SpectraCat
Science Advisor
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conway said:The nine tensors correspond in my picture to the nine d-orbitals: a single spin-zero (with two spherical nodes), three spin-one (with a single spherical node), and five spin-two elements.
There are five d-orbitals, not 9 ... d-orbitals correspond to l=2, the degeneracy is 2l+1=5. If you consider pure Cartesian functions (xx, xy, xz, yy, yz, and zz), there you can get 6 basic functions that look like d-orbitals, but this set has a linear dependency since the combination xx + yy + zz has spherical symmetry. I have no idea what you are talking about with 9 functions here.
You've seen the weird pictures of the electron clouds in chemistry textbooks. The peculiar thing is that these are usually shown with an implied z-axis symmetry, including the funny vertical dumbbell with the ring around the outside. I don't know if I will succede in describing in words how this lines up to the vector picture I talked about for spin-one, but I can try.
The vector picture for orbital angular momentum of 2 (i.e. d-orbitals) is simple. There are 5 degenerate states (the d-orbitals), each corresponding to an angular momentum vector of length sqrt[l(l+1)]=sqrt(6). Each orbital has a different ml quantum number describing the projection of each angular momentum vector on an arbitrarily chosen space-fixed axis. By convention the z-axis is chosen because the differential operator Lz has a very simple form .. it is just:
-i\hbar\frac{\partial}{\partial\phi}, where \phi is the polar angle in spherical polar coordinates. It is trivial to solve for the eigenstates of this operator ... they are just e^{i m_l \phi}, where ml can take values from -l to +l. These are the complex orbitals conway was referring to ... they cannot be easily visualized due to the complex phase. Therefore, we generally take linear combinations of them to create pure-real functions that can visualized. They are eigenfunctions of the L2[/SUB] operator (any linear combination of degenerate eigenstates is also an eigenstate), but they are not eigenstates of Lz, however they can be plotted in 3-D. We take balanced symmetric and anti-symmetric combinations of the ml=+/-2 orbitals to make the dxy and dx2-y2 orbitals, we construct the dxy and dxy by combining the ml=+/-1 orbitals, and the ml=0 orbital and dz2 orbital are identical.
First of all, let me ask if you will agree with my picture for the p-orbitals. Let me first ignore the "physicist's" orbitals with their swirlling complex amplitudes, and concentrate on the "chemist's" orbitals, the three dumbbells aligned along the x,y, and z axis. I am going to ask you to consider what happens if we add a small component of p orbitals in any combination to the ground state, e.g:
0.955{|s>} + 0.2{|p_x>} + 0.2{|p_y>} + 0.1|p_z>
I wonder if you will agree that the effect of this superposition in, say, the hydrogen atom, is essentially to displace the ground state a small distance in the direction (2,2,1)? So basically, to a good approximation, the whole cloud just moves a little bit in that direction.
This is most definitely not correct ... the cloud does not move in the (2,2,1) direction in space. What happens is mixing in the p-character in the way you describe would create an oblate distortion of the spherically symmetric s-cloud in the x-y plane. The linear combination:
0.2(p_x + p_y) is just 0.2\sqrt(2)p_1, which is a toroid with complex phase around the z-axis. If you added 0.2sqrt(2)p_z, then you would exactly balance that toroidal contribution and recover the spherical symmetry ... the fact that only 0.1 was added means that there will be a slight bulge in the x-y plane.
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