The Wavefunction

Peter Joshua Atkins, Julio de Paula, Ronald Friedman

Contents Postulate I: the wavefunction 42 Brief illustration 5.1: The wavefunction 43 Postulate II: the Born interpretation 43 Probabilities and probability densities 43 Example 5.1: Interpreting a wavefunction 44 Normalization 44 Example 5.2: Normalizing a wavefunction 45 Constraints on the...

Michelle Richer, Taewon David Kim, Paul W. Ayers

ABSTRACT We consider wavefunctions built from antisymmetrized products of two‐electron wavefunctions (geminals), which is arguably the simplest extension of the antisymmetrized product of one‐electron wavefunctions (orbitals) (i.e., a Slater determinant). Extensive use of geminals in wavefunctions has been limited by their high cost stemming from the many combinations of the two‐electron basis functions (orbital pairs) used to build the geminals. When evaluating the overlap of the APG wavefunction with an orthogonal Slater determinant, this cost can be interpreted as the cost of evaluating the permanent, resulting from the symmetry with respect to the interchange of orbital pairs, and the cost of assigning the occupied orbitals to the orbital pairs of the wavefunction. Focusing on the latter, we present a graphical interpretation of the Slater determinant and utilize the maximum weighted matching algorithm to estimate the combination of orbital pairs with the largest contribution to the overlap. Then, the cost due to partitioning the occupied orbitals in the overlap is reduced from to . Computational results show that many of these combinations are not necessary to obtain an accurate solution to the wavefunction. Because the APG wavefunction is the most general of the geminal wavefunctions, this approach can be applied to any of the simpler geminal wavefunction ansätze. In fact, this approach may even be extended to generalized quasiparticle wavefunctions, opening the door to tractable wavefunctions built using components of arbitrary numbers of electrons, not just two electrons.

Galina A. Nemova

Peter Joshua Atkins, Julio de Paula, James Keeler

This chapter examines the interpretation of the wavefunction, and specifically what it reveals about the location of a particle. In quantum mechanics, all the properties of a system are expressed in terms of a wavefunction, which is obtained by solving the equation proposed by Erwin Schrödinger. Indeed, wavefunctions provide the essential foundation for understanding the properties of electrons in atoms and molecules, and are central to explanations in chemistry. The chapter then considers how, according to the Born interpretation, the probability density at a point is proportional to the square of the wavefunction at that point. A wavefunction is normalized if the integral over all space of its square modulus is equal to 1. Ultimately, a wavefunction must be single-valued, continuous, not infinite over a finite region of space, and have a continuous slope. The quantization of energy stems from the constraints that an acceptable wavefunction must satisfy.