Gauge-origin independent calculations of electric-field-induced second-harmonic generation circular intensity difference using London atomic orbitals. (17th January 2017)

• Record Type: Journal Article
• Authors: Anelli, Marco; Ringholm, Magnus; Ruud, Kenneth
• Is Part Of: Molecular physics. Volume 115:Number 1/2(2017)
• Page Start: 241
• Page End: 251
• Publication Date: 2017-01-17
• Subjects: Molecular properties -- London atomic orbitals -- electric-field-induced second-harmonic generation -- circular intensity differences; Molecules -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Molécules -- Périodiques; Chimie physique et théorique -- Périodiques; 539.6.05
• DOI: 10.1080/00268976.2016.1249979
• Languages: English
• ISSNs: 0026-8976

Abstract

ABSTRACT: We present the first gauge-origin independent calculations of the circular intensity difference (CID) in electric-field-induced second-harmonic generation (EFISHG), including all contributions up to the electric-quadrupole–magnetic-dipole level. A recursive, open-ended response theory framework in combination with the use of London atomic orbitals allows us to ensure gauge-origin independent results. We apply this approach to study EFISHG-CID in a collection of chiral amino acids. We demonstrate that diffuse polarising basis functions are critical in order to obtain accurate CIDs, and that a basis set of at least aug-cc-pVTZ quality is needed in order to obtain results close to the basis-set limit. The use of London orbitals does not lead to significantly faster basis set convergence, although the improved basis set convergence allows the aug-cc-pVDZ basis set to be used with some confidence for larger molecules. Abstract :