A time-dependent density functional theory investigation on the nature of the electronic transitions involved in the nonlinear optical response of [Ru(CF3CO2)3T] (T = 4'-(C6H4-p-NBu2)-2,2':6',2”-terpyridine). Export

@article{citeulike:840857, abstract = {We report a theoretical study based on density functional theory (DFT) and time-dependent DFT (TDDFT) calculations on the nature and role of the absorption bands involved in the nonlinear optical response of the complexes [Ru(CF3CO2)3T] (T = T1, T2; T1 = 4'-(C6H4-p-NBu2)-2,2':6',2''-terpyridine, T2 = 4'-(C6H4-p-NMe2)-2,2':6',2''-terpyridine). Geometry optimizations, performed without any symmetry constraints, confirm a twisting of the -C6H4-p-NBu2 moiety with respect to the plane of the chelated terpyridine. Despite this lack of strong pi interaction, TDDFT excited states calculations of the electronic spectrum in solution provide evidence of a relevant role of the NBu2 donor group in the low-energy LMCT band at 911 nm. Calculations also show that the two bands at higher energy (508 and 455 nm) are not attributable only to LMCT and ILCT transitions but to a mixing of ILCT/MLCT and ILCT/pi-pi* transitions, respectively. The 911 nm LMCT band, appearing at lower wavelength of the second harmonic (670 nm) of the EFISH experiment, controls the negative value of the second-order NLO response. This is confirmed by our calculations of the static component beta0(zzz) of the quadratic hyperpolarizability tensor, showing a large positive value. In addition we have found that the increase of the dipole moment upon excitation occurs, in all the characterized transitions, along the dipole moment axis, thus explaining why the EFISH and solvatochromic experimental values of the quadratic hyperpolarizability agree as sign and value.}, address = {Istituto di Scienze e Tecnologie Molecolari del CNR (ISTM-CNR), c/o Dipartimento di Chimica, Via Elce di Sotto 8, I-06123, Perugia, Italy.}, author = {De Angelis, F. and Fantacci, S. and Sgamelotti, A. and Cariati, F. and Roberto, D. and Tessore, F. and Ugo, R.}, citeulike-article-id = {840857}, citeulike-linkout-0 = {http://dx.doi.org/10.1039/b509123c}, citeulike-linkout-1 = {http://view.ncbi.nlm.nih.gov/pubmed/16437181}, citeulike-linkout-2 = {http://www.hubmed.org/display.cgi?uids=16437181}, day = {14}, doi = {10.1039/b509123c}, issn = {1477-9226}, journal = {Dalton Trans}, keywords = {hyperpolarizability, tddft, theory}, month = {February}, number = {6}, pages = {852--859}, posted-at = {2006-09-12 11:23:49}, priority = {2}, title = {A time-dependent density functional theory investigation on the nature of the electronic transitions involved in the nonlinear optical response of [Ru(CF3CO2)3T] (T = 4'-(C6H4-p-NBu2)-2,2':6',2''-terpyridine).}, url = {http://dx.doi.org/10.1039/b509123c}, year = {2006} }

TY - JOUR ID - citeulike:840857 L3 - citeulike-article-id:840857 N2 - We report a theoretical study based on density functional theory (DFT) and time-dependent DFT (TDDFT) calculations on the nature and role of the absorption bands involved in the nonlinear optical response of the complexes [Ru(CF3CO2)3T] (T = T1, T2; T1 = 4'-(C6H4-p-NBu2)-2,2':6',2''-terpyridine, T2 = 4'-(C6H4-p-NMe2)-2,2':6',2''-terpyridine). Geometry optimizations, performed without any symmetry constraints, confirm a twisting of the -C6H4-p-NBu2 moiety with respect to the plane of the chelated terpyridine. Despite this lack of strong pi interaction, TDDFT excited states calculations of the electronic spectrum in solution provide evidence of a relevant role of the NBu2 donor group in the low-energy LMCT band at 911 nm. Calculations also show that the two bands at higher energy (508 and 455 nm) are not attributable only to LMCT and ILCT transitions but to a mixing of ILCT/MLCT and ILCT/pi-pi* transitions, respectively. The 911 nm LMCT band, appearing at lower wavelength of the second harmonic (670 nm) of the EFISH experiment, controls the negative value of the second-order NLO response. This is confirmed by our calculations of the static component beta0(zzz) of the quadratic hyperpolarizability tensor, showing a large positive value. In addition we have found that the increase of the dipole moment upon excitation occurs, in all the characterized transitions, along the dipole moment axis, thus explaining why the EFISH and solvatochromic experimental values of the quadratic hyperpolarizability agree as sign and value. IS - 6 JF - Dalton Trans SN - 1477-9226 AD - Istituto di Scienze e Tecnologie Molecolari del CNR (ISTM-CNR), c/o Dipartimento di Chimica, Via Elce di Sotto 8, I-06123, Perugia, Italy. EP - 859 TI - A time-dependent density functional theory investigation on the nature of the electronic transitions involved in the nonlinear optical response of [Ru(CF3CO2)3T] (T = 4'-(C6H4-p-NBu2)-2,2':6',2''-terpyridine). SP - 852 KW - hyperpolarizability KW - tddft KW - theory AU - De Angelis, F AU - Fantacci, S AU - Sgamelotti, A AU - Cariati, F AU - Roberto, D AU - Tessore, F AU - Ugo, R PY - 2006/02/14/ UR - http://dx.doi.org/10.1039/b509123c ER -