On the Role of the Metal-to-Ligand Charge Transfer States in the Light-Induced Spin Crossover in FeII(bpy)3

被引:44
作者
De Graaf, Coen [1 ,2 ]
Sousa, Carmen [3 ,4 ]
机构
[1] Univ Rovira & Virgili, Dept Quim Fis & Inorgan, Tarragona 43007, Spain
[2] ICREA, Barcelona 08010, Spain
[3] Univ Barcelona, Dept Quim Fis, E-08028 Barcelona, Spain
[4] Univ Barcelona, Inst Quim Teor & Computac, E-08028 Barcelona, Spain
关键词
LIESST; ab initio; spin crossover; caspt2; 2ND-ORDER PERTURBATION-THEORY; DENSITY-FUNCTIONAL THEORY; AB-INITIO; EXCITED-STATE; STRUCTURAL DIFFERENCES; COORDINATION-COMPOUNDS; AQUEOUS-SOLUTION; ENERGY; DYNAMICS; COMPLEX;
D O I
10.1002/qua.22991
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 light-induced spin crossover in Fe(II)complexes is studied with complete active space second-order perturbation theory. The potential energy surfaces of the low-spin and high-spin states are determined as function of the Fe ligand distance interpolating between the high-spin and low-spin equilibrium geometries. In addition, we calculate the relative energies of the lowest excited Fe-3d(6) states along this coordinate. To address the mechanism of spin crossover, the metal-to-ligand charge transfer states with singlet, triplet, and quintet spin coupling were also treated. The curves of the singlet and triplet MLCT states nearly coincide, but the quintet MLCT curve is higher in energy and the equilibrium distance displaced to larger distances. The possible deactivation mechanisms of the (MLCT)-M-1 state are discussed considering the relative energies and spin-orbit coupling matrix elements of the relevant electronic states. (C) 2011 Wiley Periodicals, Inc. Int J Quantum Chem 111: 3385-3393, 2011
引用
收藏
页码:3385 / 3393
页数:9
相关论文
共 77 条
[1]   2ND-ORDER PERTURBATION-THEORY WITH A COMPLETE ACTIVE SPACE SELF-CONSISTENT FIELD REFERENCE FUNCTION [J].
ANDERSSON, K ;
MALMQVIST, PA ;
ROOS, BO .
JOURNAL OF CHEMICAL PHYSICS, 1992, 96 (02) :1218-1226
[2]   THE CR-2 POTENTIAL-ENERGY CURVE STUDIED WITH MULTICONFIGURATIONAL 2ND-ORDER PERTURBATION-THEORY [J].
ANDERSSON, K ;
ROOS, BO ;
MALMQVIST, PA ;
WIDMARK, PO .
CHEMICAL PHYSICS LETTERS, 1994, 230 (4-5) :391-397
[3]   2ND-ORDER PERTURBATION-THEORY WITH A CASSCF REFERENCE FUNCTION [J].
ANDERSSON, K ;
MALMQVIST, PA ;
ROOS, BO ;
SADLEJ, AJ ;
WOLINSKI, K .
JOURNAL OF PHYSICAL CHEMISTRY, 1990, 94 (14) :5483-5488
[4]   Cholesky decomposition-based multiconfiguration second-order perturbation theory (CD-CASPT2):: Application to the spin-state energetics of CoIII(diiminato)(NPh) [J].
Aquilante, Francesco ;
Malmqvist, Per-Ake ;
Pedersen, Thomas Bondo ;
Ghosh, Abhik ;
Roos, Bjoern Olof .
JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 2008, 4 (05) :694-702
[5]   Low-cost evaluation of the exchange Fock matrix from Cholesky and density fitting representations of the electron repulsion integrals [J].
Aquilante, Francesco ;
Pedersen, Thomas Bondo ;
Lindh, Roland .
JOURNAL OF CHEMICAL PHYSICS, 2007, 126 (19)
[6]   Software News and Update MOLCAS 7: The Next Generation [J].
Aquilante, Francesco ;
De Vico, Luca ;
Ferre, Nicolas ;
Ghigo, Giovanni ;
Malmqvist, Per-Ake ;
Neogrady, Pavel ;
Pedersen, Thomas Bondo ;
Pitonak, Michal ;
Reiher, Markus ;
Roos, Bjorn O. ;
Serrano-Andres, Luis ;
Urban, Miroslav ;
Veryazov, Valera ;
Lindh, Roland .
JOURNAL OF COMPUTATIONAL CHEMISTRY, 2010, 31 (01) :224-247
[7]   Photoinduced Magnetization on Mo Ion in Copper Octacyanomolybdate: An X-ray Magnetic Circular Dichroism Investigation [J].
Arrio, Marie-Anne ;
Long, Jerome ;
Moulin, Christophe Cartier Dit ;
Bachschmidt, Anne ;
Marvaud, Valerie ;
Rogalev, Andrei ;
Mathoniere, Corine ;
Wilhelm, Fabrice ;
Sainctavit, Philippe .
JOURNAL OF PHYSICAL CHEMISTRY C, 2010, 114 (01) :593-600
[8]   Exploring the sloped-to-peaked S2/S1 seam of intersection of thymine with electronic structure and direct quantum dynamics calculations [J].
Asturiol, David ;
Lasorne, Benjamin ;
Worth, Graham A. ;
Robb, Michael A. ;
Blancafort, Lluis .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2010, 12 (19) :4949-4958
[9]   Modeling thymine photodimerizations in DNA: Mechanism and correlation diagrams [J].
Blancafort, Lluis ;
Migani, Annapaola .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (47) :14540-+
[10]   Photoinduced ferrimagnetic systems in Prussian blue analogues Cx(I)Co4[Fe(CN)6]y (CI = alkali cation).: 1.: Conditions to observe the phenomenon [J].
Bleuzen, A ;
Lomenech, C ;
Escax, V ;
Villain, F ;
Varret, F ;
Moulin, CCD ;
Verdaguer, M .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (28) :6648-6652