Hyperpolarizabilities of extended molecular mechanical systems. Issue 12 (8th March 2016)

• Record Type: Journal Article
• Authors: Harczuk, Ignat; Vahtras, Olav; Ågren, Hans
• Is Part Of: Physical chemistry chemical physics. Volume 18:Issue 12(2016)
• Page Start: 8710
• Page End: 8722
• Publication Date: 2016-03-08
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c5cp06688c
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : The equations for decomposition of the molecular hyperpolarizabilty into atomic sites is derived alongside with equations to calculate the cluster hyperpolarizability as resulting from the second order induced dipole moments in the point-dipole model. Abstract : We propose and evaluate algorithms for the calculation of molecular polarizabilities and hyperpolarizabilities of extended chemical systems. These algorithms are generalizations of the Silberstein–Applequist procedure involving interacting induced classical dipoles through the localized polarizabilities and hyperpolarizabilities. The models are evaluated in terms of interacting molecular units as well as interacting atomic units that result from the atomic decomposition scheme known as the LoProp transformation. We introduce a generalized LoProp scheme which applies to hyperpolarizabilities as well as to polarizabilities. The accuracy of the second-order Applequist method is tested for the first hyperpolarizability for the TIP3P water model using both Hartree–Fock and density functional theory evaluated with different basis sets. Possible applications and ramifications of the scheme are discussed.