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The MP2/CC2 and CASSCF theoretical approaches have been employed to determine the excited state proton transfer and photophysical nature of the four organic compounds, having the main frame of hydroxyphenyl-imidzaopyridine (HPIP). The nitrogen insertion effect, in addition to amine (-NH 2 ) substitution has been investigated extensively by following the transition energies and deactivation pathways of resulted HPIP derivatives. It has been predicted that the excited state intramolecular proton transfer with or without small barrier is the most important feature of these compounds. Also, for all of the considered HPIP derivatives, a conical intersection (CI) between ground and the S 1 excited state has been predicted. The strong non-adiabatic coupling in the CI (S 1 /S 0 ), drives the system back to the ground state in which the proton may either return to the phenoxy unit and thus close the photocycle, or the system can continue the twisting motion that results in formation of a γ-photochromic species. This latter species can be responsible for photochromism of HPIP derivative systems.

The potential energy profiles of neutral and protonated anisole and p-fluoroanisole at different electronic states have been investigated extensively by the RI-MP2 and RI-CC2 methods. The calculations reveal that the relaxation dynamics in protonated anisole and p-fluoroanisole are essentially different from those of the neutral analogues. In neutral anisole/p-fluoroanisole, the (1)πσ* state plays a vital relaxation role along the O-CH3 coordinate, yielding the CH3 radical. For both of these molecules, the calculations indicate conical intersections (CIs) between the ground and excited state potential energy (PE) curves, hindered by a small barrier, and providing non-adiabatic gates for radiation-less deactivation to the ground state. Nevertheless, for the protonated cases, besides the prefulvenic deformation of the benzene ring, it has been predicted that the lowest (1)(σ,n)π* state along the C-O-C bond angle plays an important role in photochemistry and the relaxation dynamics. The S1, S0 PE profiles of protonated anisole along with the former reaction coordinate (out-of-plane deformation) show a barrierless relaxation pathway, which can be responsible for the ultrafast deactivation of excited systems to the ground state via the low-lying S1/S0 conical intersection. Moreover, the later reaction coordinate in protonated species (C-O-C angle from 120°-180°) is consequently accompanied with the bond cleavage of C-OCH3 at the (1)(σ,n)π* state, hindered by a barrier of ∼0.51 eV, and can be responsible for the relaxation of excited systems with significant excess energy (hν≥ 5 eV). Furthermore, according to the RI-CC2 calculated results, different effects on the S1-S0 electronic transition energy of anisole and p-fluoroanisole upon protonation have been predicted. The first electronic transitions of anisole and p-fluoroanisole shift by ∼0.3 and 1.3 eV to the red respectively due to protonation.

The CC2 (second order approximate coupled cluster method) has been applied to investigate protonation effect on electronic transition energies of 2-pyridone (2PY), 2-pyridone dimer, and micro-solvated 2-pyridone (0-2 water molecules). The PE profiles of protonated 2-pyridone (2PYH(+)) as well as monohydrated 2PYH(+) at the different electronic states have been investigated. The (1)πσ∗ state in protonated species (2PYH(+)) is a barrier free and dissociative state along the O-H stretching coordinate. In this reaction coordinate, the lowest lying (1)πσ∗ predissociates the bound S1((1)ππ∗) state, connecting the latter to a conical intersection with the S0 state. These conical intersections lead the (1)ππ∗ state to proceed as predissociative state and finally direct the excited system to the ground state. Furthermore, in presence of water molecule, the (1)πσ∗ state still remains dissociative but the conical intersection between (1)πσ∗ and ground state disappears. In addition, according to the CC2 calculation results, it has been predicted that protonation significantly blue shifts the S1-S0 electronic transition of monomer, dimer, and microhydrated 2-pyridone.

Vibrational and electronic photodissociation spectra of mass-selected protonated benzaldehyde- (water)n clusters, [BZ-(H2O)n]H+ with n ≤ 5, are analyzed by quantum chemical calculations to determine the protonation site in the ground electronic state (S0) and ππ ∗ excited state (S1) as a function of microhydration. IR spectra of [BZ-(H2O)n]H+ with n ≤ 2 are consistent with BZH+-(H2O)n type structures, in which the excess proton is localized on benzaldehyde. IR spectra of clusters with n ≥ 3 are assigned to structures, in which the excess proton is located on the (H2O)n solvent moiety, BZ-(H2O)nH+. Quantum chemical calculations at the B3LYP, MP2, and ri-CC2 levels support the conclusion of proton transfer from BZH+ to the solvent moiety in the S0 state for hydration sizes larger than the critical value nc = 3. The vibronic spectrum of the S1 ← S0 transition (ππ ∗) of the n = 1 cluster is consistent with a cis-BZH+-H2O structure in both electronic states. The large blueshift of the S1 origin by 2106 cm−1 upon hydration with a single H2O ligand indicates that the proton affinity of BZ is substantially increased upon S1 excitation, thus strongly destabilizing the hydrogen bond to the solvent. The adiabatic S1 excitation energy and vibronic structure calculated at the ri-CC2/aug-cc-pVDZ level agrees well with the measured spectrum, supporting the notion of a cis-BZH+-H2O geometry. The doubly hydrated species, cis-BZH+-(H2O)2, does not absorb in the spectral range of 23 000–27 400 cm−1, because of the additional large blueshift of the ππ ∗ transition upon attachment of the second H2O molecule. Calculations predict roughly linear and large incremental blueshifts for the ππ ∗ transition in [BZ-(H2O)n]H+ as a function of n. In the size range n ≥ 3, the calculations predict a proton transfer from the (H2O)nH+ solvent back to the BZ solute upon electronic ππ ∗ excitation. [ABSTRACT FROM AUTHOR]