Response of a General Restricted Open-Shell Hartree–Fock Wave Function. I: Formalism, Analytic Gradients, and Electric and Magnetic Response Properties
Frank Neese
TL;DR
This paper introduces a new quantum chemistry method for calculating properties of open-shell molecules with complex spin states.
Contribution
A general restricted open-shell Hartree–Fock response theory is developed for arbitrary spin configurations.
Findings
The g-ROHF method enables accurate electric and magnetic property calculations for complex open-shell systems.
New vector-coupling coefficients allow proper spin density calculations in general-spin systems.
The method successfully computes g-tensors and hyperfine couplings in transition-metal complexes and metal–radical assemblies.
Abstract
In this work, the formal development and implementation of a general restricted open-shell Hartree–Fock (g-ROHF) response theory is presented. The theory enables analytic computation of electric and magnetic response properties for arbitrarily complex open-shell configurations. In contrast to traditional ROHF methods, which are typically restricted to high-spin cases, the g-ROHF formulation supports general-spin couplings and orbital degeneracies while preserving the spin purity. A new set of vector-coupling coefficients is introduced that allows for the calculation of a proper spin density from a g-ROHF wave function. Analytic nuclear derivatives, along with the electric and magnetic orbital Hessians, are derived in a unified framework. Special attention is given to the treatment of SCF instabilities and the projection of unphysical modes from the response space. An efficient AO-driven…
Genes, proteins, chemicals, diseases, species, mutations and cell lines named across the full text — each resolved to its canonical identifier and authoritative record.
Click any figure to enlarge with its caption.
Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9
Figure 10
Figure 11
Figure 12
Figure 13
Figure 14
Figure 15
Figure 16
Figure 17
Figure 18
Figure 19
Figure 20
Figure 21
Figure 22
Figure 23
Figure 24
Figure 25
Figure 26
Figure 27
Figure 28
Figure 29
Figure 30
Figure 31
Figure 32
Figure 33
Figure 34
Figure 35
Figure 36
Figure 37
Figure 38
Figure 39
Figure 40
Figure 41
Figure 42
Figure 43
Figure 44
Figure 45
Figure 46
Figure 47
Figure 48
Figure 49
Figure 50Peer Reviews
No public reviews on file for this paper yet. If you reviewed it on a platform where reviews are public (OpenReview, ICLR, NeurIPS, ICML), you can paste yours below so the community can read it here.
Videos
No videos yet. Explain this paper in a talk, walkthrough, or lecture? Add one.
Taxonomy
TopicsAdvanced Chemical Physics Studies · Spectroscopy and Quantum Chemical Studies · Magnetism in coordination complexes