Structural and thermochemical properties of a photoresponsive spiropyran and merocyanine pair: Basis set and solvent dependence in density functional predictions

被引：21

作者：

Balasubramanian, Ganesh ^{[1
]}

Schulte, Joachim ^{[2
]}

Mueller-Plathe, Florian ^{[1
]}

Boehm, Michael C. ^{[1
]}

机构：

[1] Tech Univ Darmstadt, Eduard Zintl Inst Anorgan & Phys Chem, D-64287 Darmstadt, Germany

[2] Brucker Biospin GmbH, D-76287 Rheinstetten, Germany

来源：

CHEMICAL PHYSICS LETTERS | 2012年 / 554卷

关键词：

AB-INITIO; NITROSUBSTITUTED SPIROPYRAN; TEMPERATURE; PHOTOPROCESSES; ISOMERIZATION; PHOTOCHROMISM; ABSORPTION; ISOMERS; SYSTEM;

D O I：

10.1016/j.cplett.2012.10.014

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：

We investigate structural and thermochemical properties of photoresponsive closed (SP) and open (MC) form moieties of nitro-substituted spirobenzopyran (1',3'-dihydro-1',3',3'-trimethyl-6-nitro-spiro[2H-1-benzopyran-2,2'-[2H]indole]) in different solvents. Density functional calculations reveal that in addition to the solvent, polarization and diffuse functions in the computational basis set exert a significant influence. Unlike in vacuum, in water all MC conformers are more stable than SP. The higher entropies and thus lower free energies of the flexible open forms strongly stabilize them in comparison to SP. The partial atomic charges, which are amplified in solvents, and the bond lengths are consistent with a quinoid structure of stable MC conformers. (C) 2012 Elsevier B.V. All rights reserved.

引用

页码：60 / 66

页数：7

共 41 条

[1] Solvent Dependence of Structure, Charge Distribution, and Absorption Spectrum in the Photochromic Merocyanine-Spiropyran Pair
Murugan, N. Arul
Chakrabarti, Swapan
Agren, Hans
JOURNAL OF PHYSICAL CHEMISTRY B, 2011, 115 (14): : 4025 - 4032
[2] Density functional and basis set dependence of hydrated Ln(III) properties
Clark, Aurora E.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 2008, 4 (05) : 708 - 718
[3] Basis set dependence of phosphate frequencies in density functional theory calculations
Rudbeck, Maria
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 2012, 112 (11) : 2435 - 2439
[4] Performance and basis set dependence of density functional theory dipole and quadrupole moments
De Proft, F
Tielens, F
Geerlings, P
JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, 2000, 506 : 1 - 8
[5] Basis set and density functional dependence of vibrational Raman optical activity calculations
Reiher, M
Liégeois, V
Ruud, K
JOURNAL OF PHYSICAL CHEMISTRY A, 2005, 109 (33): : 7567 - 7574
[6] Complete basis set and hybrid density functional theory resolution of silicon dicarbide structural and energetic properties.
Jursic, BS
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 1998, 215 : U547 - U547
[7] Energetic and structural properties of silicon dicarbides calculated with complete basis set and hybrid density functional theory methods
Jursic, BS
JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, 1999, 458 (03): : 257 - 261
[8] Molecular energies and properties from density functional theory: Exploring basis set dependence of Kohn-Sham equation using several density functionals
Scheiner, AC
Baker, J
Andzelm, JW
JOURNAL OF COMPUTATIONAL CHEMISTRY, 1997, 18 (06) : 775 - 795
[9] Localized orbital corrections applied to thermochemical errors in density functional theory: The role of basis set and application to molecular reactions
Goldfeld, Dahlia A.
Bochevarov, Arteum D.
Friesner, Richard A.
JOURNAL OF CHEMICAL PHYSICS, 2008, 129 (21):
[10] Density Functional Theory Study on B30N20 Nanocage in Structural Properties and Thermochemical Outlook
Monajjemi, M.
Azan, M. Jafari
Mollaamin, F.
FULLERENES NANOTUBES AND CARBON NANOSTRUCTURES, 2013, 21 (06) : 503 - 515

← 1 2 3 4 5 →