A computational approach for modeling electronic circular dichroism of solvated chromophores. Issue 30 (22nd September 2022)

• Record Type: Journal Article
• Authors: Monti, Marta; Stener, Mauro; Aschi, Massimiliano
• Is Part Of: Journal of computational chemistry. Volume 43:Issue 30(2022)
• Page Start: 2023
• Page End: 2036
• Publication Date: 2022-09-22
• Subjects: CD spectroscopy -- DFT -- essential dynamics -- molecular dynamics -- TDDFT; Chemistry -- Data processing -- Periodicals; 542.85
• DOI: 10.1002/jcc.27001
• Languages: English
• ISSNs: 0192-8651

Abstract

Abstract: The present study consists in a novel computational protocol to model the UV‐circular dichroism spectra of solvated species. It makes use of quantum‐chemical calculations on a series of conformations of a flexible chromophore or on a series of chromophore/solvent clusters extracted from molecular dynamic simulations. The protocol is described and applied to the aqueous cationic tripeptide GAG + and to the aqueous neutral decapeptide (GVGVP)2 . The protocol has proven able to: (i) properly consider the conformational motion of solute in the given environment; (ii) give the actual statistical weight of each conformational state; (iii) provide a reliable quantum mechanical method able to reproduce the spectral features. Temperature effects on conformations and spectral properties are properly taken into account. The role of explicit solvent on the conformational analysis and the spectra calculation is discussed. The comparison of the calculated circular dichroism spectra with experimental ones recorded at different temperatures represents a strict validation test of the method. Abstract : A new computational protocol to model the UV‐circular dichroism spectra of solvated species is presented. It makes use of quantum‐chemical calculations on a series of conformations of a flexible chromophore or on a series of chromophore/solvent clusters extracted from molecular dynamic simulations. The protocol is described and applied to the aqueous cationic tripeptide GAG + and to the aqueous neutral decapeptide (GVGVP)2 . Temperature effects on conformations and spectral properties are properly taken into account. The role of explicit solvent on the conformational analysis and the spectra calculation is discussed.