Homework 7 Spring 2008 1) a) Energy of an electron in a 1-D box. n 2h 2 En = 8mL2 h2 (6.626 1034 J s) 2 E1 = = = 8.605 1019 J 2 31 11 2 8me L 8(9.

.109 10 kg)(5 5.292 10 m) b) Energy of each electron the box representing an H2 molecule. (6.626 1034 J s)2 E1(H 2 ) = = 5.22 1019 J 31 2 11 2 8(9.109 10 kg)(5 + 0.75) (5.292 10 m) c) Bond formation energy of forming the H2 molecule. E = 2E1(H 2 ) 2E1(H) = 2(5.22 1019 ) 2(8.605 1019 ) = 6.76 1019 J d) Convert bond formation energy and compare to 430kJ/mol. E = (6.76 1019 J)(6.023 10 23 mol1 ) /1000 = 407.3kJ /mol The approximation is not perfect but of the right magnitude. This agreement suggests that delocalization of the electron density in H2, which lowers the kinetic energy of the ground state, plays a key role in covalent bond formation. 2) a) Calculate the energy of an electron in H2+. + E B = E1(H 2 ) E1 (H) let H me

H e4 (9.109 1031 kg)(1.602 1019 C) 4 = = 2.177 1021 J 32 2 2 h 2 32 2 (8.854 1012 C 2 J 1m1 ) 2 (1.055 1034 Js) 2 6.023 1023 E1(H) = (2.177 1021 J) = 1310.6kJ /mol 10 3
E1(H) =
+ E1(H 2 ) = E B + E1 (H) = 210 + 1310.6 = 1520.6kJ /mol

b) Since bond formation energy for each electron are additive: EB EB 2+ + H 2 + 2e H 2 + e H 2

E B (H 2 ) = 2(210kJ /mol) = 420kJ /mol

c) Compared to experimental bond formation energy of 430kJ/mol, possible differences could be: Bond lengths of the two molecules are different; H2+ has a longer bond than H2 Electron-electron repulsion has been neglected.

3) a) Secular Determinants For Linear H 3

For cyclic H 3

E 0 E =0 0 E

E E =0 E

b) Solve the Secular Determinants ( E) 3 2 2 ( E) = 0 ( E) 3 + 2 3 3 2 ( E) = 0

( E)[( E) 2 2 2 ] = 0 E = , 2
c) Remember that = 210kJ /mol

[( - E) - ]2 [( E) + 2 ] = 0 E = , , + 2

2 > 2 so the E + for the cyclic geometry will be more stable as it is a lower energy. We can also calculate the bond formation energy for both geometries. E B (linear) = 2( + 2 ) 2 = 2 2 = 590kJ /mol Cyclic H + is more stable. 3 E B (cyclic) = 2( + 2 ) 2 = 4 = 840kJ /mol

d) Formation energy for cyclic geometry was performed in part c, compare to 849kJ/mol. The Huckel approximation is a slightly less negative number, but is a very good approximation. e) Note that H3 has 3 electrons so 2 electrons will go into the lowest energy state while 1 electron will have to go into the higher energy state. H3- has 4 electrons so 2 electrons will go into the lowest energy state and 2 electrons will go into the next higher energy state. For the linear structure we know that the possible energies are: , 2 . For H 3

E B = 2( + 2 ) + 3 = 2 2 = 594kJ /mol For H -3

E B = 2( + 2 ) + 2 4 = 2 2 = 594kJ /mol So linear H3 and H3- are stable when compared to each other, but not as stable as H3+.
For the cyclic structure we know that the possible energies are: , , + 2 . For H 3

E B = 2( + 2 ) + ( ) 3 = 3 = 630kJ /mol For H -3

E B = 2( + 2 ) + 2( ) 4 = 2 = 420kJ /mol So cyclic H3 is more stable than linear form or either form of H3-, but still not as stable as H3+.

4) a) Solve the secular determinant to find the energies. E =0 E

E =

b) =-80 kJ/mol so E B = 2( + ) 2 = 2 = 160kJ /mol c)

ground (in phase)

excited (out of phase)

Note that these orbitals also resemble the ground and first excited states of a particle in a box, as the ground state has no node and the excited state has one node (as is also the case for the ground, , and excited, *, states of H2). d) Secular determinant is the same as that of linear H3+

e) =-80 kJ/mol so E B (allyl) = 2( + 2 ) 2 = 2 2 = 226kJ /mol f)

ground

excited

g) Energy gained by delocalizing the three carbon atom pz electrons over the molecular orbital. h) E deloc = E allyl E ethene = 2 2 2 = (2 2 2) 0.84 = 67.2kJ /mol