An infrared study of π-hydrogen bonds in micro-solvated phenol:: OH stretching vibrations of phenol-X (X = C6H6, C2H4, and C2H2) clusters in the neutral and cationic ground states

被引:76
作者
Fujii, A [1 ]
Ebata, T [1 ]
Mikami, N [1 ]
机构
[1] Tohoku Univ, Grad Sch Sci, Dept Chem, Sendai, Miyagi 9808578, Japan
关键词
D O I
10.1021/jp0208992
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Infrared spectra of phenol-X (X = C6H6, C2H4, and C2H2) clusters in the neutral and cationic ground states were observed in the OH stretching vibrational region. For the neutral ground state, infrared-ultraviolet double resonance spectroscopy was utilized to observe the infrared spectra. A small low-frequency shift of the OH vibration of the phenol site in all the clusters represented the characteristic feature for their pi-hydrogen-bonded structures, which were also confirmed by density functional theoretical calculations. The OH frequency shifts did not remarkably depend on the type of the pi-electrons. The correlation between the proton affinity of X and the OH frequency shift, which has been known for conventional a-hydrogen-bonded phenol clusters, was held in phenol-C2H4 and -C2H2, while phenol-C6H6 showed a clear deviation from the correlation. For the cationic ground state, infrared photodissociation spectroscopy was used to observe the infrared spectra. The OH frequency of these clusters exhibited an extremely large low-frequency shift upon ionization, reflecting the significant enhancement of the pi-hydrogen bond strength. The pi-hydrogen bond energies in the cations were estimated on the basis of both the experiments and the theoretical calculations.
引用
收藏
页码:8554 / 8560
页数:7
相关论文
共 42 条
[21]   DENSITY-FUNCTIONAL THEORY AND MOLECULAR CLUSTERS [J].
HOBZA, P ;
SPONER, J ;
RESCHEL, T .
JOURNAL OF COMPUTATIONAL CHEMISTRY, 1995, 16 (11) :1315-1325
[22]   Evaluated gas phase basicities and proton affinities of molecules: An update [J].
Hunter, EPL ;
Lias, SG .
JOURNAL OF PHYSICAL AND CHEMICAL REFERENCE DATA, 1998, 27 (03) :413-656
[23]  
INOKUCHI Y, 1999, ANN REV I MOL SCI, P66
[24]   Infrared spectroscopy of hydrogen-bonded phenol-amine clusters in supersonic jets [J].
Iwasaki, A ;
Fujii, A ;
Watanabe, T ;
Ebata, T ;
Mikami, N .
JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (40) :16053-16057
[25]  
Jeffrey G.A., 1997, An Introduction to Hydrogen Bonding, VVolume 12
[26]   REACTIVITY OF MOLECULAR CLUSTERS IN THE GAS-PHASE - PROTON-TRANSFER REACTION IN NEUTRAL PHENOL-(NH3)N AND PHENOL-(C2H5NH2)N [J].
JOUVET, C ;
LARDEUXDEDONDER, C ;
RICHARDVIARD, M ;
SOLGADI, D ;
TRAMER, A .
JOURNAL OF PHYSICAL CHEMISTRY, 1990, 94 (12) :5041-5048
[27]   PICOSECOND PHOTOFRAGMENT SPECTROSCOPY .3. VIBRATIONAL PREDISSOCIATION OF VANDERWAALS CLUSTERS [J].
KNEE, JL ;
KHUNDKAR, LR ;
ZEWAIL, AH .
JOURNAL OF CHEMICAL PHYSICS, 1987, 87 (01) :115-127
[28]  
LIDE DR, 1995, CRC HDB CHEM PHYSICS
[29]   PHOTODISSOCIATION OF THE HYDROGEN-BONDED HETERODIMER ION [C6H5OH-NH3]+ [J].
MIKAMI, N ;
OKABE, A ;
SUZUKI, I .
JOURNAL OF PHYSICAL CHEMISTRY, 1988, 92 (07) :1858-1862
[30]   Photodissociation spectroscopy of (benzene-toluene)+.: Charge delocalization in the hetero-dimer ion [J].
Ohashi, K ;
Nakane, Y ;
Inokuchi, Y ;
Nakai, Y ;
Nishi, N .
CHEMICAL PHYSICS, 1998, 239 (1-3) :429-436