Szabo-Ostlund. Exercise 2.13 Evaluate the matrix element Ψr |O1 |Ψs , where O1 is a sum of one-electron a b operators h(i).

Background Slater determinant short hand notation for normalized determinant, including the normalization constant, only showing diagonal elements, (Szabo-Ostlund eq 2.38): Ψ (x1 , x2 , ..., xN ) = |χi (x1 )χj (x2 ) · · · χk (xN ) Electron labels always chosen to be in order x1 , x2 , ..., xN , further shortening of notation (Szabo-Ostlund eq 2.39): Ψ (x1 , x2 , ..., xN ) = |χi χj · · · χk Interchange of two columns changes sign of determinant (Szabo Ostlund eq 2.40): | · · · χm · · · χn · · · = −| · · · χn · · · χm · · · Definition of Hartree-Fock ground state (Szabo-Ostlund eq 2.64): |Ψ0 = |χ1 χ2 · · · χa χb · · · χN Definition of singly excited state (Szabo-Ostlund eq 2.65): |Ψr = |χ1 χ2 · · · χr χb · · · χN a Example (p.69): To use the rules from tables 2.3/2.4 and 2.5/2.6, the determinants |K and |L need to be in maximum conincidence: Ψ1 = |abcd Ψ2 = |crds Ψ2 can be rearranged by switching columns and introducing minus sign: Ψ2 = |crds = −|crsd = |srcd then Ψ1 |O1 |Ψ2 = 0 (case 3, table 2.3). Exercise: Now Ψr |O1 |Ψs . a b If a = b and r = s: The matrix element is 0 according to case 3 of table 2.3. If a = b and r = s: The matrix element is written as · · · χr χb · · · |O1 | · · · χa χs · · · . Now, on the left side, I switch the two spin-orbitals, to bring the spin-orbitals χa and χb into maximum conicidende, since from the definition they are equal and evaluate the matrix element using case 2 from table 2.3. This introduces a minus sign: · · · χr χb · · · |O1 | · · · χa χs · · · = − · · · χb χr · · · |O1 | · · · χa χs · · · = − r|h|s (Case 2) However, this should be r|h|s , without a minus. Where am I going wrong here??? 1