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

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 TiO(2), 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.

Oxalic acid at the TiO 2 /water interface under UV(A) illumination: Surface reaction mechanisms

“…Different from other solid-state methods currently available, MSINDO-CCM allows excited-state calculations for periodic systems at the configuration interaction (CI) level. Recently, the CI with singles (CIS) method was implemented in MSINDO-CCM [38]. Analytical gradients allow structure optimization of adsorbed molecules on surfaces in the excited state [39].…”

Quantum mechanical modeling of excited electronic states and their relationship to cathodoluminescence of BaZrO3

“…However, accurate excited electronic states calculation of periodic systems still represents a challenge for quantum-chemical methods. 39 An excited state is obtained by imposing a low and high spin state that must promote an electron from the VB to the CB. Per unit cell, this transaction corresponds to imposing two electrons with the opposite (singlet) and same spin (triplet).…”

Local ab initio methods for calculating optical bandgaps in periodic systems. II. Periodic density fitted local configuration interaction singles method for solids

“…1 Recently, also a 3D periodic semiempirical CIS implementation, based on the intermediate neglect of differential overlap approximation, has been reported. 13 There exists also a periodic implementation of the algebraic diagrammatic construction scheme for the self-energy in the canonical representation. 14 An alternative technique to evaluate the TD-HF excitation energies in periodic systems has been developed in Ref.…”