Vibrational dynamics of the CO stretching mode of 9-fluorenone in alcohol solution

Hirai, Satori; Banno, Motohiro; Ohta, Kaoru; Palit, Dipak K.; Tominaga, Kazuhiro

doi:10.1016/j.cplett.2007.10.090

Cited by 25 publications

(50 citation statements)

References 17 publications

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“…We observed the absorption band due to the CO stretching mode of FL in 1-octanol that shows a similar spectral pattern with two peaks and one shoulder. 18 We concluded that the two peaks result from a FL monomer and a complex of FL with one methanol molecule, and the shoulder results from a complex of FL with two methanol molecules. In an analogous manner, the bands at 1731 and 1706 cm 1 were assigned to complexes of MA with one methanol molecule (1 : 1 complex) and of MA with two methanol molecules (1 : 2 complex), respectively.…”

Section: Ground-state Infrared Absorption Spectramentioning

confidence: 99%

“…A similar result was observed for FL in 1-octanol. 18 The 1 : 1 complex is thermodynamically less stable than the MA monomer, because the 1 : 1 complex is stabilized by intermolecular hydrogen bonds. However, the free energy of the solvation complex is dominated not only by intermolecular hydrogen bonds but also by other solute-solvent interactions such as the interaction between the hydrophobic groups.…”

Section: Ground-state Infrared Absorption Spectramentioning

confidence: 99%

“…It is of interest that this ratio is about 2 for the system of FL in 1-octanol. 18 In terms of the Fermi golden rule, the VER rate is controlled by the following factors: the anharmonic coupling between the excited vibrational mode and the energy-accepting mode, the energy difference between them, and the vibrational density of states (VDOS) around the wavenumber of the excited vibrational mode. It is unlikely that the intramolecular anharmonic coupling is affected largely by intermolecular interactions such as hydrogen bonds.…”

Section: Vibrational Energy Relaxation Processmentioning

confidence: 99%

“…15,16 In a series of IR pump-probe spectroscopic studies, we investigated the VER processes of the CO stretching modes of acetic acid in D 2 O 17 and 9-fluorenone (FL) in methanol. 18 When carbonyl compounds are dissolved into a protic solvent, intermolecular hydrogen bonds are formed between the oxygen atom of the carbonyl group and the hydroxyl group of the solvent molecules. The temporal evolution of the transient IR absorption spectra of the acetic acid and FL systems is interpreted in terms of two and three dynamical components with different time constants, respectively.…”

Section: Introductionmentioning

confidence: 99%

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Ultrafast vibrational dynamics and solvation complexes of methyl acetate in methanol studied by sub‐picosecond infrared spectroscopy

Banno

Ohta

Tominaga

2008

J Raman Spectroscopy

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The vibrational dynamics of the CO stretching mode of methyl acetate (MA) in methanol was studied by time-resolved infrared (IR) pump-probe spectroscopy. The vibrational energy relaxation (VER) process includes two components with time constants of 1.3 ± 0.1 and 4.0 ± 0.2 ps. These components result from the vibrational excitations of the hydrogen-bonding complex of MA with one methanol and the MA monomer, respectively. The difference in the VER time is explained by the increase of the vibrational density of states (VDOS) by the intermolecular hydrogen bond. The time constants and the decayassociated spectra are almost identical between the CH 3 OH and the CH 3 OD solutions. The vibrational modes localized in the intramolecular OH/OD bond of the solvent methanol have little effect on the vibrational dynamics of MA.

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Section: Ground-state Infrared Absorption Spectramentioning

confidence: 99%

Section: Ground-state Infrared Absorption Spectramentioning

confidence: 99%

Section: Vibrational Energy Relaxation Processmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Ultrafast vibrational dynamics and solvation complexes of methyl acetate in methanol studied by sub‐picosecond infrared spectroscopy

Banno

Ohta

Tominaga

2008

J Raman Spectroscopy

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“…[19] In addition, the dynamics of hydrogen-bonding interaction in the ground electronic state of fluorenone in alcoholic solvents have also been investigated using a time-resolved IR pump-IR probe spectroscopic technique. [20] Zhao and Han used time-dependent density functional theory (TDDFT) to investigate the excited-state hydrogen-bonding dynamics of fluorenone as well as other kinds of probes in the hydrogenbond-donating solvent methanol. [21] They demonstrated that an intermolecular hydrogen bond C=O···HÀO is formed between fluorenone and methanol in the ground state, and that this bond is significantly strengthened in the electronically excited state following photoexcitation.…”

Section: Introductionmentioning

confidence: 99%

Ultrafast Relaxation Dynamics of the Excited States of 1‐Amino‐ and 1‐(N,N‐Dimethylamino)‐fluoren‐9‐ones

et al. 2009

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The dynamics of the excited states of 1-aminofluoren-9-one (1AF) and 1-(N,N-dimethylamino)-fluoren-9-one (1DMAF) are investigated by using steady-state absorption and fluorescence as well as subpicosecond time-resolved absorption spectroscopic techniques. Following photoexcitation of 1AF, which exists in the intramolecular hydrogen-bonded form in aprotic solvents, the excited-state intramolecular proton-transfer reaction is the only relaxation process observed in the excited singlet (S(1)) state. However, in protic solvents, the intramolecular hydrogen bond is disrupted in the excited state and an intermolecular hydrogen bond is formed with the solvent leading to reorganization of the hydrogen-bond network structure of the solvent. The latter takes place in the timescale of the process of solvation dynamics. In the case of 1DMAF, the main relaxation pathway for the locally excited singlet, S(1)(LE), or S(1)(ICT) state is the configurational relaxation, via nearly barrierless twisting of the dimethylamino group to form the twisted intramolecular charge-transfer, S(1)(TICT), state. A crossing between the excited-state and ground-state potential energy curves is responsible for the fast, radiationless deactivation and nonemissive character of the S(1)(TICT) state in polar solvents, both aprotic and protic. However, in viscous but strong hydrogen-bond-donating solvents, such as ethylene glycol and glycerol, crossing between the potential energy surfaces for the ground electronic state and the hydrogen-bonded complex formed between the S(1)(TICT) state and the solvent is possibly avoided and the hydrogen-bonded complex is weakly emissive.

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Ultrafast Dynamics of the Excited States of Hydrogen‐Bonded Complexes and Solvation

Palit¹

2010

Hydrogen Bonding and Transfer in the Excited State

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In solutions, solute and solvent molecules interact to minimize the free-energy of the solute-solvent system [1][2][3][4][5]. Each solute molecule is surrounded by a shell of more or less tightly bound solvent molecules because of intermolecular forces between them; the phenomenon is well-known as "solvation" and "solvation energy" can be defined as the change of Gibb's free energy when a molecule is transferred from the gas phase into the solvent. Solvation interaction mainly arises due to the columbic forces between the dipoles of the solute and solvent molecules [6]. This is a long-range interaction, also known as a "non-specific" interaction, and for a particular solute molecule, the solvation energy is solely determined by the dielectric properties of the solvent. However, in addition to the dipolar solvation energy, the free energy of the solute-solvent system may be further lowered if a hydrogen bond is formed between the solute and a solvent molecule [7,8]. Since two specific solute and solvent molecules are involved in formation of the hydrogen bond, this kind of solvation interaction is known as "specific" interaction [9], which will be described here as formation of hydrogenbonded complex.Following photoexcitation of a solute molecule, the electronic charge distribution is changed. In such a case, in which the molecule is excited directly to an excited state having intramolecular charge transfer (ICT) character, the instantaneous and significant change in the polarity of the molecule following photoexcitation drives the dipoles of the surrounding solvent molecules to reorganize themselves to minimize the free energy of the solute-solvent system. This phenomenon is popularly known as "dipolar solvation" [10][11][12][13][14][15]. Following photoexcitation of the hydrogen-bonded complex formed in the ground electronic state of the solute, the

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Vibrational dynamics of the CO stretching mode of 9-fluorenone in alcohol solution

Cited by 25 publications

References 17 publications

Ultrafast vibrational dynamics and solvation complexes of methyl acetate in methanol studied by sub‐picosecond infrared spectroscopy

Ultrafast vibrational dynamics and solvation complexes of methyl acetate in methanol studied by sub‐picosecond infrared spectroscopy

Ultrafast Relaxation Dynamics of the Excited States of 1‐Amino‐ and 1‐(N,N‐Dimethylamino)‐fluoren‐9‐ones

Ultrafast Dynamics of the Excited States of Hydrogen‐Bonded Complexes and Solvation

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