Phenol-water1⩽n⩽3 revisited: An ab initio study on the photophysics of these clusters at the level of coupled cluster response theory

Abstract

The S1(pi*<--pi) state surfaces of the phenol-water(1<or=n<or=3) clusters are reexplored at the level of coupled cluster response theory. The global minima for n=2 and n=3 so obtained are qualitatively different from those reported so far, which were obtained with methods such as configuration interaction singles or complete active space self-consistent field lacking dynamical electron correlation effects. Furthermore, the minimum-energy points on the conical intersection seams were located in this work. The results of these calculations offer a qualitative explanation for the anomalous photophysical behavior (broad congested absorption band structure, low quantum yield, short lifetime) of n=2 and the observed predissociation of n=3 at excess energies beyond approximately 100 cm(-1), resolving a disagreement between theory and experiment which persisted for almost a decade.

Combined Monte Carlo and quantum mechanics study of the solvatochromism of phenol in water. The origin of the blue shift of the lowest π–π* transition

“…60 For the dihydrated complexes less information is available. In this case the first structure (Ph:W:W1) has been obtained before 63,[65][66][67] whereas the second (Ph:W:W2) is similar to the structure obtained by coupled cluster response theory CC2 model in ref. 65.…”

“…The hydrogen-bonded complexes of phenol with water have been intensely studied experimentally and theoretically, both the ground and the first S 1 excited state, with the aim of characterizing the structure, the rotation and vibration spectra and the fluorescence emission. 7,10,17,[51][52][53][54][55][56][57][58][59][60][61][62][63][64][65] Although the mono-hydrated Ph:W and W:Ph are of most interest here, in addition, two dihydrated complexes were also considered (Fig. 3).…”

Flickering dipoles in the gas phase: Structures, internal dynamics, and dipole moments of β-naphthol-H2O in its ground and excited electronic states

“…Recently, theoretical work has elegantly explained the strange R2PI spectra of doubly-hydrated 2HN and phenol. 7,49 High resolution spectra of the sharp features observed in these experiments would provide the structure in S 0 and S 1 of these three-bodied clusters, as well as their associated electronic properties. Since these structures are expected to involve π hydrogen bonds, the energetics of which have recently have been quantified using the high resolution technique, 50 new information on weak and strong solvation effects could be measured.…”

Interactions of Aromatic Radicals with Water

“…[1] Hobza et al used ab initio methods to calculate several hydrogen-bonded structures and one hemibonded structure of the phenol-water cation radical. [1] Hobza et al used ab initio methods to calculate several hydrogen-bonded structures and one hemibonded structure of the phenol-water cation radical.…”

“…Phenol-water complexes have been investigated in a number of theoretical studies. [1] Hobza et al used ab initio methods to calculate several hydrogen-bonded structures and one hemibonded structure of the phenol-water cation radical. They found that the most stable structure has C s symmetry and features a linear hydrogen bond between the proton of the OH group of the phenol cation radical and the oxygen atom of water, with the water hydrogen atoms pointing away from the phenyl ring.…”