High-Polarity Solvents Decreasing the Two-Photon Transition Probability of Through-Space Charge-Transfer Systems - A Surprising In Silico Observation.
In the Letter, we address the question as to why larger two-photon absorption cross sections are observed in nonpolar than in polar solvents for through-space charge-transfer (TSCT) systems such as [2,2]-paracyclophane derivatives. In order to answer this question, we have performed ab initio calculations on two well-known TSCT systems, namely, a [2.2]-paracyclophane derivative and a molecular tweezer-trinitrofluorinone complex, and found that the two-photon transition probability values of these systems decreases with increasing solvent polarity. To rationalize this result, we have analyzed the role of different optical channels associated with the two-photon process and noticed that, in TSCTs, the interference between the optical channels is mostly destructive and that its magnitude increases with increasing solvent polarity. Moreover, it is also found that a destructive interference may sometimes even become a constructive one in a nonpolar solvent, making the two-photon activity of TSCTs in polar solvents less than that in nonpolar solvents.
†Department of Chemistry, University of Calcutta, 92 A. P. C. Road, Kolkata 700009.
Md Mehboob
MM
Alam
†Department of Chemistry, University of Calcutta, 92 A. P. C. Road, Kolkata 700009.
Mausumi
M
Chattopadhyaya
†Department of Chemistry, University of Calcutta, 92 A. P. C. Road, Kolkata 700009.
Swapan
S
Chakrabarti
‡Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø, N-9037 Tromsø, Norway.
Kenneth
K
Ruud
[2.2]-paracyclophane; generalized few-state model; quadratic response theory; solvent effect; tweezer−TNF