Nodal variational principle for excited states

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2018-07-31
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Zahariev, Federico
Gordon, Mark
Levy, Mel
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Ames National Laboratory

Ames National Laboratory is a government-owned, contractor-operated national laboratory of the U.S. Department of Energy (DOE), operated by and located on the campus of Iowa State University in Ames, Iowa.

For more than 70 years, the Ames National Laboratory has successfully partnered with Iowa State University, and is unique among the 17 DOE laboratories in that it is physically located on the campus of a major research university. Many of the scientists and administrators at the Laboratory also hold faculty positions at the University and the Laboratory has access to both undergraduate and graduate student talent.

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Chemistry

The Department of Chemistry seeks to provide students with a foundation in the fundamentals and application of chemical theories and processes of the lab. Thus prepared they me pursue careers as teachers, industry supervisors, or research chemists in a variety of domains (governmental, academic, etc).

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The Department of Chemistry was founded in 1880.

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1880-present

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Ames National LaboratoryChemistry
Abstract

It is proven that the exact excited-state wave function and energy may be obtained by minimizing the energy expectation value of trial wave functions that are constrained only to have the correct nodes of the state of interest. This excited-state nodal minimum principle has the advantage that it requires neither minimization with the constraint of wave-function orthogonality to all lower eigenstates nor the antisymmetry of the trial wave functions. It is also found that the minimization over the entire space can be partitioned into several interconnected minimizations within the individual nodal regions, and the exact excited-state energy may be obtained by a minimization in just one or several of these nodal regions. For the proofs of the theorem, it is observed that the many-electron eigenfunction (excited state as well as ground state), restricted to a nodal region, is equivalent to a ground-state wave function of one electron in a higher-dimensional space; and, alternatively, an explicit excited-state energy variational expression is utilized by generalizing the Jacobi method of multiplicative variation. In corollaries, error functions are constructed for cases for which the nodes are not necessarily exact. The exact nodes minimize the energy error functions with respect to nodal variations. Simple numerical illustrations of the error functions are presented.

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