Conical intersection properties unraveled by the position spread tensor

• Published in: Theoretical chemistry accounts Vol. 137; no. 12; pp. 1 - 9
• Main Authors: Segalina, Alekos, Francés-Monerris, Antonio, Pastore, Mariachiara, Leininger, Thierry, Evangelisti, Stefano, Monari, Antonio
• Format: Journal Article
• Language: English
• Published: Berlin/Heidelberg Springer Berlin Heidelberg 01.12.2018; Springer Nature B.V; Springer Verlag
• Subjects: Atomic/Molecular Structure and Spectra; Chemical Sciences; Chemiluminescence; Chemistry; Chemistry and Materials Science; Electronic structure; In Memoriam of János Ángyán; Inorganic Chemistry; Intersections; Mathematical analysis; or physical chemistry; Organic Chemistry; Physical Chemistry; Position measurement; Regular Article; Self consistent fields; Tensors; Theoretical and; Theoretical and Computational Chemistry; Position spread tensor; Branching space; Conical intersections; CASSCF; Photophysics and photochemistry
• ISSN: 1432-881X; 1432-2234
• DOI: 10.1007/s00214-018-2377-y

We explore the application of the electron position spread tensor, i.e., a quantitative measure of the electron delocalization and mobility, to the conical intersection regions of three relevant compounds showing either photoisomerization or chemiluminescence properties. The electronic structure of the involved states has been solved using the complete active space self-consistent field method, and the position spread tensor has been computed at the same level of theory. In particular, we show that the total position spread tensor is degenerate between the ground and the excited states, because of the inversion of the electronic nature of the states happening at the crossing areas. We also show that the ground-state position spread tensor shows a discontinuity that may be used to locate conical intersections without the need to explicitly compute the excited-state wavefunction. Furthermore, we also report that the spin partition position spread tensor shows a peculiar behavior presenting values close to zero in two of its principal components. We associate those small values to the degeneracy-lifting coordinates and hence to the conical intersection branching space.