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We will put electronic structure theory into perspective and define the general problem that has to be solved. We discuss antisymmetry of the wave function in some detail and introduce a basis of Slater determinants, which are the antisymmetrized equivalent of the pure Hartree products of one-electron orbitals. This allows us to formulate the linear variation problem in the space of all determinants that can be formed from a finite set of spin-orbitals. This defines the Full CI solution in quantum chemistry, and it serves as a benchmark for accurate approximation methods. The reading material is Szabo and Ostlund pages 39 to 64. Our second topic concerns the vibrational problem, primarily in one dimension (diatomics), and the use of operator algebra to recast the problem and to find solutions. This provides a convenient introduction to the language of second quantization, that we will later on use also for the electronic structure problem. You will receive a set of hand written lecture notes. The problem set below has some problems on electronic structure theory, but the majority of the problem set focuses on operator algebra for vibrational problems. The last two questions require you to use Maple. This is a symbolic algebra package that has been developed at the University of Waterloo. On Nexus you can find version 8 under “Programs” → “Math and Science” → “Maple 8”. You can find a brief tutorial on Maple with some examples on the Nooijen web site. The file maple_basics.mws can be opened in the Maple program. First go through a brief tutorial in Maple, then see what is done in the sample file, and off you go to do some calculations in Maple. The problem set is quite extended, not in the least because of the last two problems.

as well as the Hermiticty of p ˆ and q ˆ ˆ − ip ˆ ).(b ) = n(b ) . b = n(b) . 2. and that it has the same parity as P ˆ .e.2. The following problems are on vibrational problems and using the bose operator algebra. where p b ∂q 2 2 in your proofs. FYI the antisymmetrizer is transpositions or interchanges.. ˆ. It then acts as a projection operator on the antisymmetric subspace. ˆ† 1 4. The operators b * ∀φ . You can use the commutation relations b b = .1.. the definitions ∂ ˆ† = 1 ( q ˆ = 1 (q ˆ = −i . b. Every permutation can be written as a product of transpositions P i 1 2 k shown in class that every transposition is Hermitian. i. which one might expect. 2. ˆ = TT ˆ ˆ .Problem Set 1. Szabo and Ostlund: 2. It was 3.T ˆ . and is its own inverse.4. 2. Show the following. where the sum runs over all N! permutations of N coordinates. φ b ˆ† ψ = ψ b ˆφ a.5.. Use these permutation operator is unitary: P i i i results to show that the antisymmetrization operator is Hermitian.7 2. Show that AA N! ˆ'= 1 ˆ . In this case applying the sometimes normalized differently as A (−) pi P ∑ i N ! i=1 antisymmetrization operator twice yields the same result. The N-particle antisymmetrization operator can be given in the following ˆ= ˆ . and form A ∑ (−) pi P i i =1 N! pi is the parity of the permutation that indicates if it consists of an even or odd number of ˆ ˆ = N !A ˆ . 2. ˆ† and b ˆ are Hermitian conjugates. (b) .ψ ˆ ˆ† n ˆ† n−1 ˆ n ˆ† ˆ n−1 b. b ˆ + ip ˆ ). Show that the ˆ † = P −1 .

and d. where 0 is normalized to unity. ˆ† n = n + 1 n + 1 b. Position. x b. b d. it follows that the functions n are orthonormal.5. The orthonormal eigenfunctions of the harmonic oscillator are defined as n = 1 ˆ† n (b ) 0 . Using the relations discussed in the n! previous question show: a. b ˆ n = n n −1 c. n is indeed normalized to 1. Write the following operators in terms of the b operators are defined in terms of the dimensionless coordinates q = conjugate momentum operator i a. Kinetic energy operator − d. n ≠ m . ˆ† and b ˆ . n m = 0. The Hamiltonian − =2 ∂ 2 1 + mω 2 x 2 2 2m ∂x 2 . remembering that these 6. Potential energy 1 mω 2 x 2 2 e. Momentum −i= ∂ ∂x =2 ∂ 2 2m ∂x 2 mω x and the = ∂ . From a. ∂q c.

operators are to the left of b Examples are given below.. n m = δ . To this end we wish to evaluate the general form for the matrix elements n H ˆ and b ˆ† . This is called “normal order”. ˆ (b + b) = ((b ) + 3(b q 4 2 1 ∂2 1 2 + q + λ q 4 in 2 2 ∂q 2 Now derive the complete formula for the Hamiltonian H = − second quantization. So the operators b ˆ act first. = (b b b + 3b 2 2 ˆ 3 for yourself. Consider the Hamiltonian of the following form H = − 1 ∂2 1 2 + q + λ q 4 . We want to (b ) 0 . to find approximate energy eigenvalues of H n! ˆ m . We will use 2 2 ∂q 2 the linear variational principle using a finite set of harmonic oscillator basis states n = 1 ˆ† n ˆ .... b ˆ† operators in a product of We want to write the operator λ q 4 in a form that all of the b ˆ . b ˆ n = n n − 1 . ˆ= q 1 ˆ† ˆ (b + b) 2 1 ˆ † ˆ ˆ† ˆ 1 ˆ † ˆ † ˆ† ˆ ˆ ˆ† ˆ ˆ 1 ˆ † ˆ † ˆ†b ˆ + bb ˆ ˆ + 1) ˆ 2 = (b + b)(b + b) = (b b + b b + bb + bb) = (b b + 2b q 2 2 2 ˆ3 = q 1 2 ˆ† ˆ 1 ˆ† ˆ† ˆ†b ˆ + bb ˆ ˆ + 1)(b ˆ† + b ˆ) ˆ (b + b) = (b b + 2b q 2 2 2 1 ˆ† ˆ† ˆ† ˆ†b ˆ†b ˆ + 3b ˆ† + 3b ˆ + 3b ˆ†bb ˆ ˆ + bbb ˆ ˆ ˆ) = . in particular: ˆ(b ˆ† ) n = (b ˆ† ) n b ˆ + n(b ˆ† ) n−1 . Let us do it in steps. filling in the appropriate steps. You can make use of the express the Hamiltonian in terms of the operators b relations expressed under question 4. ˆ m . (b ˆ) n b ˆ† = b ˆ† (b ˆ) n + n(b ˆ) n−1 . Finally Derive the formula for q ˆ4 = q 1 3 ˆ† ˆ 1 ˆ† 3 ˆ† ) 2 b ˆ + 3b ˆ† + 3b ˆ + 3b ˆ† (b ˆ) 2 + (b ˆ)3 )(b ˆ† + b ˆ) = .7. where you can make repeated use of the Next evaluate the matrix elements n H ˆ† n = n + 1 n + 1 . As a check on your results confirm that your Hamiltonian is Hermitian. For example: relations b nm .

Diagonalize the Hamiltonian for M=1. including the pure harmonic part of the potential as a function of q . Plot the total potential. Always plot the potential to see if you are on the right track. Choose λ = 0. + q − µq2 + λq4 = b with corresponding Hamiltonian H = − 2 2 ∂q 2 Taking µ = 1 and λ = 0.05 defines a nice double well potential. You can create the matrix elements for the Hamiltonian in n=0 M Maple. in analogy to what is done in the sample Maple page on the web site. Do you observe something remarkable? In this context.…. What happens to the eigenvalues if you increase the values for µ and/or decrease the value of λ . then stay the same as you increase the basis set 1 function at a time? 1 You can generate a double well potential by using the potential V (q ) = + q 2 − µ q 2 + λ q 4 2 1 ∂2 1 2 ˆ†b ˆ − µq2 + λq4 . Confirm that your results obey the interleafing theorem. why do about half the eigenvalues stay the same with every increase of the basis set? Or phrased differently why do all of the eigenvalues alternately lower .m +1m m + 1 ˆ m = mH ˆ n Again you can check your results by confirming that n H Let us now consider the linear variational principle using the following expansion for the trial function Ψ = ∑ n cn . Also calculate the eigenvectors of the Hamiltonian in Maple. Here you have matrix elements n H obtained the numerical solutions of the double well potential. This full problem set is lengthy. Can you understand the “pairing of the eigenvalues” by sketching the eigen functions in a deep double well potential? This could be a model of the umbrella tunnelling vibration in the ammonia molecule.1 .ˆ†b ˆ†b ˆm = m nb ˆ†b ˆ† m − 1 = m n b ˆ† m = m m + 1 n m + 1 = δ nb n . but it shows you clearly how nice it can be to have a convenient Mathematics program! . You can see an example in the Maple sample file. of how to set things up. Next evaluate the ˆ m as before and plot the new energy eigenvalues. 10 and plot the eigenvalues as a function of the size of the basis set.

Plot the absorption spectrum and the emission spectrum on the same energy scale. Also investigate what happens if the displacement is smaller (d=0. ∆E = 10. Use the completeness relation ∑ n = e− d 2 / 2 . What are the excitation energies of the various vibrational levels in the electronically excited state w. or larger d=3.t. but its operators b equilibrium geometry is displaced by a distance 2d . Show that 0 n Franck-Condon factors. in the reduced dimensionless coordinates. the ground state vibrational level? What is the 0-0 energy? What is the vertical excitation energy? d. Let us assume a ground state Hamiltonian H = − 1 ∂2 1 2 + q and the associated 2 ∂q 2 2 ˆ† .0). 0 of the electronic excited state in terms of b express the vibrational eigenstates n c. Using Maple. which are defined as 0 n dn .0 . and the corresponding intensities? g. d = 1. = ∆E + =ωb b 2 ˆ† . n 0 = 0 0 = 1 to derive 0 0 0n → n . 00 n! e. The excited state Hamiltonian is given by 1 ∂2 1 H = ∆E − =ω 2 + =ω ( q − 2 d ) 2 2 ∂q 2 a. . An electronically excited state has the same harmonic frequency. Show that the displaced operators satisfy the same commutation relations as b † . The intensities in the absorption spectrum are proportional to the squares of the = . b ˆ . b ˆ . In the emission spectrum the transitions are given by 0 energies. b =b ˆ − d takes the form H †b + 1 =ω .8. Show that the excited state Hamiltonian in terms of the displaced operators † = b ˆ† − d . and b. What are the transition f.5.r. and the following parameters: =ω = 1.

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