title: Reference molecules for nonlinear optics: a joint experimental and theoretical investigation.
abstract: Hyper-Rayleigh scattering (HRS) experiments and quantum chemical calculations are combined to investigate the second-order nonlinear optical responses of a series of reference molecules, namely, carbon tetrachloride, chloroform, trichloroacetonitrile, acetonitrile, and dichloromethane. The multipolar decomposition of the first hyperpolarizability tensor through the use of the spherical harmonics formalism is employed to highlight the impact of the symmetry of the molecular scatterers on their nonlinear optical responses. It is demonstrated that HRS is a technique of choice to probe the molecular symmetry of the compounds. Coupled-cluster calculations performed at the coupled-cluster level with singles, doubles, and perturbative triples in combination with highly extended basis sets and including environment effects by using the polarizable continuum model qualitatively reproduce the molecular first hyperpolarizabilities and depolarization ratios of the molecular scatterers.
authors.affiliation: Université de Bordeaux, Institut des Sciences Moléculaires, 351 Cours de la Libération, 33405 Talence, France. f.castet@ism.u-bordeaux1.fr
authors.forename: Frédéric
authors.initials: F
authors.lastname: Castet
authors.forename: Elena
authors.initials: E
authors.lastname: Bogdan
authors.forename: Aurélie
authors.initials: A
authors.lastname: Plaquet
authors.forename: Laurent
authors.initials: L
authors.lastname: Ducasse
authors.forename: Benoît
authors.initials: B
authors.lastname: Champagne
authors.forename: Vincent
authors.initials: V
authors.lastname: Rodriguez