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Periodic calculations of excited state properties for solids using a semiempirical approach
Immanuel Gadaczek,Kim Julia Hintze,Thomas Bredow
Physical Chemistry Chemical Physics Pub Date : 11/25/2011 00:00:00 , DOI:10.1039/C1CP22871D
Abstract

The semiempirical SCF MO method MSINDO (modified symmetrically orthogonalized intermediate neglect of differential overlap) [T. Bredow and K. Jug, Electronic Encyclopedia of Computational Chemistry, 2004] is extended to the calculation of excited state properties through implementation of the configuration interaction singles (CIS) approach. MSINDO allows the calculation of periodic systems via the cyclic cluster model (CCM) [T. Bredow et al., J. Comput. Chem., 2001, 22, 89] which is a direct-space approach and therefore can be in principle combined with all molecular quantum-chemical techniques. The CIS equations are solved for a cluster with periodic boundary conditions using the Davidson–Liu iterative block diagonalization approach. As a proof-of-principle, MSINDO-CCM-CIS is applied for the calculation of optical spectra of ZnO and TiO2, oxygen-defective rutile, and F-centers in NaCl. The calculated spectra are compared to available experimental and theoretical literature data. After re-adjustment of the empirical parameters the quantitative agreement with experiment is satisfactory. The present approximate approach is one of the first examples of a quantum-chemical methodology for solids where excited states are correctly described as n-electron state functions. After careful benchmark testing it will allow calculation of photophysical and photochemical processes relevant to materials science and catalysis.

Graphical abstract: Periodic calculations of excited state properties for solids using a semiempirical approach
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