Low-frequency vibrations of all-trans-retinal:: Far-infrared and Raman spectra and density functional calculations

被引:65
作者
Gervasio, FL
Cardini, G
Salvi, PR
Schettino, V
机构
[1] Univ Florence, Dipartimento Chim, Lab Spettroscopia Mol, I-50121 Florence, Italy
[2] European Lab Nonlinear Spect LENS, I-50125 Florence, Italy
关键词
D O I
10.1021/jp9724636
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
The infrared and Raman spectra of all-trans-retinal in the region of the low-frequency internal vibrations have been measured at room temeprature and at 15 K. The frequencies and infrared intensities of the normal modes have been calculated by means of the density functional approach using the B3-LYP exchange + correlation functional. The vibrational analysis allows a complete assignment of all the observed fundamentals, both on a frequency and on a intensity basis. The calculated vibrational modes of all-trans-retinal have been also correlated to those of the component moieties, 3,7-dimethyl-2,4,6,8-octatetraenal and 1,3,3-trimethyl-cyclohexene. This gives an idea of the degree of localization of the vibrational modes. It turns out that many of them are localized on the ring or on the chain fragment of the molecule. The chain torsional modes, which are of primary interest for the photoisomerization process, are correlated with torsional modes of bacteriorhodopsin.
引用
收藏
页码:2131 / 2136
页数:6
相关论文
共 25 条
[1]   DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].
BECKE, AD .
PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100
[2]   Ab initio molecular dynamics of retinals [J].
Bifone, A ;
deGroot, HJM ;
Buda, F .
CHEMICAL PHYSICS LETTERS, 1996, 248 (3-4) :165-172
[3]   NATURE OF THE PRIMARY PHOTOCHEMICAL EVENTS IN RHODOPSIN AND BACTERIORHODOPSIN [J].
BIRGE, RR .
BIOCHIMICA ET BIOPHYSICA ACTA, 1990, 1016 (03) :293-327
[4]   ORIGINS OF INHOMOGENEOUS BROADENING IN THE VIBRONIC SPECTRA OF VISUAL CHROMOPHORES AND VISUAL PIGMENTS [J].
BIRGE, RR ;
BOCIAN, DF ;
HUBBARD, LM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1982, 104 (05) :1196-1207
[5]   RESONANCE RAMAN-SPECTROSCOPY OF CHEMICALLY MODIFIED RETINALS - ASSIGNING CARBON-METHYL VIBRATIONS IN RESONANCE RAMAN-SPECTRUM OF RHODOPSIN [J].
COOKINGHAM, R ;
LEWIS, A .
JOURNAL OF MOLECULAR BIOLOGY, 1978, 119 (04) :569-577
[6]   VIBRATIONAL ANALYSIS OF RHODOPSIN AND BACTERIORHODOPSIN CHROMOPHORE ANALOGS - RESONANCE RAMAN AND INFRARED SPECTROSCOPY OF CHEMICALLY MODIFIED RETINALS AND SCHIFF-BASES [J].
COOKINGHAM, RE ;
LEWIS, A ;
LEMLEY, AT .
BIOCHEMISTRY, 1978, 17 (22) :4699-4711
[7]   VIBRATIONAL ANALYSIS OF ALL-TRANS-RETINAL [J].
CURRY, B ;
BROEK, A ;
LUGTENBURG, J ;
MATHIES, R .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1982, 104 (20) :5274-5286
[8]  
Frisch M.J., 1995, GAUSSIAN 94 REVISION
[9]  
GERVASIO FL, UNPUB
[10]   QUANTUM CHEMICAL VIBRATIONAL ANALYSIS OF THE CHROMOPHORE OF BACTERIORHODOPSIN [J].
GROSSJEAN, MF ;
TAVAN, P ;
SCHULTEN, K .
JOURNAL OF PHYSICAL CHEMISTRY, 1990, 94 (21) :8059-8069