Theoretical study of the solvatochromism of a merocyanine dye

被引:14
作者
Alberti, SF [1 ]
Echave, J [1 ]
机构
[1] Univ Nacl Quilmes, Ctr Estud & Invest, RA-1876 Bernal, Argentina
关键词
D O I
10.1016/S0301-0104(97)00234-6
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
Molecular dynamics (MD) simulations of a strongly polar merocyanine dye in solutions with acetone and methanol were performed using a quantum mechanical/molecular mechanical (QM/MM) mixed model. The solute was represented by its zwitterion and quinone resonance forms. The 102 nm blue shift of the W-visible absorption band observed when the dye is transferred from acetone to methanol was analysed. Semiempirical electronic structure calculations on configurations obtained randomly from the data collection period of the MD run were used to study the effect of the solvent on the W-visible spectrum. Different levels of solvent representation were considered: a self-consistent reaction field (SCRF) approach, a QM/MM mixed model and a solute-solvent supermolecule model. The semiempirical method AM1 was employed to calculate absolute energies, dipole moments and solute partial charges during the dynamics, whereas another semiempirical method, ZINDO/S, was employed to obtain the electronic spectra. The solvents considered have very similar polarities and therefore their solvatochromic effects are due mainly to specific interactions. Accordingly, we found that only the supermolecule model is able to predict the observed blue shift, that turns out to be produced by the effect of the first solvation shell over the zwitterion resonant form, that predominates over the quinone in both solvents. A detailed analysis of zwitterion-solvent specific interactions suggests that a nucleophile-carbonyl interaction in acetone and a hydrogen bond in methanol would be the main causes of the solvatochromism. (C) 1997 Elsevier Science B.V.
引用
收藏
页码:183 / 194
页数:12
相关论文
共 30 条
[1]   Rational design of molecules with large hyperpolarizabilities. Electric field, solvent polarity, and bond length alternation effects on merocyanine dye linear and nonlinear optical properties [J].
Albert, IDL ;
Marks, TJ ;
Ratner, MA .
JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (23) :9714-9725
[2]   INTERMEDIATE NEGLECT OF DIFFERENTIAL OVERLAP THEORY FOR TRANSITION-METAL COMPLEXES - FE, CO AND CU CHLORIDES [J].
BACON, AD ;
ZERNER, MC .
THEORETICA CHIMICA ACTA, 1979, 53 (01) :21-54
[3]   SOME STUDIES OF BENZENOID-QUINONOID RESONANCE .2. EFFECT OF SOLVENT POLARITY ON STRUCTURE AND PROPERTIES OF MEROCYANINE DYES [J].
BENSON, HG ;
MURRELL, JN .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS II, 1972, 68 (590) :137-&
[4]   MOLECULAR-DYNAMICS WITH COUPLING TO AN EXTERNAL BATH [J].
BERENDSEN, HJC ;
POSTMA, JPM ;
VANGUNSTEREN, WF ;
DINOLA, A ;
HAAK, JR .
JOURNAL OF CHEMICAL PHYSICS, 1984, 81 (08) :3684-3690
[5]   SOLVATOCHROMISM OF A TYPICAL MEROCYANINE DYE - A THEORETICAL INVESTIGATION THROUGH THE CNDO SCI METHOD INCLUDING SOLVATATION [J].
BOTREL, A ;
LEBEUZE, A ;
JACQUES, P ;
STRUB, H .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS II, 1984, 80 :1235-1252
[6]   COLOR AND CONSTITUTION .10. ABSORPTION OF THE MEROCYANINES [J].
BROOKER, LGS ;
KEYES, GH ;
SPRAGUE, RH ;
VANDYKE, RH ;
VANLARE, E ;
VANZANDT, G ;
WHITE, FL ;
CRESSMAN, HWJ ;
DENT, SG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1951, 73 (11) :5332-5350
[7]   COLOR AND CONSTITUTION .11. ANHYDRONIUM BASES OF PARA-HYDROXYSTYRYL DYES AS SOLVENT POLARITY INDICATORS [J].
BROOKER, LGS ;
KEYES, GH ;
HESELTINE, DW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1951, 73 (11) :5350-5356
[8]   SOLVATOCHROMISM OF A TYPICAL MEROCYANINE - STILBAZOLIUM BETAINE AND ITS 2,6-DI-TERT-BUTYL DERIVATIVE [J].
CATALAN, J ;
MENA, E ;
MEUTERMANS, W ;
ELGUERO, J .
JOURNAL OF PHYSICAL CHEMISTRY, 1992, 96 (09) :3615-3621
[9]   THEORY OF SOLVENT EFFECTS - VIRTUAL CHARGE MODEL TO REPRESENT SOLVENT POLARIZATION [J].
CONSTANCIEL, R ;
TAPIA, O .
THEORETICA CHIMICA ACTA, 1978, 48 (01) :75-86
[10]   THE DEVELOPMENT AND USE OF QUANTUM-MECHANICAL MOLECULAR-MODELS .76. AM1 - A NEW GENERAL-PURPOSE QUANTUM-MECHANICAL MOLECULAR-MODEL [J].
DEWAR, MJS ;
ZOEBISCH, EG ;
HEALY, EF ;
STEWART, JJP .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (13) :3902-3909