
77 \psi\rangle\\ | |
78 &=& \langle \psi H | H\psi \rangle\\ | |
79 &=& \langle \bar\psi | \bar\psi \rangle\\ | |
80 &=& \int_0^a \left(\frac{A\hbar^2}{m}\right)^2\;dx\\ | |
81 &=& \frac{A^2\hbar^4 a}{m^2}\\ | |
82 \end{eqnarray}\) | |
83 | |
84 For future reference, observe that this value is nonzero | |
85 (which makes sense). | |
86 | |
87 ** Second method | |
88 We can also calculate the average energy-squared of $|\psi\rangle$ in the | |
89 following way. | |
90 | |
91 \begin{eqnarray} | |
92 \langle \psi | H^2 |\psi\rangle &=& \langle \psi | H\,H \psi \rangle\\ | |
93 &=& \langle \psi |H \bar\psi \rangle\\ | |
94 &=&\int_0^a Ax(x-a) | |
95 \left(\frac{-\hbar^2}{2m}\frac{d^2}{dx^2}\right)\frac{-A\hbar^2}{m}\;dx\\ | |
96 &=& 0\quad (!)\\ | |
97 \end{eqnarray} | |
98 | |
99 The second-to-last term must be zero because the second derivative | |
100 of a constant \(\left(\frac{-A\hbar^2}{m}\right)\) is zero. | |
101 | |
102 * What is the problem? | |
103 | |
104 To recap: We used two different methods to calculate the average | |
105 energy-squared of a state $|\psi\rangle$. For the first method, we | |
106 used the fact that $H$ is a hermitian operator, replacing \(\langle | |
107 \psi H^\dagger | H \psi\rangle\) with \(\langle \psi H | H | |
108 \psi\rangle\). Using this substitution rule, we calculated the answer. | |
109 | |
110 For the second method, | |
111 #we didn't use the fact that $H$ was hermitian; | |
112 we instead used the fact that we know how to represent $H$ and $\psi$ | |
113 as functions of $x$: $H$ is a differential operator | |
114 \(\frac{-\hbar^2}{2m}\frac{d^2}{dx^2}\) and $\psi$ is a quadratic | |
115 function of $x$. By applying $H$ to $\psi$, we took several | |
116 derivatives and arrived at our answer. | |
117 | |
118 These two methods gave different results. In the following sections, | |
119 I'll describe and analyze the source of this difference. | |
120 | |
121 ** Physical operators only act on physical wavefunctions | |
122 :PROPERTIES: | |
123 :ORDERED: t | |
124 :END: | |
125 #In quantum mechanics, an operator is a function that takes in a | |
126 #physical state and produces another physical state as ouput. Some | |
127 #operators correspond to physical quantities such as energy, | |
128 #momentum, or position; the mathematical properties of these operators correspond to | |
129 #physical properties of the system. | |
130 | |
131 #Eigenstates are an example of this correspondence: an | |
132 | |
133 Physical states are represented as wavefunctions in quantum | |
134 mechanics. Just as we disallow certain physically nonsensical states | |
135 in classical mechanics (for example, we consider it to be nonphysical | |
136 for an object to spontaneously disappear from one place and reappear | |
137 in another), we also disallow certain wavefunctions in quantum | |
138 mechanics. | |
139 | |
140 For example, since wavefunctions are supposed to correspond to | |
141 probability amplitudes, we require wavefunctions to be normalized | |
142 \((\langle \psi |\psi \rangle = 1)\). Generally, we disallow | |
143 wavefunctions that do not satisfy this property (although there are | |
144 some exceptions[fn:2]). | |
145 | |
146 As another example, we generally expect probability to vary smoothly\mdash{}if | |
147 a particle is very likely or very unlikely to be found at a particular | |
148 location, it should also be somewhat likely or somewhat unlikely to be | |
149 found /near/ that location. In more precise terms, we expect that for | |
150 physically meaningful wavefunctions, the probability | |
151 \(\text{Pr}(x)=\int^x \psi^*\psi\) should be a continuous function of | |
152 $x$ and, again, we disallow wavefunctions that do not satisfy this | |
153 property because we consider them to be physically nonsensical. | |
154 | |
155 So, physical wavefunctions must satisfy certain properties | |
156 like the two just described. Wavefunctions that do not satisfy these properties are | |
157 rejected for being physically nonsensical: even though we can perform | |
158 calculations with them, the mathematical results we obtain do not mean | |
159 anything physically. | |
160 | |
161 Now, in quantum mechanics, an *operator* is a function that converts | |
162 states into other states. Some operators correspond to | |
163 physical quantities such as energy, momentum, or position, and as a | |
164 result, the mathematical properties of these operators correspond to | |
165 physical properties of the system. Such operators are called | |
166 /hermitian operators/; one important property of hermitian operators | |
167 is this rule: | |
168 | |
169 #+begin_quote | |
170 *Hermitian operator rule:* A hermitian operator must only operate on | |
171 the wavefunctions we have deemed physical, and must only produce | |
172 physical wavefunctions[fn:: If you require a hermitian operator to | |
173 have physical eigenstates (which is reasonable), you get a very strong result: you guarantee | |
174 that the operator will convert every physical wavefunction into | |
175 another physical wavefunction: | |
176 | |
177 For any linear operator $\Omega$, the eigenvalue equation is | |
178 \(\Omega|\omega\rangle = \omega |\omega\rangle\). Notice that if an | |
179 eigenstate $|\omega\rangle$ is a physical wavefunction, the | |
180 eigenvalue equation forces $\Omega|\omega\rangle$ to be a | |
181 physical wavefunction as well. To elaborate, if the eigenstates of | |
182 $\Omega$ are physical functions, then $\Omega$ is guaranteed to | |
183 convert them into other physical functions. Even more is true if the | |
184 operator $\Omega$ is also hermitian: there is a theorem which states | |
185 that \ldquo{}If \Omega is hermitian, then every physical wavefunction | |
186 can be written as a weighted sum of eigenstates of \Omega.\rdquo{} This | |
187 theorem implies that /if $\Omega$ is hermitian/, and /if the eigenstates | |
188 of \Omega are physically allowed/, then \Omega is guaranteed to | |
189 convert every physically allowed wavefunction into another physically | |
190 allowed wavefunction.]. | |
191 #+end_quote | |
192 | |
193 As you can see, this rule comes in two pieces. The first part is a | |
194 constraint on *you*, the physicist: you must never feed a nonphysical | |
195 state into a Hermitian operator, as it may produce nonsense. The | |
196 second part is a constraint on the *operator*: the operator is | |
197 guaranteed only to produce physical wavefunctions. | |
198 | |
199 In fact, this rule for hermitian operators is the source of our | |
200 problem, as we unknowingly violated it when applying our second | |
201 method! | |
202 | |
203 ** The Hamiltonian is nonphysical | |
204 You'll remember that in the second method we had wavefunctions within | |
205 the well | |
206 | |
207 \( | |
208 \begin{eqnarray} | |
209 \psi(x) &=& A\;x(x-a)\\ | |
210 \bar\psi(x)&\equiv& H|\psi\rangle = \frac{-A\hbar^2}{m}\\ | |
211 \end{eqnarray} | |
212 \) | |
213 | |
214 Using this, we wrote | |
215 | |
216 | |
217 \(\begin{eqnarray} | |
218 \langle \psi | H^2 |\psi\rangle &=& \langle \psi | H\,H \psi \rangle\\ | |
219 &=& \langle \psi |H \bar\psi \rangle\\ | |
220 & \vdots&\\ | |
221 &=& 0\\ | |
222 \end{eqnarray}\) | |
223 | |
224 However, there are two issues here. First, we were not allowed to operate with $H$ on the wavefunction | |
225 $|\bar \psi\rangle$, because $H$ is supposed to be a physical operator and $|\bar | |
226 \psi\rangle$ is a nonphysical state. Indeed, the constant function $|\bar\psi\rangle$ does | |
227 not approach zero at the edges of the well. By | |
228 feeding $H$ a nonphysical wavefunction, we obtained nonsensical | |
229 results. | |
230 | |
231 Second, and more importantly, we were wrong to claim that $H$ was a | |
232 physical operator\mdash{}that $H$ was hermitian. According to the | |
233 rule, a hermitian operator must convert physical states into other | |
234 physical states. But $|\psi\rangle$ is a physical state, as we said | |
235 when we first introduced it \mdash{}it is a normalized, continuous | |
236 function which approaches zero at the edges of the well and doesn't | |
237 exist outside it. On the other hand, $|\bar\psi\rangle$ is nonphysical | |
238 because it does not go to zero at the edges of the well. It is | |
239 therefore impermissible for $H$ to transform the physical state | |
240 $|\psi\rangle$ into the nonphysical state $|\bar\psi\rangle$. Because | |
241 $H$ converts some physical states into nonphysical states, it cannot | |
242 be a hermitian operator as we assumed. | |
243 | |
244 # Boundary conditions affect hermiticity | |
245 ** Boundary conditions alter hermiticity | |
246 It may surprise you (and it certainly surprised me) to find that the | |
247 Hamiltonian is not hermitian. One of the fundamental principles of | |
248 quantum mechanics is that hermitian operators correspond to physically | |
249 observable quantities; for this reason, surely the | |
250 Hamiltonian\mdash{}the operator corresponding to energy\mdash{}ought to be hermitian? | |
251 | |
252 But we must understand the correspondence between physically | |
253 observable quantities and hermitian operators: every hermitian | |
254 operator corresponds to a physically observable quantity, but not | |
255 every quantity that intuitively \ldquo{}ought\rdquo{} to be observable | |
256 will correspond to a hermitian operator[fn::For a simple example, | |
257 consider the differential operator \(D=\frac{d}{dx}\); although our | |
258 intuitions might suggest that $D$ is observable which leads us to | |
259 guess that $D$ is hermitian, it isn't. Still, the very closely related | |
260 operator $P=i\hbar\frac{d}{dx}$ /is/ hermitian. The point is that we | |
261 ought to validate our intuitions by checking the definitions.]. The | |
262 true definition of a hermitian operator imply that the Hamiltonian | |
263 stops being hermitian in the infinitely deep well. Here we arrive at a | |
264 crucial point: | |
265 | |
266 Operators do not change /form/ between problems: the one-dimensional | |
267 Hamiltonian is always $H=\frac{-\hbar^2}{2m}\frac{d^2}{dx^2}+V$, the | |
268 one-dimensional canonical momentum is always $P=i\hbar\frac{d}{dx}$, | |
269 and so on. | |
270 | |
271 However, operators do change in this respect: hermitian operators must | |
272 only take in physical states, and must only produce physical states; because | |
273 in different problems we /do/ change the requirements for being a | |
274 physical state, we also change what it takes for | |
275 an operator to be called hermitian. As a result, an operator that | |
276 is hermitian in one setting may fail to be hermitian in another. | |
277 | |
278 Having seen how boundary conditions can affect hermiticity, we | |
279 ought to be extra careful about which conditions we impose on our | |
280 wavefunctions. | |
281 | |
282 ** Choosing the right constraints | |
283 | |
284 We have said already that physicists | |
285 require wavefunctions to satisfy certain properties in order to be | |
286 deemed \ldquo{}physical\rdquo{}. To be specific, wavefunctions in the | |
287 infinitely deep well | |
288 - Must be *normalizable*, because they correspond to | |
289 probability amplitudes. | |
290 - Must have *smoothly-varying probability*, because if a particle is very | |
291 likely to be at a location, it ought to be likely to be /near/ | |
292 it as well. | |
293 - Must *not exist outside the well*, because it | |
294 would take an infinite amount of energy to do so. | |
295 | |
296 These conditions are surely reasonable. However, physicists sometimes | |
297 assert that in order to satisfy the second and third conditions, | |
298 physical wavefunctions | |
299 | |
300 - (?) Must *smoothly approach zero* towards the edges of the well. | |
301 | |
302 This final constraint is our reason for rejecting $|\bar\psi\rangle$ | |
303 as nonphysical and is consequently the reason why $H$ is not hermitian. If | |
304 we can convince ourselves that the final constraint is unnecessary, | |
305 $H$ may again be hermitian. This will satisfy our intuitions that the | |
306 energy operator /ought/ to be hermitian. | |
307 | |
308 But in fact, we have the following mathematical observation to save | |
309 us: a function $f$ does not need to be continuous in order for the | |
310 integral \(\int^x f\) to be continuous. As a particularly relevant | |
311 example, you may now notice that the function $\bar\psi(x)$ is not | |
312 itself continuous, although the integral $\int_0^x \bar\psi$ /is/ | |
313 continuous. Evidently, it doesn't matter that the wavefunction | |
314 $\bar\psi$ itself is not continuous; the probability corresponding to | |
315 $\bar\psi$ /does/ manage to vary continuously anyways. Because the | |
316 probability corresponding to $\bar\psi$ is the only aspect of | |
317 $\bar\psi$ which we can detect physically, we /can/ safely omit the | |
318 final constraint while keeping the other three. | |
319 | |
320 ** Symmetric operators look like hermitian operators, but sometimes aren't. | |
321 | |
322 | |
323 #+end_quote | |
324 ** COMMENT Re-examining physical constraints | |
325 | |
326 We have now discovered a flaw: when applied to the state | |
327 $|\psi\rangle$, the second method violates the rule that physical | |
328 operators must only take in physical states and must only produce | |
329 physical states. Let's examine the problem more closely. | |
330 | |
331 We have said already that physicists require wavefunctions to satisfy | |
332 certain properties in order to be deemed \ldquo{}physical\rdquo{}. To | |
333 be specific, wavefunctions in the infinitely deep well | |
334 - Must be *normalizable*, because they correspond to | |
335 probability amplitudes. | |
336 - Must have *smoothly-varying probability*, because if a particle is very | |
337 likely to be at a location, it ought to be likely to be /near/ | |
338 it as well. | |
339 - Must *not exist outside the well*, because it | |
340 would take an infinite amount of energy to do so. | |
341 | |
342 We now have discovered an important flaw in the second method: when | |
343 applied to the state $|\bar\psi\rangle$, the second method violates | |
344 the rule that physical operators must only take in | |
345 physical states and must only produce physical states. The problem is | |
346 even more serious, however | |
347 | |
348 | |
349 | |
350 [fn:1] I'm defining a new variable just to make certain expressions | |
351 look shorter; this cannot affect the content of the answer we'll | |
352 get. | |
353 | |
354 [fn:2] For example, in vaccuum (i.e., when the potential of the | |
355 physical system is $V(x)=0$ throughout all space), the momentum | |
356 eigenstates are not normalizable\mdash{}the relevant integral blows | |
357 up to infinity instead of converging to a number. Physicists modify | |
358 the definition of normalization slightly so that | |
359 \ldquo{}delta-normalizable \rdquo{} functions like these are included | |
360 among the physical wavefunctions. | |
361 | |
362 | |
363 | |
364 * COMMENT: What I thought I knew | |
365 | |
366 The following is a list of things I thought were true of quantum | |
367 mechanics; the catch is that the list contradicts itself. | |
368 | |
369 1. For any hermitian operator: Eigenstates with different eigenvalues are orthogonal. | |
370 2. For any hermitian operator: Any physically allowed state can be | |
371 written as a linear sum of eigenstates of the operator. | |
372 3. The momentum operator and energy operator are hermitian, because | |
373 momentum and energy are measureable quantities. | |
374 4. In the vacuum potential, the momentum and energy operators have these eigenstates: | |
375 - the momentum operator has an eigenstate | |
376 \(p(x)=\exp{(ipx/\hbar)}\) for each value of $p$. | |
377 - the energy operator has an eigenstate \(|E\rangle = | |
378 \alpha|p\rangle + \beta|-p\rangle\) for any \(\alpha,\beta\) and | |
379 the particular choice of momentum $p=\sqrt{2mE}$. | |
380 5. In the infinitely deep potential well, the momentum and energy | |
381 operators have these eigenstates: | |
382 - The momentum eigenstates and energy eigenstates have the same form | |
383 as in the vacuum potential: $p(x) = | |
384 \exp{(ipx/\hbar)}$ and $|E\rangle = \alpha|p\rangle + \beta|-p\rangle$. | |
385 - Even so, because of the boundary conditions on the | |
386 well, we must make the following modifications: | |
387 + Physically realistic states must be impossible to find outside the well. (Only a state of infinite | |
388 energy could exist outside the well, and infinite energy is not | |
389 realistic.) This requirement means, for example, that momentum | |
390 eigenstates in the infinitely deep well must be | |
391 \(p(x) | |
392 = \begin{cases}\exp{(ipx/\hbar)},& \text{for }0\lt{}x\lt{}a; | |
393 \\0, & \text{for }x<0\text{ or }x>a. \\ \end{cases}\) | |
394 + Physically realistic states must vary smoothly throughout | |
395 space. This means that if a particle in some state is very unlikely to be | |
396 /at/ a particular location, it is also very unlikely be /near/ | |
397 that location. Combining this requirement with the above | |
398 requirement, we find that the momentum operator no longer has | |
399 an eigenstate for each value of $p$; instead, only values of | |
400 $p$ that are integer multiples of $\pi \hbar/a$ are physically | |
401 realistic. Similarly, the energy operator no longer has an | |
402 eigenstate for each value of $E$; instead, the only energy | |
403 eigenstates in the infinitely deep well | |
404 are $E_n(x)=\sin(n\pi x/ a)$ for positive integers $n$. | |
405 | |
406 * COMMENT: | |
407 | |
408 ** Eigenstates with different eigenvalues are orthogonal | |
409 | |
410 #+begin_quote | |
411 *Theorem:* Eigenstates with different eigenvalues are orthogonal. | |
412 #+end_quote | |
413 | |
414 ** COMMENT : | |
415 I can prove this: if $\Lambda$ is any linear operator, suppose $|a\rangle$ | |
416 and $|b\rangle$ are eigenstates of $\Lambda$. This means that | |
417 | |
418 | |
419 \( | |
420 \begin{eqnarray} | |
421 \Lambda |a\rangle&=& a|a\rangle,\\ | |
422 \Lambda|b\rangle&=& b|b\rangle.\\ | |
423 \end{eqnarray} | |
424 \) | |
425 | |
426 If we take the difference of these eigenstates, we find that | |
427 | |
428 \( | |
429 \begin{eqnarray} | |
430 \Lambda\;\left(|a\rangle-|b\rangle\right) &=& \Lambda |a\rangle - \Lambda |b\rangle | |
431 \qquad \text{(because $\Lambda$ is linear.)}\\ | |
432 &=& a|a\rangle - b|b\rangle\qquad\text{(because $|a\rangle$ and | |
433 $|b\rangle$ are eigenstates of $\Lambda$)} | |
434 \end{eqnarray}\) | |
435 | |
436 | |
437 which means that $a\neq b$. | |
438 | |
439 ** Eigenvectors of hermitian operators span the space of solutions | |
440 | |
441 #+begin_quote | |
442 *Theorem:* If $\Omega$ is a hermitian operator, then every physically | |
443 allowed state can be written as a linear sum of eigenstates of | |
444 $\Omega$. | |
445 #+end_quote | |
446 | |
447 | |
448 | |
449 ** Momentum and energy are hermitian operators | |
450 This ought to be true because hermitian operators correspond to | |
451 observable quantities. Since we expect momentum and energy to be | |
452 measureable quantities, we expect that there are hermitian operators | |
453 to represent them. | |
454 | |
455 | |
456 ** Momentum and energy eigenstates in vacuum | |
457 An eigenstate of the momentum operator $P$ would be a state | |
458 \(|p\rangle\) such that \(P|p\rangle=p|p\rangle\). | |
459 | |
460 ** Momentum and energy eigenstates in the infinitely deep well | |
461 | |
462 | |
463 | |
464 * COMMENT Can you measure momentum in the infinitely deep well? | |
465 In summary, I thought I knew: | |
466 1. For any hermitian operator: eigenstates with different eigenvalues | |
467 are orthogonal. | |
468 2. For any hermitian operator: any physically realistic state can be | |
469 written as a linear sum of eigenstates of the operator. | |
470 3. The momentum operator and energy operator are hermitian, because | |
471 momentum and energy are observable quantities. | |
472 4. (The form of the momentum and energy eigenstates in the vacuum potential) | |
473 5. (The form of the momentum and energy eigenstates in the infinitely deep well potential) | |
474 | |
475 Additionally, I understood that because the infinitely deep potential | |
476 well is not realistic, states of such a system are not necessarily | |
477 physically realistic. Instead, I understood | |
478 \ldquo{}realistic states\rdquo{} to be those that satisfy the physically | |
479 unrealistic Schr\ouml{}dinger equation and its boundary conditions. | |
480 | |
481 With that final caveat, here is the problem: | |
482 | |
483 According to (5), the momentum eigenstates in the well are | |
484 | |
485 \(p(x)= \begin{cases}\exp{(ipx/\hbar)},& \text{for }0\lt{}x\lt{}a;\\0, & \text{for }x<0\text{ or }x>a. \\ \end{cases}\) | |
486 | |
487 (Additionally, we require that $p$ be an integer multiple of $\pi\hbar/a$.) | |
488 | |
489 However, /these/ states are not orthogonal, which contradicts the | |
490 assumption that (3) the momentum operator is hermitian and (2) | |
491 eigenstates of a hermitian are orthogonal if they have different eigenvalues. | |
492 | |
493 #+begin_quote | |
494 *Problem 1. The momentum eigenstates of the well are not orthogonal* | |
495 | |
496 /Proof./ If $p_1\neq p_2$, then | |
497 | |
498 \(\begin{eqnarray} | |
499 \langle p_1 | p_2\rangle &=& \int_{\infty}^\infty p_1^*(x)p_2(x)\,dx\\ | |
500 &=& \int_0^a p_1^*(x)p_2(x)\,dx\qquad\text{ Since }p_1(x)=p_2(x)=0\text{ | |
501 outside the well.}\\ | |
502 &=& \int_0^a \exp{(-ip_1x/\hbar)\exp{(ip_2x/\hbar)\,dx}}\\ | |
503 &=& \int_0^a \exp{\left[i(p_1-p_2)x/\hbar\right]}\,dx\\ | |
504 \end{eqnarray}\) | |
505 $\square$ | |
506 | |
507 #+end_quote | |
508 | |
509 | |
510 | |
511 ** COMMENT Momentum eigenstates | |
512 | |
513 In free space, the Hamiltonian is \(H=\frac{1}{2m}P^2\) and the | |
514 momentum operator $P$ has eigenstates \(p(x) = \exp{(-ipx/\hbar)}\). | |
515 | |
516 In the infinitely deep potential well, the Hamiltonian is the same but | |
517 there is a new condition in order for states to qualify as physically | |
518 allowed: the states must not exist anywhere outside of well, as it | |
519 takes an infinite amount of energy to do so. | |
520 | |
521 Notice that the momentum eigenstates defined above do /not/ satisfy | |
522 this condition. | |
523 | |
524 | |
525 | |
526 * COMMENT | |
527 For each physical system, there is a Schr\ouml{}dinger equation that | |
528 describes how a particle's state $|\psi\rangle$ will change over | |
529 time. | |
530 | |
531 \(\begin{eqnarray} | |
532 i\hbar \frac{\partial}{\partial t}|\psi\rangle &=& | |
533 H |\psi\rangle \equiv\frac{P^2}{2m}|\psi\rangle+V|\psi\rangle \end{eqnarray}\) | |
534 | |
535 This is a differential equation; each solution to the | |
536 Schr\ouml{}dinger equation is a state that is physically allowed for | |
537 our particle. Here, physically allowed states are | |
538 those that change in physically allowed ways. However, like any differential | |
539 equation, the Schr\ouml{}dinger equation can be accompanied by | |
540 /boundary conditions/\mdash{}conditions that further restrict which | |
541 states qualify as physically allowed. | |
542 | |
543 | |
544 | |
545 | |
546 ** Eigenstates of momentum | |
547 | |
548 | |
549 | |
550 | |
551 #In the infinitely deep well potential $V(x)=0$, the Schr\ouml{}dinger | |
552 | |
553 #\(i\hbar\frac{\partial}{\partial t}|\psi\rangle = H|\psi\rangle\) | |
554 | |
555 | |
556 | |
557 | |
558 | |
559 | |
560 | |
561 * COMMENT | |
562 | |
563 #* The infinite square well potential | |
564 | |
565 A particle exists in a potential that is | |
566 infinite everywhere except for a region of length \(a\), where the potential is zero. This means that the | |
567 particle exists in a potential[fn:coords][fn:infinity] | |
568 | |
569 | |
570 \(V(x)=\begin{cases}0,&\text{for }\;0< x< a;\\\infty,&\text{for | |
571 }\;x<0\text{ or }x>a.\end{cases}\) | |
572 | |
573 The Schr\ouml{}dinger equation describes how the particle's state | |
574 \(|\psi\rangle\) will change over time in this system. | |
575 | |
576 \(\begin{eqnarray} | |
577 i\hbar \frac{\partial}{\partial t}|\psi\rangle &=& | |
578 H |\psi\rangle \equiv\frac{P^2}{2m}|\psi\rangle+V|\psi\rangle \end{eqnarray}\) | |
579 | |
580 This is a differential equation; each solution to the | |
581 Schr\ouml{}dinger equation is a state that is physically allowed for | |
582 our particle. Here, physically allowed states are | |
583 those that change in physically allowed ways. However, like any differential | |
584 equation, the Schr\ouml{}dinger equation can be accompanied by | |
585 /boundary conditions/\mdash{}conditions that further restrict which | |
586 states qualify as physically allowed. | |
587 | |
588 | |
589 Whenever possible, physicists impose these boundary conditions: | |
590 - A physically allowed state ought to be a /smoothly-varying function of position./ This means | |
591 that if a particle in the state is likely to be /at/ a particular location, | |
592 it is also likely to be /near/ that location. | |
593 | |
594 These boundary conditions imply that for the square well potential in | |
595 this problem, | |
596 | |
597 - Physically allowed states must be totally confined to the well, | |
598 because it takes an infinite amount of energy to exist anywhere | |
599 outside of the well (and physically allowed states ought to have | |
600 only finite energy). | |
601 - Physically allowed states must be increasingly unlikely to find very | |
602 close to the walls of the well. This is because of two conditions: the above | |
603 condition says that the particle is /impossible/ to find | |
604 outside of the well, and the smoothly-varying condition says | |
605 that if a particle is impossible to find at a particular location, | |
606 it must be unlikely to be found nearby that location. | |
607 | |
608 #; physically allowed states are those that change in physically | |
609 #allowed ways. | |
610 | |
611 | |
612 #** Boundary conditions | |
613 Because the potential is infinite everywhere except within the well, | |
614 a realistic particle must be confined to exist only within the | |
615 well\mdash{}its wavefunction must be zero everywhere beyond the walls | |
616 of the well. | |
617 | |
618 | |
619 [fn:coords] I chose my coordinate system so that the well extends from | |
620 \(0<x<a\). Others choose a coordinate system so that the well extends from | |
621 \(-\frac{a}{2}<x<\frac{a}{2}\). Although both coordinate systems describe the same physical | |
622 situation, they give different-looking answers. | |
623 | |
624 [fn:infinity] Of course, infinite potentials are not | |
625 realistic. Instead, they are useful approximations to finite | |
626 potentials when \ldquo{}infinity\rdquo{} and \ldquo{}the actual height | |
627 of the well\rdquo{} are close enough for your own practical | |
628 purposes. Having introduced a physical impossibility into the problem | |
629 already, we don't expect to get physically realistic solutions; we | |
630 just expect to get mathematically consistent ones. The forthcoming | |
631 trouble is that we don't. |