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HW1 2014

(1) The document provides instructions for a homework assignment on a two-atom quantum mechanical system. It defines the Hamiltonian and basis states for the system and instructs the reader to calculate the matrix elements and eigenenergies. (2) The reader is asked to construct the 2x2 Hamiltonian matrix using the calculated matrix elements and determine the eigenenergies and eigenvectors of the system for given parameter values. (3) The reader must then calculate probabilities of finding the electron localized around each atom for both the ground and excited states and identify the type of chemical bond corresponding to a given parameter set.

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Protik Das
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137 views2 pages

HW1 2014

(1) The document provides instructions for a homework assignment on a two-atom quantum mechanical system. It defines the Hamiltonian and basis states for the system and instructs the reader to calculate the matrix elements and eigenenergies. (2) The reader is asked to construct the 2x2 Hamiltonian matrix using the calculated matrix elements and determine the eigenenergies and eigenvectors of the system for given parameter values. (3) The reader must then calculate probabilities of finding the electron localized around each atom for both the ground and excited states and identify the type of chemical bond corresponding to a given parameter set.

Uploaded by

Protik Das
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd

EE 208, HW 1, due Wed. Jan. 22. Will discuss in Discussion Section Mon. Jan. 20. 1:10 - 2pm.

Consider a 2-atom system for which the initial energies of the isolated atoms are unequal (nondegenerate), i.e. p2 + Va | s a 2m p2 + Vc | s c 2m = a | sa = c | sc (1) (2)

where c > a . |sa and |sc are the s orbitals of atoms a and c, respectively, and sa |sc = a,c . Both are real functions of r. In the language we have been using, |sa and |sc are the two basis vectors or basis states in a two dimensional vector (Hilbert) space. Any vector (function) in this space is represented as a linear combination of |sa and |sc . Va (r) is the potential of the nucleus of atom a, and Vc (r) is the potential of the nucleus of atom c. The eigenvectors of the combined system satisfy p2 (3) + Va + Vc | i = E i | i 2m To nd the eigenvalues, Ei , and eigenvectors, |i , we construct the 2 2 Hamiltonian matrix [H ] p2 by calculating the matrix elements Hi,j = si |H |sj of the Hamiltonian H = 2 m + Va + Vc . (1) Following the steps in class, determine expressions for the matrix elements Ha,a = Sa |H |Sa , Ha,b , Hb,a , and Hb,b . (2) The Hamiltonian matrix can be written in the form [H ] = t a t c . (4)

Dene each element of the matrix in terms of the elements calculated in (1). Note that the negative sign has been explicitly taken out of the o-diagonal elements, so that now t > 0. (3) Using the Hamiltonian matrix from Eq. (4), calculate the eigenenergies, E0 and E1 . Write them in terms of = ( a+ c )/2, = ( c a )/2, and t. (4) Let a = 9 eV, c = 5 eV, and t = 3 eV. Determine numerical values for the eigenenergies E0 and E1 . (5) Using the numerical values from problem (4), nd the 2 eigenvectors |0 and |1 corresponding to the two eigenvalues E0 and E1 . Your answer should be of the form |0 = a1 |sa + a2 |sc and |1 = b1 |sa + b2 |sc where the ai and bi are real coecients. Normalize the eigenvectors. (6) (a) In the ground state, what is the probability of nding the electron localized around atom a, i.e. what is | sa |0 |2 ? 1

(b) In the excited state, what is the probability of nding the electron localized around atom c, i.e. what is | sc |1 |2 ? (7) Now, let a = c = 5 eV and t = 3 eV. (a) In the ground state, what is the probability of nding the electron localized around atom a, i.e. what is | sa |0 |2 ? (b) In the excited state, what is the probability of nding the electron localized around atom c, i.e. what is | sc |1 |2 ? (c) This situation corresponds to what type of chemical bond? (8) What would be an appropriate parameter to use to estimate the energies a and c from atomic data?

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