Vibrational nonlinear optical properties of spatially confined weakly bound complexesElectronic supplementary information (ESI) available. See DOI: 10.1039/c7cp04259k

• Main Authors: Zale ny, Robert, Cho uj, Marta, Koz owska, Justyna, Bartkowiak, Wojciech, Luis, Josep M
• Format: Journal Article
• Language: English
• Published: 13.09.2017
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/c7cp04259k

This study focuses on the theoretical description of the influence of spatial confinement on the electronic and vibrational contributions to (hyper)polarizabilities of two dimeric hydrogen bonded systems, namely HCN HCN and HCN HNC. A two-dimensional analytical potential is employed to render the confining environment ( e.g. carbon nanotube). Based on the results of the state-of-the-art calculations, performed at the CCSD(T)/aug-cc-pVTZ level of theory, we established that: (i) the influence of spatial confinement increases with increasing order of the electrical properties, (ii) the effect of spatial confinement is much larger in the case of the electronic than vibrational contribution (this holds for each order of the electrical properties) and (iii) the decrease in the static nuclear relaxation first hyperpolarizability upon the increase of confinement strength is mainly due to changes in the harmonic term, however, in the case of nuclear relaxation second hyperpolarizability the anharmonic terms contribute more to the drop of this property. Vibrational nonlinear optical properties of weakly bound complexes are less susceptible to spatial confinement than their electronic counterparts - a novel inference from high-level ab initio computations.