Spatial localization in nuclear spin-induced circular dichroism – a quadratic response function analysis. Issue 33 (30th May 2019)

• Record Type: Journal Article
• Authors: Štěpánek, Petr; Coriani, Sonia
• Is Part Of: Physical chemistry chemical physics. Volume 21:Issue 33(2019)
• Page Start: 18082
• Page End: 18091
• Publication Date: 2019-05-30
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c9cp01716j
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : A new computational method for nuclear spin-induced circular dichroism allows analysis of localization of individual excited states within a molecule. Abstract : Nuclear magneto-optic (NMO) effects are recently described phenomena originating from the interaction of light with local magnetic fields produced by nuclear spins. The phenomena border nuclear magnetic resonance and optical spectroscopy and are expected to provide rather unique spectroscopic features, borrowing from both localized response of the atomic nuclei as well as more global excitation properties of the whole molecule or its chromophore moieties. A number of quantum-chemical computational studies have been carried out, offering a reasonable agreement with nuclear magneto-optics experiments performed so far. However, the detailed structure-spectra relation is still poorly understood. In this report we address the question of locality of one of the NMO effects, namely nuclear spin-induced circular dichroism (NSCD). We implement an alternative computational approach for calculation of the NSCD intensities, based on residues of quadratic response functions, and use it to investigate the NSCD response of different nuclei in a model molecular system with well-defined separate chromophores. The results show that significant NSCD at a given energy only occurs at the nuclei which are located in the chromophore that is excited. We rationalize these findings using analysis via difference densities, and approximate sum-over-states calculations. This behaviour of NSCD opens a way to experimental studies of localization of excited states in molecules, potentially with resolution down to the order of bond-length.