What is the role of the spin variable in quantum chemistry?

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Discussion Overview

The discussion centers around the role of the spin variable in quantum chemistry, particularly in the context of spin wave functions and their integration in calculations involving matrix elements. Participants explore the implications of treating spin as a discrete variable versus an integrated variable, and how this affects the formulation of electronic wave functions and Slater determinants.

Discussion Character

  • Technical explanation
  • Debate/contested

Main Points Raised

  • One participant notes that spin wave functions are often represented as alpha and beta, which are used in constructing Slater determinants, but questions the treatment of spin as a variable in integrations.
  • Another participant suggests that the notation used in quantum chemistry may be confusing, indicating that the integral sign can represent both sums and integrals, particularly in the context of spin degrees of freedom.
  • A participant clarifies that the spin variable is one of the four non-relativistic coordinates of an electron and explains that "spin integration" is a term used to denote summation over the two possible spin states, rather than actual integration.
  • There is a reiteration of the previous point about spin integration being a shorthand for summation, emphasizing that it is a notational convenience rather than a complex mathematical operation.
  • One participant expresses confusion regarding the integration over the spin variable as presented in the literature, seeking further clarification on this practice.

Areas of Agreement / Disagreement

Participants express differing views on the treatment of the spin variable in calculations, with some supporting the idea of treating it as a discrete sum while others acknowledge the use of integration notation. The discussion remains unresolved regarding the appropriateness of integrating over the spin variable.

Contextual Notes

Some participants highlight potential confusion arising from notational choices in quantum chemistry texts, particularly regarding the distinction between integration and summation over spin variables. There is an acknowledgment of the need for clarity in how these concepts are presented in educational materials.

Amok
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In various quantum chemistry books and course booklets I came across spin wave functions (usually referred to as alpha and beta for spin and up and down, respectively) that depend on a so called spin-variable. They are usually used to construct slater determinants. An example of this is Modern Quantum Chemistry (a great book). My problem is that sometimes, when matrix elements are computed, integrations over the spin-variable are made (e.g http://en.wikipedia.org/wiki/Franck–Condon_principle). My teacher told me this makes no sense since spin is supposed to be a discrete variable, so it should be a sum. What is this spin variable? Does it have anything to do with the actual 'spin' observable? I think it is a bit of a construct for when you actually have to write down matrix elements as integrals and not as scalar products using braket notation. Can anyone clarify this for me?
 
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I suspect this is simply slightly confusing notational choice. It is not uncommon to use the integral sign abstractly to represent a large variety of sums and integrals. Unless one is integrating over spin coherent states (an overcomplete basis), the sum over spin degrees of freedom is always discrete.
 
The spin variable is one of the four non-relativistic coordinates of an electron, the other three being (for example) spatial positions:
\vec x = (\vec r, s)
where s is either alpha or beta (or up or down) -- the spin variable. The electronic wave function of N electrons is a function of N such x variables and antisymmetric with respect to the exchange of them (of full x'es, not only r's or s's individually).

"Spin integration" is used as a synonym for "spin summation", and means summing over the two possible states of each spin variable. This is just a form for avoiding cumbersome notation by artificially splitting up the x = (r,s) integrations into r-integrations and s-summations. No advanced magic going on here.
 
cgk said:
The spin variable is one of the four non-relativistic coordinates of an electron, the other three being (for example) spatial positions:
\vec x = (\vec r, s)
where s is either alpha or beta (or up or down) -- the spin variable. The electronic wave function of N electrons is a function of N such x variables and antisymmetric with respect to the exchange of them (of full x'es, not only r's or s's individually).

"Spin integration" is used as a synonym for "spin summation", and means summing over the two possible states of each spin variable. This is just a form for avoiding cumbersome notation by artificially splitting up the x = (r,s) integrations into r-integrations and s-summations. No advanced magic going on here.

I get the notation when you integrate over x = (r,s), but in the book I mentioned the actually integrate over the spin-variable (over s).
 

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