Max Diem

Quantum Mechanical Foundations of Molecular Spectroscopy


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alt="left-bracket ModifyingAbove p With Ì‚ Subscript x Baseline comma ModifyingAbove x With Ì‚ right-bracket"/> of the momentum operator ModifyingAbove p With Ì‚ Subscript x and the position operator ModifyingAbove x With Ì‚ when applied to a function f(x), i.e. determine

      (E2.2.1)ModifyingAbove p With Ì‚ Subscript x Baseline ModifyingAbove x With Ì‚ f left-parenthesis x right-parenthesis minus ModifyingAbove x With Ì‚ ModifyingAbove p With Ì‚ Subscript x Baseline f left-parenthesis x right-parenthesis equals

      (E2.2.2)equals minus i normal h with stroke StartFraction normal d Over normal d x EndFraction left-parenthesis ModifyingAbove x With Ì‚ f left-parenthesis x right-parenthesis right-parenthesis minus ModifyingAbove x With Ì‚ left-parenthesis minus i normal h with stroke StartFraction normal d Over normal d x EndFraction f left-parenthesis x right-parenthesis right-parenthesis

      Answer:

      The derivative of the product left-parenthesis ModifyingAbove x With Ì‚ f left-parenthesis x right-parenthesis right-parenthesis needs to be evaluated using the product rule of differentiation. Thus,

      (E2.2.3)equals minus i normal h with stroke left-parenthesis f left-parenthesis x right-parenthesis plus ModifyingAbove x With Ì‚ StartFraction normal d f left-parenthesis x right-parenthesis Over normal d x EndFraction minus ModifyingAbove x With Ì‚ StartFraction normal d f left-parenthesis x right-parenthesis Over normal d x EndFraction right-parenthesis

      (E2.2.4)equals minus i normal h with stroke f left-parenthesis x right-parenthesis equals StartFraction normal h with stroke Over i EndFraction f left-parenthesis x right-parenthesis

      Thus, the commutator

      which predicts that the position and momentum of a moving particle cannot be determined simultaneously. This was stated earlier in Eq. (2.1) as the Heisenberg uncertainty principle as

      (2.1)normal upper Delta p Subscript x Baseline normal upper Delta x greater-than-or-equal-to StartFraction normal h with stroke Over 2 EndFraction

Schematic illustration of the potential energy functions and analytical expressions for (a) molecular vibrations and (b) an electron in the field of a nucleus. Here, f is a force constant, k is the Coulombic constant, and e is the electron charge.

      In Postulate 2, the kinetic energy T was substituted by the operator

      (2.4)ModifyingAbove upper T With Ì‚ equals minus StartFraction normal h with stroke squared Over 2 m EndFraction StartFraction partial-differential squared Over partial-differential x squared EndFraction

      When these potential energy expressions are substituted into the Schrödinger equation

      (2.7)ModifyingAbove upper H With Ì‚ normal psi left-parenthesis x right-parenthesis equals left-brace minus StartFraction normal h with stroke squared Over 2 m EndFraction StartFraction partial-differential squared Over partial-differential x squared EndFraction plus upper V right-brace normal psi left-parenthesis x right-parenthesis equals upper E normal psi left-parenthesis x right-parenthesis

      one obtains a differential equation:

      for the harmonic oscillation of a diatomic molecule and