Vibrational spectrum of p-fluoroanisole in the first excited state (S1) and ab initio calculations

Xiao, Daoqing; Yu, Deshui; Xu, Xi-Ling; Zhang, Yu; Du, Yikui; Gao, Zhen; Zhu, Qihe; Zhang, Cunhao

doi:10.1016/j.molstruc.2007.09.012

Cited by 26 publications

(15 citation statements)

References 29 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The experimental setup has been described in the previous publications [25,26]. Briefly, the 3FNMA sample (Aldrich, 97% purity), heated to 340 K to obtain sufficient vapor pressure, was seeded in Ar carrier gas (ca.…”

Section: Methodsmentioning

confidence: 99%

REMPI spectroscopy and theoretical calculations of cis and trans 3-fluoro-N-methylaniline

Zhang

Liu

Dong

et al. 2014

Journal of Molecular Spectroscopy

Self Cite

View full text Add to dashboard Cite

Section: Methodsmentioning

confidence: 99%

REMPI spectroscopy and theoretical calculations of cis and trans 3-fluoro-N-methylaniline

Zhang

Liu

Dong

et al. 2014

Journal of Molecular Spectroscopy

Self Cite

View full text Add to dashboard Cite

“…To acquire sufficient vapor pressure, the sample was heated to 353 K. The experimental system consisted of a time-offlight mass spectrometer (TOF-MS) and a pulsed supersonic molecular beam source, which has been described in previous publications [16,17]. The p-chloroanisole was carried by argon (approximately 2 atm) and expanded into the source chamber through a pulsed valve (General Valve) with an orifice 0.25 mm in diameter.…”

Section: Experimental and Computational Methodsmentioning

confidence: 99%

“…The similarity of the calculated E 1 s is consistent with that of the experimental results. Table 4 lists the origins of the S 1 S 0 electronic transition energies (E 0 1 s) of phenol [27][28][29], anisole [30][31][32], aniline [33][34][35] and their para-halogen substituted derivatives [16,20,22,33,36]. The band origins of the S 1 S 0 vibrationless transitions of p-fluoroanisole and p-chloroanisole are 35 146 and 34 859 cm À1 , which are red-shifted by 1234 and 1524 cm À1 , respectively, relative to that of anisole.…”

Section: Molecular Structurementioning

confidence: 99%

Resonance-enhanced multiphoton ionization (REMPI) spectroscopy of the 35Cl and 37Cl isotopomers of p-chloroanisole

Yu¹,

Dong²,

Cheng³

et al. 2011

Journal of Molecular Spectroscopy

Self Cite

View full text Add to dashboard Cite

“…Using the high accuracy rotational spectrum of anisole, the planarity of the molecule in both the ground and excited states has been clearly demonstrated. 46,52 In addition, the rotationally resolved S 1 -S 0 electronic spectra of anisole and its hydrogen bonded complex containing one water molecule has been obtained by J. W. Ribblett et al 59 Also D. Xiao and coworkers 65 recorded the vibronic structure of p-fluoroanisole in the first excited state (S 1 ) with mass selected resonance-enhanced two photon ionization spectroscopy. The band origin of the S 1 -S 0 transition of p-fluoroanisole has been measured as 35 149 cm À1 (4.358 eV), which is red-shifted by 1234 cm À1 with respect to that of anisole.…”

Section: Introductionmentioning

confidence: 99%

Excited state deactivation pathways of neutral/protonated anisole and p-fluoroanisole: a theoretical study

Omidyan

Rezaei

2014

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

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.

show abstract

Vibrational spectrum of p-fluoroanisole in the first excited state (S1) and ab initio calculations

Cited by 26 publications

References 29 publications

REMPI spectroscopy and theoretical calculations of cis and trans 3-fluoro-N-methylaniline

REMPI spectroscopy and theoretical calculations of cis and trans 3-fluoro-N-methylaniline

Resonance-enhanced multiphoton ionization (REMPI) spectroscopy of the 35Cl and 37Cl isotopomers of p-chloroanisole

Excited state deactivation pathways of neutral/protonated anisole and p-fluoroanisole: a theoretical study

Contact Info

Product

Resources

About